CA2878189A1 - Elastomeric coatings having hydrophobic and/or oleophobic properties - Google Patents
Elastomeric coatings having hydrophobic and/or oleophobic properties Download PDFInfo
- Publication number
- CA2878189A1 CA2878189A1 CA2878189A CA2878189A CA2878189A1 CA 2878189 A1 CA2878189 A1 CA 2878189A1 CA 2878189 A CA2878189 A CA 2878189A CA 2878189 A CA2878189 A CA 2878189A CA 2878189 A1 CA2878189 A1 CA 2878189A1
- Authority
- CA
- Canada
- Prior art keywords
- particles
- coating
- component
- microns
- combination according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
- B65D83/75—Aerosol containers not provided for in groups B65D83/16 - B65D83/74
- B65D83/752—Aerosol containers not provided for in groups B65D83/16 - B65D83/74 characterised by the use of specific products or propellants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Abstract
This disclosure provides novel formulations to create highly durable hydrophobic, superhydrophobic, oleophobic and/or superoleophobic surfaces that can be nearly transparent.
More specifically, the disclosure provides a system for forming a coating comprising (A) a first component which comprises (i) an elastomeric binder comprising one or more styrenic block copolymers; (ii) one or more independently selected first particles; and (iii) one or more solvents; and (B) a second component which either comprises (i) one or more independently selected second particles which comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, and (ii) optionally, one or more solvents;
or comprises (i) one or more independently selected second particles which either comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, or comprise one or more siloxanes or silazanes associated with the second particles; (ii) a fluorinated polyolefin; or a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer; and (iii) one or more solvents.
More specifically, the disclosure provides a system for forming a coating comprising (A) a first component which comprises (i) an elastomeric binder comprising one or more styrenic block copolymers; (ii) one or more independently selected first particles; and (iii) one or more solvents; and (B) a second component which either comprises (i) one or more independently selected second particles which comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, and (ii) optionally, one or more solvents;
or comprises (i) one or more independently selected second particles which either comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, or comprise one or more siloxanes or silazanes associated with the second particles; (ii) a fluorinated polyolefin; or a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer; and (iii) one or more solvents.
Description
2 ELASTOMERIC COATINGS HAVING HYDROPHOBIC AND/OR OLEOPHOBIC
PROPERTIES
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No.
61/663,985, filed June 25, 2012; U.S. Provisional Application No. 61/708,760, filed October 2, 2012; and U.S.
Provisional Application No. 61/768,290, filed February 22, 2013, the entirety of each of which application is incorporated herein by reference.
BACKGROUND
The surfaces of objects that are exposed to the environment come into contact with a variety of agents, including dust, moisture, water, and oils. In industrial applications, surfaces may be exposed to a variety of agents in addition to water, such as aqueous salt solutions, solutions of aqueous acid or base, and chemical components that may be dissolved or suspended in aqueous compositions or other liquids, including those used in manufacturing processes. Not only are the surfaces of objects exposed to a variety of chemical agents, but the temperatures to which the surfaces are exposed can also affect their interaction with those agents and the performance of the coated surfaces of objects. For example, freezing liquids, such as water, can result in frozen deposits tightly attached to the surfaces that prevent access to the surfaces and in some instances prevent proper operation of equipment bound by the frozen liquid. In addition, elevated temperatures can accelerate processes such as corrosion or leaching.
SUMMARY
Embodiments of coatings and surface treatments are provided herein that can provide advantageous surface properties including, but not limited to, hydrophobicity or superhydrophobicity (collectively HP), oleophobicity or superoleophobicity (collectively OP), and resistance to ice formation, adherence and/or accumulation. Embodiments of the coatings described herein that are HP and OP, and which may also display anti-icing behavior, may be applied to a surface using two or more steps. Embodiments of methods of applying such coatings and surface treatments also are provided, together with embodiments of compositions for applying such coatings and surface treatments, and surfaces and/or objects so treated and coated are provided as well.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic showing an embodiment of a polystyrene and rubber elastomeric copolymer. Figure 2 is a schematic showing various spatial orientations of embodiments of polystyrene and rubber copolymers. S is styrene and B is a rubber phase (i.e.
butylene).
Figure 3 shows some solvents suitable for dissolving styrene (styrenic) block copolymers (SBCs). The scale represents suitable solvents that can be used as SBC
copolymers. Letters to the left axis are indicators of: S (styrene), B butylene (polybutadiene), I
(polyisoprene), and EB
(ethylene/butylene). Those solvents indicated as "Good Solvents" are solvents that tend to dissolve or suspend SBC polymers.
Figure 4 depicts a shower test apparatus. The upper panel shows the showerhead with 70 nozzles with a 1 mm diameter orifice arranged in 5 spokes of 5 nozzles and 15 spokes of 3 nozzles about a central point on a circular showerhead. For testing the showerhead delivers approximately 6 liters of potable tap water per minute using about 137900 Pa (Pascals) to 310275 Pa. The lower panel depicts a sample, which is placed about 1.5 meters below the showerhead and subject to the shower.
Figure 5 shows a plot of "glove rubs," which are an estimate of the surface resistance to the loss of either or both of HP or OP properties as a function of percentage of EXPANCEL first particles employed in a nearly transparent coating prepared without colorants.
The glove rub estimates tend to trend in the same direction as loss of HP or OP properties due to handling, abrasion resistance, and/or the shower time. The weight percent of EXPANCEL
particles is given as the percentage of the base coat formulation weight as opposed to a dry weight basis (see Example 1).
Figure 6 shows the variation in the resistance to the loss of superhydrophobic behavior of an elastomeric binder system due to wear based on "glove rubs" and exposure to a shower of water using five different types of EXPANCEL particles. Duplicate samples containing EXPANCEL
031 DU 400 heated before or after the second component (referred to as "top coat") comprising hydrophobic fumed silica in acetone is applied. See Example 2 for details.
Figure 7 shows the effect of coating thickness on coating resistance to the loss of superhydrophobic behavior due to wear based on Taber Abraser testing using a 1,000g load and CS-10 wheels on 10x10 cm plates treated with 2 or 4 ml of top coat (second component) applied over the base coating. See Example 5 for details.
Figure 8 shows Thermogravimetric Analysis (TGA) data for a nearly transparent elastomeric coating incorporating EXPANCEL461 EXPANCEL DE 40 D 25 microspheres.
Figure 9 shows TGA data for an embodiment of a non-transparent HP/OP
elastomeric coating incorporating SoftSandTm rubber particles.
DETAILED DESCRIPTION
Embodiments of elastomeric coating methods, compositions, and treatments are provided that impart a variety of desirable characteristics to objects and their surfaces, including hydrophobicity (including superhydrophobicity), oleophobicity (including superoleophobicity), and/or anti-icing. As used herein, the term "hydrophobicity" and the abbreviation HP includes superhydrophobicity, and the term "oleophobicity" and the abbreviation OP
includes superoleophobicity. The abbreviation "HP/OP" is used collectively herein to mean HP and/or OP and may also include anti-icing properties (including ice formation, adherence and/or accumulation). Treating surfaces with coatings having HP/OP characteristics can result in objects and surfaces with a variety of advantageous properties including, but not limited to, resistance to wetting, corrosion, swelling, rotting, cracking or warping, exfoliation, fouling, dust and/or dirt accumulation on surfaces (self cleaning), and resistance to surface ice formation, adherence and/or accumulation. Not only do embodiments of the coating compositions and treatments described herein provide properties including HP/OP, but the coatings also are durable in that they substantially retain those properties despite some amount of mechanical abrasion. In addition to providing durable HP/OP behavior, embodiments of the elastomeric coatings can also remain flexible and provide substantial resistance to cracking, peeling, and delamination from the coated surface over a wide range of temperatures.
Further, embodiments of the coatings can readily be repaired where the surface has been abraded sufficiently to compromise the coating's properties including HP/OP behavior.
Embodiments of the HP/OP elastomeric coatings described herein may be applied in a process comprising two or more steps in which the first component applied comprises an elastomeric binding agent and optionally comprises first particles. Once applied, the coating formed by the first component is termed a "substrate coating," a "base coating," or a "base coat"
particularly when dried. Following the application of the elastomer base coat, an amount of second component is applied to the base coat. The second component comprises second particles that are treated to cause the second particles, and the coatings into which they are suitably incorporated, to display advantageous properties including HP/OP
and/or anti-icing behavior. The second component may be applied to an elastomeric base coat after the base coat is applied, but before it is dried and/or set. Alternatively, depending on the carrier/solvent used with the second component, the second component may be applied to the elastomer after the base coat is dried and/or set.
PROPERTIES
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No.
61/663,985, filed June 25, 2012; U.S. Provisional Application No. 61/708,760, filed October 2, 2012; and U.S.
Provisional Application No. 61/768,290, filed February 22, 2013, the entirety of each of which application is incorporated herein by reference.
BACKGROUND
The surfaces of objects that are exposed to the environment come into contact with a variety of agents, including dust, moisture, water, and oils. In industrial applications, surfaces may be exposed to a variety of agents in addition to water, such as aqueous salt solutions, solutions of aqueous acid or base, and chemical components that may be dissolved or suspended in aqueous compositions or other liquids, including those used in manufacturing processes. Not only are the surfaces of objects exposed to a variety of chemical agents, but the temperatures to which the surfaces are exposed can also affect their interaction with those agents and the performance of the coated surfaces of objects. For example, freezing liquids, such as water, can result in frozen deposits tightly attached to the surfaces that prevent access to the surfaces and in some instances prevent proper operation of equipment bound by the frozen liquid. In addition, elevated temperatures can accelerate processes such as corrosion or leaching.
SUMMARY
Embodiments of coatings and surface treatments are provided herein that can provide advantageous surface properties including, but not limited to, hydrophobicity or superhydrophobicity (collectively HP), oleophobicity or superoleophobicity (collectively OP), and resistance to ice formation, adherence and/or accumulation. Embodiments of the coatings described herein that are HP and OP, and which may also display anti-icing behavior, may be applied to a surface using two or more steps. Embodiments of methods of applying such coatings and surface treatments also are provided, together with embodiments of compositions for applying such coatings and surface treatments, and surfaces and/or objects so treated and coated are provided as well.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic showing an embodiment of a polystyrene and rubber elastomeric copolymer. Figure 2 is a schematic showing various spatial orientations of embodiments of polystyrene and rubber copolymers. S is styrene and B is a rubber phase (i.e.
butylene).
Figure 3 shows some solvents suitable for dissolving styrene (styrenic) block copolymers (SBCs). The scale represents suitable solvents that can be used as SBC
copolymers. Letters to the left axis are indicators of: S (styrene), B butylene (polybutadiene), I
(polyisoprene), and EB
(ethylene/butylene). Those solvents indicated as "Good Solvents" are solvents that tend to dissolve or suspend SBC polymers.
Figure 4 depicts a shower test apparatus. The upper panel shows the showerhead with 70 nozzles with a 1 mm diameter orifice arranged in 5 spokes of 5 nozzles and 15 spokes of 3 nozzles about a central point on a circular showerhead. For testing the showerhead delivers approximately 6 liters of potable tap water per minute using about 137900 Pa (Pascals) to 310275 Pa. The lower panel depicts a sample, which is placed about 1.5 meters below the showerhead and subject to the shower.
Figure 5 shows a plot of "glove rubs," which are an estimate of the surface resistance to the loss of either or both of HP or OP properties as a function of percentage of EXPANCEL first particles employed in a nearly transparent coating prepared without colorants.
The glove rub estimates tend to trend in the same direction as loss of HP or OP properties due to handling, abrasion resistance, and/or the shower time. The weight percent of EXPANCEL
particles is given as the percentage of the base coat formulation weight as opposed to a dry weight basis (see Example 1).
Figure 6 shows the variation in the resistance to the loss of superhydrophobic behavior of an elastomeric binder system due to wear based on "glove rubs" and exposure to a shower of water using five different types of EXPANCEL particles. Duplicate samples containing EXPANCEL
031 DU 400 heated before or after the second component (referred to as "top coat") comprising hydrophobic fumed silica in acetone is applied. See Example 2 for details.
Figure 7 shows the effect of coating thickness on coating resistance to the loss of superhydrophobic behavior due to wear based on Taber Abraser testing using a 1,000g load and CS-10 wheels on 10x10 cm plates treated with 2 or 4 ml of top coat (second component) applied over the base coating. See Example 5 for details.
Figure 8 shows Thermogravimetric Analysis (TGA) data for a nearly transparent elastomeric coating incorporating EXPANCEL461 EXPANCEL DE 40 D 25 microspheres.
Figure 9 shows TGA data for an embodiment of a non-transparent HP/OP
elastomeric coating incorporating SoftSandTm rubber particles.
DETAILED DESCRIPTION
Embodiments of elastomeric coating methods, compositions, and treatments are provided that impart a variety of desirable characteristics to objects and their surfaces, including hydrophobicity (including superhydrophobicity), oleophobicity (including superoleophobicity), and/or anti-icing. As used herein, the term "hydrophobicity" and the abbreviation HP includes superhydrophobicity, and the term "oleophobicity" and the abbreviation OP
includes superoleophobicity. The abbreviation "HP/OP" is used collectively herein to mean HP and/or OP and may also include anti-icing properties (including ice formation, adherence and/or accumulation). Treating surfaces with coatings having HP/OP characteristics can result in objects and surfaces with a variety of advantageous properties including, but not limited to, resistance to wetting, corrosion, swelling, rotting, cracking or warping, exfoliation, fouling, dust and/or dirt accumulation on surfaces (self cleaning), and resistance to surface ice formation, adherence and/or accumulation. Not only do embodiments of the coating compositions and treatments described herein provide properties including HP/OP, but the coatings also are durable in that they substantially retain those properties despite some amount of mechanical abrasion. In addition to providing durable HP/OP behavior, embodiments of the elastomeric coatings can also remain flexible and provide substantial resistance to cracking, peeling, and delamination from the coated surface over a wide range of temperatures.
Further, embodiments of the coatings can readily be repaired where the surface has been abraded sufficiently to compromise the coating's properties including HP/OP behavior.
Embodiments of the HP/OP elastomeric coatings described herein may be applied in a process comprising two or more steps in which the first component applied comprises an elastomeric binding agent and optionally comprises first particles. Once applied, the coating formed by the first component is termed a "substrate coating," a "base coating," or a "base coat"
particularly when dried. Following the application of the elastomer base coat, an amount of second component is applied to the base coat. The second component comprises second particles that are treated to cause the second particles, and the coatings into which they are suitably incorporated, to display advantageous properties including HP/OP
and/or anti-icing behavior. The second component may be applied to an elastomeric base coat after the base coat is applied, but before it is dried and/or set. Alternatively, depending on the carrier/solvent used with the second component, the second component may be applied to the elastomer after the base coat is dried and/or set.
3 The use of second component coating compositions comprising solvents that can be applied to the elastomeric base coat after it has dried and set permits repair of coatings that have been abraded or otherwise damaged to the point where the desired HP/OP
properties is/are no longer observed. Provided the base coat is intact, or the base coat has not been damaged to the point that material underlying the base coat is exposed, repair is accomplished by the reapplication of the second component which comprises second particles.
Where the HP/OP elastomeric coatings have been abraded so as to compromise the elastomer binder coating or its properties (e.g., abraded, worn too thin, or damaged to the point where the surface of the coated object or underlying material such as a primer is exposed), the coating may be reapplied to the abraded area (i.e., it may be repaired) by repeating the application of both the first and second components. Suitable repair/preparation of exposed/damaged surfaces and/or underlying primers may be required prior to the reapplication of the elastomeric coating. In contrast, other HP or OP coatings using non-elastomeric binder systems (e.g., polyurethane systems) may not be as readily repaired because the HP/OP behavior of the original coating that remains in place can prevent newly applied coating compositions from binding to the surface.
In one embodiment, a method of applying a HP/OP coating to a substrate comprises the steps of:
a) applying to the substrate a first component comprising: i) an elastomeric binder comprising one or more styrenic block copolymers, and optionally comprising ii) first particles having a size of about 1 micron to about 300 microns (e.g., 10 microns to about 100 microns), to provide a base coating; and b) applying to the base coating a second component comprising second particles having a size of about 1 nanometer to 25 microns, where the second particles are associated with one or more siloxanes and/or have one or more independently selected alkyl, haloalkyl, or perfluoroalkyl groups covalently bound, either directly or indirectly, to the second particles, and wherein the second component optionally comprises an agent to suspend or assist in suspending the particles (e.g., a solvent such as hexane or tert-butyl acetate).
To assist in the application process, embodiments of the first and second components may include any necessary solvents, liquids or propellants.
In some embodiments of the application method, the base coating is treated with the second component after drying and curing the base coating at room temperature (e.g., about 18 to about 23 C) or at an elevated temperature (e.g., about 30 to about 100 C, about 30 to about 60 C, about 50 to about 100 C, or about 40 to about 90 C). In other embodiments,
properties is/are no longer observed. Provided the base coat is intact, or the base coat has not been damaged to the point that material underlying the base coat is exposed, repair is accomplished by the reapplication of the second component which comprises second particles.
Where the HP/OP elastomeric coatings have been abraded so as to compromise the elastomer binder coating or its properties (e.g., abraded, worn too thin, or damaged to the point where the surface of the coated object or underlying material such as a primer is exposed), the coating may be reapplied to the abraded area (i.e., it may be repaired) by repeating the application of both the first and second components. Suitable repair/preparation of exposed/damaged surfaces and/or underlying primers may be required prior to the reapplication of the elastomeric coating. In contrast, other HP or OP coatings using non-elastomeric binder systems (e.g., polyurethane systems) may not be as readily repaired because the HP/OP behavior of the original coating that remains in place can prevent newly applied coating compositions from binding to the surface.
In one embodiment, a method of applying a HP/OP coating to a substrate comprises the steps of:
a) applying to the substrate a first component comprising: i) an elastomeric binder comprising one or more styrenic block copolymers, and optionally comprising ii) first particles having a size of about 1 micron to about 300 microns (e.g., 10 microns to about 100 microns), to provide a base coating; and b) applying to the base coating a second component comprising second particles having a size of about 1 nanometer to 25 microns, where the second particles are associated with one or more siloxanes and/or have one or more independently selected alkyl, haloalkyl, or perfluoroalkyl groups covalently bound, either directly or indirectly, to the second particles, and wherein the second component optionally comprises an agent to suspend or assist in suspending the particles (e.g., a solvent such as hexane or tert-butyl acetate).
To assist in the application process, embodiments of the first and second components may include any necessary solvents, liquids or propellants.
In some embodiments of the application method, the base coating is treated with the second component after drying and curing the base coating at room temperature (e.g., about 18 to about 23 C) or at an elevated temperature (e.g., about 30 to about 100 C, about 30 to about 60 C, about 50 to about 100 C, or about 40 to about 90 C). In other embodiments,
4 the solvent used to apply the base coat is allowed to evaporate until the coating is no longer liquid and cannot be removed by contact (i.e., dry to the touch); however, the base coating is not fully dried and cured when treated with the second component containing second particles. In still other embodiments, the composition comprising second particles may be applied directly to the base coat before solvents used in the application of the base coating have fully, substantially, or partly evaporated.
Diverse elastomeric binders, first particles, and second particles may be employed in the methods and compositions described herein. In some embodiments, first particles may be filler particles. In some embodiments second particles may be considered nanoparticles. In some embodiments described herein, the coating formed by the application of the first and second components will be nearly transparent to visible light. In other embodiments, the coatings may be colored but nearly transparent to visible light that is not absorbed by the coating components and/or colorants. In still other embodiments, the coatings will have colorants (e.g., insoluble pigments or colored first and/or second particles) that will render them opaque or block the transmission of light. Embodiments of such coating components, materials, and compositions are described more fully below.
A skilled artisan will readily understand that the selection of first particles and second particles needs to include consideration of not only the desired properties of the coating and the ultimate conditions to which the coating will be subject in use, but also the process used to prepare the coating. Where, for example, particles must withstand elevated temperatures or specific solvents in the coating process, they should be selected so as to be suitable for use in the required temperature ranges or in the required solvents. For example, in those embodiments where coatings or the first and/or second particles are intended for use at elevated temperatures (e.g., above room temperature), the particles need to be compatible with the elevated temperatures that the coatings will be subjected to when in use and/or in processes employed to prepare the coatings. Similarly, the particles should be selected to be compatible with solvents used in the application process and with solvents the coatings will become exposed to in use.
In methods described herein, where second particles are applied to a base coat on a substrate, which may be coated with a primer, the methods can produce coatings having (i) a surface in contact with said substrate (or primer) and (ii) an exposed surface that is not in contact with the substrate (or primer) where these surfaces bear different amounts of first particles, second particles, or both first and second particles. In some embodiments the exposed surface can have a greater amount of first and/or second particles on, at, or adjacent to the exposed surface, compared to the amount of first and/or second particles at or adjacent to the surface of
Diverse elastomeric binders, first particles, and second particles may be employed in the methods and compositions described herein. In some embodiments, first particles may be filler particles. In some embodiments second particles may be considered nanoparticles. In some embodiments described herein, the coating formed by the application of the first and second components will be nearly transparent to visible light. In other embodiments, the coatings may be colored but nearly transparent to visible light that is not absorbed by the coating components and/or colorants. In still other embodiments, the coatings will have colorants (e.g., insoluble pigments or colored first and/or second particles) that will render them opaque or block the transmission of light. Embodiments of such coating components, materials, and compositions are described more fully below.
A skilled artisan will readily understand that the selection of first particles and second particles needs to include consideration of not only the desired properties of the coating and the ultimate conditions to which the coating will be subject in use, but also the process used to prepare the coating. Where, for example, particles must withstand elevated temperatures or specific solvents in the coating process, they should be selected so as to be suitable for use in the required temperature ranges or in the required solvents. For example, in those embodiments where coatings or the first and/or second particles are intended for use at elevated temperatures (e.g., above room temperature), the particles need to be compatible with the elevated temperatures that the coatings will be subjected to when in use and/or in processes employed to prepare the coatings. Similarly, the particles should be selected to be compatible with solvents used in the application process and with solvents the coatings will become exposed to in use.
In methods described herein, where second particles are applied to a base coat on a substrate, which may be coated with a primer, the methods can produce coatings having (i) a surface in contact with said substrate (or primer) and (ii) an exposed surface that is not in contact with the substrate (or primer) where these surfaces bear different amounts of first particles, second particles, or both first and second particles. In some embodiments the exposed surface can have a greater amount of first and/or second particles on, at, or adjacent to the exposed surface, compared to the amount of first and/or second particles at or adjacent to the surface of
5 the coating that is in contact with the substrate (or primer). In one embodiment the coatings have a greater amount of second particles on, at, or adjacent to the exposed surface than the surface of the coating that is in contact with the substrate (or primer). In embodiments where a greater amount of first and/or second particles may be present at the exposed surface, the coatings may be considered composite coatings.
The amount of particles in any portion of a coating may be assessed by any means known in the art including, but not limited to, microscopy or electron microscopy. Using those techniques on cross or oblique sections of coatings, the amount (e.g., the number) of particles can be determined. In addition, where it is possible to remove coatings, or where the substrate permits (e.g., it is transparent), the surfaces can be examined directly using microscopy or electron microscopy to determine the amount of particles present at the exposed surface or adjacent to the substrate.
Embodiments of the coatings described herein are durable in that they can withstand some amount of abrasion without a substantial loss of HP/OP properties. To provide an endpoint for the loss of superhydrophobic (SH) behavior as a result of abrasion testing, substantially planar abraded surfaces are tested for their propensity to shed water droplets at an indicated angle of incline (5 degrees unless indicated otherwise). Typically, twenty droplets are placed on the surface to be assessed, which is inclined at the desired angle.
The end of SH
behavior is indicated when more than half (ten or more drops) stay in place.
While such measurements provide a consistent endpoint, a skilled artisan will understand that, even when the endpoint is reached, the abraded surfaces may still be quite hydrophobic, e.g., having water contact angles greater than 130 or 140 in many instances.
Resistance to abrasion may be measured using any method known in the art including, but not limited to, mechanized or manual assessment with a Taber abrasion-testing instrument (e.g., a Taber "Abraser") or a Crockmeter. Alternatively, a manual measure used to assess the durability of surfaces is a glove rub (GR) test. Each of those tests is described in more detail below.
For the purpose of this application, wherever Taber testing results are recited, the tests are conducted on a Taber Model 503 instrument using CS-0 or CS10 wheels with 250 g or 1,000 g loads as indicated. Unless indicated otherwise, a load of 1,000 g was employed, and tests were conducted at room temperature at a speed of 95 rpm.
Where resistance to the loss of HP is measured with a Crockmeter, a motorized American Association of Textile Chemists and Colorists (AATCC) CM-5 Crockmeter is employed. The finger of the Crockmeter is fitted with a 14/20 white rubber septum having an
The amount of particles in any portion of a coating may be assessed by any means known in the art including, but not limited to, microscopy or electron microscopy. Using those techniques on cross or oblique sections of coatings, the amount (e.g., the number) of particles can be determined. In addition, where it is possible to remove coatings, or where the substrate permits (e.g., it is transparent), the surfaces can be examined directly using microscopy or electron microscopy to determine the amount of particles present at the exposed surface or adjacent to the substrate.
Embodiments of the coatings described herein are durable in that they can withstand some amount of abrasion without a substantial loss of HP/OP properties. To provide an endpoint for the loss of superhydrophobic (SH) behavior as a result of abrasion testing, substantially planar abraded surfaces are tested for their propensity to shed water droplets at an indicated angle of incline (5 degrees unless indicated otherwise). Typically, twenty droplets are placed on the surface to be assessed, which is inclined at the desired angle.
The end of SH
behavior is indicated when more than half (ten or more drops) stay in place.
While such measurements provide a consistent endpoint, a skilled artisan will understand that, even when the endpoint is reached, the abraded surfaces may still be quite hydrophobic, e.g., having water contact angles greater than 130 or 140 in many instances.
Resistance to abrasion may be measured using any method known in the art including, but not limited to, mechanized or manual assessment with a Taber abrasion-testing instrument (e.g., a Taber "Abraser") or a Crockmeter. Alternatively, a manual measure used to assess the durability of surfaces is a glove rub (GR) test. Each of those tests is described in more detail below.
For the purpose of this application, wherever Taber testing results are recited, the tests are conducted on a Taber Model 503 instrument using CS-0 or CS10 wheels with 250 g or 1,000 g loads as indicated. Unless indicated otherwise, a load of 1,000 g was employed, and tests were conducted at room temperature at a speed of 95 rpm.
Where resistance to the loss of HP is measured with a Crockmeter, a motorized American Association of Textile Chemists and Colorists (AATCC) CM-5 Crockmeter is employed. The finger of the Crockmeter is fitted with a 14/20 white rubber septum having an
6 outside diameter of 13 mm and an inside diameter of 7 mm with a contact surface area of 94 mm2(Ace Glass, Inc., Vineland, NJ, Catalog No. 9096-244). The septum is brought into contact with the coating with a force of 9N (Newtons). The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied to the tested surface (typically 20 droplets) to run (roll) off when the surface is inclined at 5 degrees from horizontal. Abrasion resistance may also be measured using a manually operated AATCC Crockmeter.
Although an absolute correlation between Taber Abraser Testing, Crockmeter testing, and glove-rub testing is not provided, the manual glove-rub test is useful as an indication of the durability of the coated surface and its ability to be handled. Coatings applied to primed surfaces incorporating rigid particles (e.g., EXTENDO SPHERES) typically give a ratio of about 4.5 glove rubs/Taber Abraser cycles (250 g load) with CS-0 wheels and a ratio of about
Although an absolute correlation between Taber Abraser Testing, Crockmeter testing, and glove-rub testing is not provided, the manual glove-rub test is useful as an indication of the durability of the coated surface and its ability to be handled. Coatings applied to primed surfaces incorporating rigid particles (e.g., EXTENDO SPHERES) typically give a ratio of about 4.5 glove rubs/Taber Abraser cycles (250 g load) with CS-0 wheels and a ratio of about
7.5 glove rubs/Taber cycles with CS-10 wheels. Coatings incorporating flexible first particles (e.g., black rubber particles) typically give a ratio of about 7.6 glove rubs/Taber Abraser cycles (250 g load) with CS-0 wheels and a ratio of about 12.9 with CS-10 wheels.
Results are given below for coatings of several thicknesses, where the thickness measurement includes the thickness of the primer layer. The number of strokes observed in Crockmeter testing is generally about one fourth of the number of "glove rubs" observed in the manual glove rub testing.
Nearly transparent coating with clear hollow rigid thermoplastic first particles CS-0 Wheel CS-10 Wheel Approximate Ratio Ratio Glove Rubs Thickness Taber GR/Taber Thickness Taber GR/Taber to loss of SH (mils) Cycles cycle (mils) Cycles cycle 500 1.1 130 3.8 1 60
Results are given below for coatings of several thicknesses, where the thickness measurement includes the thickness of the primer layer. The number of strokes observed in Crockmeter testing is generally about one fourth of the number of "glove rubs" observed in the manual glove rub testing.
Nearly transparent coating with clear hollow rigid thermoplastic first particles CS-0 Wheel CS-10 Wheel Approximate Ratio Ratio Glove Rubs Thickness Taber GR/Taber Thickness Taber GR/Taber to loss of SH (mils) Cycles cycle (mils) Cycles cycle 500 1.1 130 3.8 1 60
8.3 500 2.1 100 5.0 2 70 7.1 500 3.5 110 4.5 3.5 60 8.3 500 4 110 4.5 4.5 80 6.3 Nontransparent coating with flexible black rubber first particles CS-0 Wheel CS-10 Wheel Approximate Ratio Ratio Glove Rubs Thickness Taber GR/Taber Thickness Taber GR/Taber to loss of SH (mils) Cycles cycle (mils) cycles cycle 700 2.7 100 7.0 2.6 60 11.7 700 4.9 90 7.8 4.8 50 700 7.5 90 7.8 7.2 50 700 9.5 90 7.8 8.5 60 11.7 In addition to resisting the loss of HP/OP properties from abrasion, the compositions provided herein also provide durability in the form of resistance to other conditions. The coatings also resist loss of those properties when subject to:
= Submersion in water (the duration a coating resists wetting at different depths in water);
= Flowing water (the ability of a coating or surface treatment to resist the impact of flowing water such as a shower of water);
= Exposure to liquids other than water (chemical durability and resistance to acids, alkalis, salts, and certain organic solvents such as alcohols);
= Ultraviolet (UV) radiation;
= Boiling water; and = Salt water, in the form of immersion, spray, or fog.
The elastomer-based coatings described herein have a variety of properties in addition to resisting the loss of HP/OP from abrasion including, but not limited to, resisting ice formation and/or adherence on the coating and flexibility over a wide range of temperatures (e.g., -35 C to 205 C).
In one embodiment, the HP/OP elastomeric coatings comprising plastic, glass or rubber first particles (e.g., EXPANCEL spheres or micronized rubber) have a relative electrical permittivity at 100 MHz from about 0.2 to about 4 at about 22 C (e.g., a permittivity from about 0.2 to about 1, from about 1 to about 2, from about 2 to about 3, or from about 3 to about 4) as measured by ASTM D150 using a single 0.11 mm thick film, or three layers of 0.11 mm film to achieve a 0.33 mm thickness.
In addition to their other properties, the HP/OP coatings described herein can be described by their characteristic roughness that may be measured by any means known in the art.
In some embodiments, the surface roughness is measured using a Mahr Pocket Surf PS1 (Mahr Federal Inc., Providence, RI). The roughness of a surface can be expressed using a variety of mathematical expressions including, but not limited to, its Arithmetical Mean Roughness and its Ten-Point Mean Roughness.
The coatings resulting from the application of the compositions provided for herein have in some embodiments a surface with an arithmetical mean roughness in a range selected from:
greater than about 3 microns to about 4 microns; from about 4 microns to about 6 microns; from about 4 microns to about 8 microns; from about 4 microns to about 12 microns;
from about 4 microns to about 20 microns; from about 5 microns to about 10 microns; from about 5 microns to about 12 microns; from about 5 microns to about 20 microns; from about 6 microns to about microns; or from about 6 microns to about 14 microns.
In other embodiments, the coatings, resulting from the application of the compositions provided for herein, have in some embodiments a surface with a ten point mean roughness 5 selected from: from about 7 microns to about 60 microns; from about 7 microns to about 70 microns; from about 7 microns to about 80 microns; from about 7 microns to about 100 microns;
from about 8 microns to about 60 microns; from about 8 microns to about 80 microns; from about 8 microns to about 100 microns; from about 12 microns to about 60 microns; from about 12 microns to about 100 microns; from about 15 microns to about 60 microns; or from about 15 10 microns to about 100 microns.
A more complete discussion of the coating compositions, their methods of preparation and application, and their properties follows. A skilled artisan will understand that the description and examples set forth herein are provided as guidance, and are not limiting to the scope of the methods and compositions described herein.
1.0 Definitions For the purposes of this disclosure, a HP material or surface is one that results in a water droplet forming a surface contact angle exceeding about 90 at room temperature (which is about 18 C to about 23 C for purposes of this disclosure). Similarly, for the purposes of this disclosure, a SH material or surface is one that results in a water droplet forming a surface contact angle exceeding 150 but less than the theoretical maximum contact angle of 180 at room temperature. As SH surface behavior encompasses water contact angles from about 150 to about 180 , SH behavior is considered to include what is sometimes referred to as "ultrahydrophobic" behavior. For the purpose of this disclosure the term hydrophobic (HP) shall include superhydrophobic (SH) behavior unless stated otherwise, and any and all embodiments, claims, and aspects of this disclosure reciting hydrophobic behavior may be limited to either hydrophobic behavior that is not superhydrophobic (contact angles from 90 -150 ) or superhydrophobic behavior (contact angles of 150 or greater).
For the purposes of this disclosure an OP material or surface is one that results in a droplet of light mineral oil forming a surface contact angle exceeding about 90 . Similarly, for the purposes of this disclosure a SOP material or surface is one that results in a droplet of light mineral oil forming a surface contact angle exceeding 150 but less than the theoretical maximum contact angle of 180 at room temperature. For the purpose of this disclosure the term oleophobic (OP) shall include superoleophobic (SOP) behavior unless stated otherwise, and any and all embodiments, claims, and aspects of this disclosure reciting oleophobic behavior
= Submersion in water (the duration a coating resists wetting at different depths in water);
= Flowing water (the ability of a coating or surface treatment to resist the impact of flowing water such as a shower of water);
= Exposure to liquids other than water (chemical durability and resistance to acids, alkalis, salts, and certain organic solvents such as alcohols);
= Ultraviolet (UV) radiation;
= Boiling water; and = Salt water, in the form of immersion, spray, or fog.
The elastomer-based coatings described herein have a variety of properties in addition to resisting the loss of HP/OP from abrasion including, but not limited to, resisting ice formation and/or adherence on the coating and flexibility over a wide range of temperatures (e.g., -35 C to 205 C).
In one embodiment, the HP/OP elastomeric coatings comprising plastic, glass or rubber first particles (e.g., EXPANCEL spheres or micronized rubber) have a relative electrical permittivity at 100 MHz from about 0.2 to about 4 at about 22 C (e.g., a permittivity from about 0.2 to about 1, from about 1 to about 2, from about 2 to about 3, or from about 3 to about 4) as measured by ASTM D150 using a single 0.11 mm thick film, or three layers of 0.11 mm film to achieve a 0.33 mm thickness.
In addition to their other properties, the HP/OP coatings described herein can be described by their characteristic roughness that may be measured by any means known in the art.
In some embodiments, the surface roughness is measured using a Mahr Pocket Surf PS1 (Mahr Federal Inc., Providence, RI). The roughness of a surface can be expressed using a variety of mathematical expressions including, but not limited to, its Arithmetical Mean Roughness and its Ten-Point Mean Roughness.
The coatings resulting from the application of the compositions provided for herein have in some embodiments a surface with an arithmetical mean roughness in a range selected from:
greater than about 3 microns to about 4 microns; from about 4 microns to about 6 microns; from about 4 microns to about 8 microns; from about 4 microns to about 12 microns;
from about 4 microns to about 20 microns; from about 5 microns to about 10 microns; from about 5 microns to about 12 microns; from about 5 microns to about 20 microns; from about 6 microns to about microns; or from about 6 microns to about 14 microns.
In other embodiments, the coatings, resulting from the application of the compositions provided for herein, have in some embodiments a surface with a ten point mean roughness 5 selected from: from about 7 microns to about 60 microns; from about 7 microns to about 70 microns; from about 7 microns to about 80 microns; from about 7 microns to about 100 microns;
from about 8 microns to about 60 microns; from about 8 microns to about 80 microns; from about 8 microns to about 100 microns; from about 12 microns to about 60 microns; from about 12 microns to about 100 microns; from about 15 microns to about 60 microns; or from about 15 10 microns to about 100 microns.
A more complete discussion of the coating compositions, their methods of preparation and application, and their properties follows. A skilled artisan will understand that the description and examples set forth herein are provided as guidance, and are not limiting to the scope of the methods and compositions described herein.
1.0 Definitions For the purposes of this disclosure, a HP material or surface is one that results in a water droplet forming a surface contact angle exceeding about 90 at room temperature (which is about 18 C to about 23 C for purposes of this disclosure). Similarly, for the purposes of this disclosure, a SH material or surface is one that results in a water droplet forming a surface contact angle exceeding 150 but less than the theoretical maximum contact angle of 180 at room temperature. As SH surface behavior encompasses water contact angles from about 150 to about 180 , SH behavior is considered to include what is sometimes referred to as "ultrahydrophobic" behavior. For the purpose of this disclosure the term hydrophobic (HP) shall include superhydrophobic (SH) behavior unless stated otherwise, and any and all embodiments, claims, and aspects of this disclosure reciting hydrophobic behavior may be limited to either hydrophobic behavior that is not superhydrophobic (contact angles from 90 -150 ) or superhydrophobic behavior (contact angles of 150 or greater).
For the purposes of this disclosure an OP material or surface is one that results in a droplet of light mineral oil forming a surface contact angle exceeding about 90 . Similarly, for the purposes of this disclosure a SOP material or surface is one that results in a droplet of light mineral oil forming a surface contact angle exceeding 150 but less than the theoretical maximum contact angle of 180 at room temperature. For the purpose of this disclosure the term oleophobic (OP) shall include superoleophobic (SOP) behavior unless stated otherwise, and any and all embodiments, claims, and aspects of this disclosure reciting oleophobic behavior
9 may be limited to either oleophobic behavior that is not superoleophobic (contact angles from 90 -150 ) or superoleophobic behavior (contact angles of 150 or greater).
Anti-icing (AI) surfaces are surfaces that are resistant to ice formation and/or accretion in dynamic testing, or that prevent ice that forms from adhering to the surface (i.e., ice that forms can be removed with less force than from untreated metal surfaces).
For the purpose of this disclosure, HP/OP denotes hydrophobic behavior (including superhydrophobic behavior) or properties and/or oleophobic (including superoleophobic behavior) behavior or properties. HP/OP behavior may be understood to include anti-icing properties and any embodiment recited as having HP/OP behavior may be recited as having anti-icing properties, unless stated otherwise in this disclosure.
Durability, unless stated otherwise, refers to the resistance to loss of superhydrophobic or superoleophobic properties due to mechanical abrasion.
Alkyl as used herein denotes a linear or branched alkyl radical or group.
Alkyl groups may be independently selected from C1 to C20 alkyl, C2 to C20 alkyl, C4 to C20 alkyl, C6 to C18 alkyl, C6 to C16 alkyl, or C6 to C20 alkyl. Unless otherwise indicated, alkyl does not include cycloalkyl.
Cycloalkyl as used herein denotes a cyclic alkyl radical or group. Cycloalkyl groups may be independently selected from: C4 to C20 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; C6 to C20 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; C6 to C20 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities;
C5 to C18 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; C6 to C18 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; or C6 to C16 alkyl comprising one, two or more C4 to C8 cycloalkyl functionalities. Where two or more cycloalkyl groups are present they may be present as fused rings or in a spiro configuration. One or more hydrogen atoms of the cycloalkyl groups may be replaced by fluorine atoms.
Haloalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by halogen atoms. Halogen atoms may be limited to chlorine or fluorine atoms in halo alkyl groups.
Fluoroalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by fluorine atoms.
Perfluoroalkyl as used herein denotes an alkyl group in which fluorine atoms have been substituted for each hydrogen atom present in the alkyl group.
Rubber phase as used herein denotes a portion of styrene block copolymers having synthetic rubber attributes. In SBCs rubber phases are typically flanked or joined by polystyrene units that may function as end blocks. Typical synthetic rubbers include an isoprenoid or a polyolefin such as polybutadiene, polyisoprene, or ethylene/butylene.
For the purpose of this disclosure, unless stated otherwise, when content is indicated as being present on a "weight basis," the content is measured as the percentage of the weight of the components indicated to the total weight of the composition (including recited/required solvents). Optional solvents are not included in the weight of the composition.
"Colorant" as used herein is a material added to the coating composition to cause a change in color, i . e . , become colored. Colorants can be dyes which bind at least a portion of the material to be colored, insoluble pigments that are dispersed in at least a portion of the material to be colored, colored chemicals that are dispersed or dissolved in at least a portion of the material to be colored, or inks, which may be any combination of dyes, pigments and colored chemicals. In some embodiments, first or second particles may comprise colorants or may be prepared from materials that are colored.
2.0 Elastomeric Binders Elastomers are polymers that are elastic (i . e . , have viscoelasticity), and which generally have a low Young's modulus and high yield strain compared with other materials. Elastomers may be thermoset materials, which require vulcanization (e.g., covalent crosslinking) during curing, or thermoplastic materials (thermoplastic elastomers), in which the crosslinks are weaker dipole or hydrogen bonds.
Elastomeric binder systems employed to make elastomeric coatings (elastomer based coatings) having HP/OP properties are typically comprised of copolymers of polystyrene and a rubber (a rubber phase) known as Styrenic Block Copolymers (SBCs). SBCs are a class of thermoplastic elastomers consisting of a two-phase structure of hard polystyrene end blocks and soft rubber midblocks. The polystyrene end blocks associate to form domains that lock the molecules into place without vulcanization. Since this is a reversible process, the material can be processed on conventional thermoplastic equipment or dissolved in a suitable solvent for application as a coating. Polystyrene end blocks impart strength and the rubber phase mid-blocks impart elasticity. Figure 1 shows a schematic of a typical SBC
copolymer, where the rubber phase is linked to the polystyrene phase. In SBCs the rubber phase can be a synthetic rubber such as, for example, ethylene/butylene (EB e.g., ¨
[CH2CH2CH2CH2CH(CH2CH3)CH2]11¨) ethylene/propylene (EP, e . g . , -[CH2CH2CH(CH3)CH2]
ii¨), polybutadiene, polyisoprene, or polyolefin (see Figure 1). Figure 2 shows that the copolymers can have various spatial orientations such as linear, radial, or star like.
SBC compositions, when used as a base coating, produce highly durable HP/OP
coatings as measured by a variety of different methods, including those described herein. Moreover, the coatings are compatible with and adhere tightly to a broad range of materials, permitting a large number and type of objects and substrates to be coated.
SBC elastomers offer a variety of advantages and properties for the preparation of base coats used to prepare HP/OP coatings. As they can be dissolved/suspended in a number of solvents, they may be formulated into compositions that are amenable to application using standard equipment including conventional spray guns and aerosol canisters (e.g., an aerosol spray container comprises a valve assembly, a dip tube, and an actuator). As a base coating composition for use in a multi-step (e.g., two-step, three-step, four-step...
) HP/OP coating process, SBC elastomer formulations offer flexibility during application and in the application of the second component of the HP/OP coating process. The elastomeric first component can be applied to form a base coating and the second component, which comprises second particles whose application renders the coating HP/OP, can be applied to the base coating when it is wet, tacky, dry to touch, or even completely dried and cured.
A variety of SBCs may be employed to prepare the HP/OP coatings described herein. In an embodiment the SBC-containing binder compositions comprise a rubber phase comprising ethylene/butylene (EB e.g., ¨[CH2CH2CH2CH2CH(CH2CH3)CH2]11¨). In another embodiment, the SBC-containing binder compositions comprise a rubber phase comprising (poly)butadiene (e.g., styrene-butadiene-styrene (SBS) elastomeric polymers. In other embodiments, the rubber phases of suitable SBC polymer compositions comprise ethylene/propylene (EP
e.g., -[CH2CH2CH(CH3)CH2]11-), polybutadiene, polyisoprene or polyolefin. In another embodiment, binder compositions used for the preparation of durable HP/OP
coatings comprise a mixture of any two, three, or four SBC elastomers having rubber phases comprising:
ethylene/butylene butadiene, ethylene/propylene polybutadiene, polyisoprene or polyolefin.
Elastomeric coatings with an elongation at break that is greater than about 500%, 600%, 700%, 750%, or about 800% are generally desirable as binders for preparing the durable HP/OP
coatings (e.g., coatings prepared with "Kraton G" elastomers), although elastomeric coating compositions with lower elongation at break values can be employed. The rubber component in the SBC copolymers of such elastomer compositions typically varies from about 69% to about 87 %, but the rubber component may be about 65% to about 90%, about 67% to about 75%, about 75% to about 87%, or about 70% to about 80% (based on the weight of the SBC
copolymer(s)). Among the commercially available SBC elastomer compositions that can be employed as binders for the HP/OP coating compositions described herein are those developed by KRATON Polymers U.S. LLC. (Houston, Texas). Various elastomeric polymers, compositions, and their properties are described, for example, in the KRATON
Polymers' Fact Sheet K0151 Americas available on the world wide web at:
docs.kraton.com/kraton/attachments/downloads/82021AM.pdf.
In one embodiment the elastomers employed as binders may be ethylene butylene (EB) elastomeric polymers which have styrene domains (endblocks) and ethylene/butylene rubber phase midblocks. Such EB elastomers may comprise about 65% to 75% rubber phase midblocks, (e.g., about 65%, about 70% or about 75% rubber phase midblocks) and have an elongation at break of 500 to 800% using ASTM D412 on films cast from toluene solution with the grip separation speed set at 10 inches per minute. Some properties of KRATON EB
elastomers are detailed in Table 1.
In one embodiment the elastomers employed as binders may be styrene-butadiene-styrene (SBS) elastomeric polymers. Such SBS elastomers comprise about 60% to 74%
butadiene by weight, and have an elongation at break of from 800 to 900% using on films cast from toluene solution with the grip separation speed set at 10 inches per minute.
Some properties of KRATON styrene-butadiene-styrene (SBS) elastomeric polymers (KRATON D SBS ) are detailed in Table 2.
Table 1 EB Based Polymers*
Property G1633 G1650 G1651 G1652 G1654 G1657 G1660 G1726 (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) Linear Linear Linear Linear Linear Linear Linear Linear Tensile Strength, 35 >28 31 >28 23 32 MPal'2 300% Modulus 5.6 4.8 2.4 5.5 MPal'2 Elongation at 500 >800 500 800 750 800 Break, % 1'2 Specific Gravity 0.91 0.91 0.91 0.91 0.91 0.89 0.91 0.91 Brookfield Viscosity, cps at C
25%w4 8,000 >50,000 1,800 >50,000 4,200 8,000 200
Anti-icing (AI) surfaces are surfaces that are resistant to ice formation and/or accretion in dynamic testing, or that prevent ice that forms from adhering to the surface (i.e., ice that forms can be removed with less force than from untreated metal surfaces).
For the purpose of this disclosure, HP/OP denotes hydrophobic behavior (including superhydrophobic behavior) or properties and/or oleophobic (including superoleophobic behavior) behavior or properties. HP/OP behavior may be understood to include anti-icing properties and any embodiment recited as having HP/OP behavior may be recited as having anti-icing properties, unless stated otherwise in this disclosure.
Durability, unless stated otherwise, refers to the resistance to loss of superhydrophobic or superoleophobic properties due to mechanical abrasion.
Alkyl as used herein denotes a linear or branched alkyl radical or group.
Alkyl groups may be independently selected from C1 to C20 alkyl, C2 to C20 alkyl, C4 to C20 alkyl, C6 to C18 alkyl, C6 to C16 alkyl, or C6 to C20 alkyl. Unless otherwise indicated, alkyl does not include cycloalkyl.
Cycloalkyl as used herein denotes a cyclic alkyl radical or group. Cycloalkyl groups may be independently selected from: C4 to C20 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; C6 to C20 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; C6 to C20 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities;
C5 to C18 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; C6 to C18 alkyl comprising one, two, or more C4 to C8 cycloalkyl functionalities; or C6 to C16 alkyl comprising one, two or more C4 to C8 cycloalkyl functionalities. Where two or more cycloalkyl groups are present they may be present as fused rings or in a spiro configuration. One or more hydrogen atoms of the cycloalkyl groups may be replaced by fluorine atoms.
Haloalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by halogen atoms. Halogen atoms may be limited to chlorine or fluorine atoms in halo alkyl groups.
Fluoroalkyl as used herein denotes an alkyl group in which some or all of the hydrogen atoms present in an alkyl group have been replaced by fluorine atoms.
Perfluoroalkyl as used herein denotes an alkyl group in which fluorine atoms have been substituted for each hydrogen atom present in the alkyl group.
Rubber phase as used herein denotes a portion of styrene block copolymers having synthetic rubber attributes. In SBCs rubber phases are typically flanked or joined by polystyrene units that may function as end blocks. Typical synthetic rubbers include an isoprenoid or a polyolefin such as polybutadiene, polyisoprene, or ethylene/butylene.
For the purpose of this disclosure, unless stated otherwise, when content is indicated as being present on a "weight basis," the content is measured as the percentage of the weight of the components indicated to the total weight of the composition (including recited/required solvents). Optional solvents are not included in the weight of the composition.
"Colorant" as used herein is a material added to the coating composition to cause a change in color, i . e . , become colored. Colorants can be dyes which bind at least a portion of the material to be colored, insoluble pigments that are dispersed in at least a portion of the material to be colored, colored chemicals that are dispersed or dissolved in at least a portion of the material to be colored, or inks, which may be any combination of dyes, pigments and colored chemicals. In some embodiments, first or second particles may comprise colorants or may be prepared from materials that are colored.
2.0 Elastomeric Binders Elastomers are polymers that are elastic (i . e . , have viscoelasticity), and which generally have a low Young's modulus and high yield strain compared with other materials. Elastomers may be thermoset materials, which require vulcanization (e.g., covalent crosslinking) during curing, or thermoplastic materials (thermoplastic elastomers), in which the crosslinks are weaker dipole or hydrogen bonds.
Elastomeric binder systems employed to make elastomeric coatings (elastomer based coatings) having HP/OP properties are typically comprised of copolymers of polystyrene and a rubber (a rubber phase) known as Styrenic Block Copolymers (SBCs). SBCs are a class of thermoplastic elastomers consisting of a two-phase structure of hard polystyrene end blocks and soft rubber midblocks. The polystyrene end blocks associate to form domains that lock the molecules into place without vulcanization. Since this is a reversible process, the material can be processed on conventional thermoplastic equipment or dissolved in a suitable solvent for application as a coating. Polystyrene end blocks impart strength and the rubber phase mid-blocks impart elasticity. Figure 1 shows a schematic of a typical SBC
copolymer, where the rubber phase is linked to the polystyrene phase. In SBCs the rubber phase can be a synthetic rubber such as, for example, ethylene/butylene (EB e.g., ¨
[CH2CH2CH2CH2CH(CH2CH3)CH2]11¨) ethylene/propylene (EP, e . g . , -[CH2CH2CH(CH3)CH2]
ii¨), polybutadiene, polyisoprene, or polyolefin (see Figure 1). Figure 2 shows that the copolymers can have various spatial orientations such as linear, radial, or star like.
SBC compositions, when used as a base coating, produce highly durable HP/OP
coatings as measured by a variety of different methods, including those described herein. Moreover, the coatings are compatible with and adhere tightly to a broad range of materials, permitting a large number and type of objects and substrates to be coated.
SBC elastomers offer a variety of advantages and properties for the preparation of base coats used to prepare HP/OP coatings. As they can be dissolved/suspended in a number of solvents, they may be formulated into compositions that are amenable to application using standard equipment including conventional spray guns and aerosol canisters (e.g., an aerosol spray container comprises a valve assembly, a dip tube, and an actuator). As a base coating composition for use in a multi-step (e.g., two-step, three-step, four-step...
) HP/OP coating process, SBC elastomer formulations offer flexibility during application and in the application of the second component of the HP/OP coating process. The elastomeric first component can be applied to form a base coating and the second component, which comprises second particles whose application renders the coating HP/OP, can be applied to the base coating when it is wet, tacky, dry to touch, or even completely dried and cured.
A variety of SBCs may be employed to prepare the HP/OP coatings described herein. In an embodiment the SBC-containing binder compositions comprise a rubber phase comprising ethylene/butylene (EB e.g., ¨[CH2CH2CH2CH2CH(CH2CH3)CH2]11¨). In another embodiment, the SBC-containing binder compositions comprise a rubber phase comprising (poly)butadiene (e.g., styrene-butadiene-styrene (SBS) elastomeric polymers. In other embodiments, the rubber phases of suitable SBC polymer compositions comprise ethylene/propylene (EP
e.g., -[CH2CH2CH(CH3)CH2]11-), polybutadiene, polyisoprene or polyolefin. In another embodiment, binder compositions used for the preparation of durable HP/OP
coatings comprise a mixture of any two, three, or four SBC elastomers having rubber phases comprising:
ethylene/butylene butadiene, ethylene/propylene polybutadiene, polyisoprene or polyolefin.
Elastomeric coatings with an elongation at break that is greater than about 500%, 600%, 700%, 750%, or about 800% are generally desirable as binders for preparing the durable HP/OP
coatings (e.g., coatings prepared with "Kraton G" elastomers), although elastomeric coating compositions with lower elongation at break values can be employed. The rubber component in the SBC copolymers of such elastomer compositions typically varies from about 69% to about 87 %, but the rubber component may be about 65% to about 90%, about 67% to about 75%, about 75% to about 87%, or about 70% to about 80% (based on the weight of the SBC
copolymer(s)). Among the commercially available SBC elastomer compositions that can be employed as binders for the HP/OP coating compositions described herein are those developed by KRATON Polymers U.S. LLC. (Houston, Texas). Various elastomeric polymers, compositions, and their properties are described, for example, in the KRATON
Polymers' Fact Sheet K0151 Americas available on the world wide web at:
docs.kraton.com/kraton/attachments/downloads/82021AM.pdf.
In one embodiment the elastomers employed as binders may be ethylene butylene (EB) elastomeric polymers which have styrene domains (endblocks) and ethylene/butylene rubber phase midblocks. Such EB elastomers may comprise about 65% to 75% rubber phase midblocks, (e.g., about 65%, about 70% or about 75% rubber phase midblocks) and have an elongation at break of 500 to 800% using ASTM D412 on films cast from toluene solution with the grip separation speed set at 10 inches per minute. Some properties of KRATON EB
elastomers are detailed in Table 1.
In one embodiment the elastomers employed as binders may be styrene-butadiene-styrene (SBS) elastomeric polymers. Such SBS elastomers comprise about 60% to 74%
butadiene by weight, and have an elongation at break of from 800 to 900% using on films cast from toluene solution with the grip separation speed set at 10 inches per minute.
Some properties of KRATON styrene-butadiene-styrene (SBS) elastomeric polymers (KRATON D SBS ) are detailed in Table 2.
Table 1 EB Based Polymers*
Property G1633 G1650 G1651 G1652 G1654 G1657 G1660 G1726 (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) Linear Linear Linear Linear Linear Linear Linear Linear Tensile Strength, 35 >28 31 >28 23 32 MPal'2 300% Modulus 5.6 4.8 2.4 5.5 MPal'2 Elongation at 500 >800 500 800 750 800 Break, % 1'2 Specific Gravity 0.91 0.91 0.91 0.91 0.91 0.89 0.91 0.91 Brookfield Viscosity, cps at C
25%w4 8,000 >50,000 1,800 >50,000 4,200 8,000 200
10%w4 50 1,800 30 410 65 50 ¨Melt Index g/10 <1 <1 <1 <1 <1 <8 <1 mm. (5kg) 200 C
230 C <1 <1 <1 5 <1 22 <1 <100 Styrene/Rubber 30/70 30/70 30/70 30/70 33/67 13/87 31/69 30/70 Ratio Fluffy Powder/ Powder/ Powder/ Powder/ Dense Powder Dense Physical Form Crumb Fluffy Fluffy Fluffy Fluffy Pellet Pellet Crumb Crumb Crumb Crumb Diblock, % <1 <1 <1 <1 29 Property (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) Linear Linear Linear Linear Linear Linear Linear Linear Comments FDA FDA FDA FDA FDA FDA FDA FDA
*polymers recited in this table supplied by KRATONC) (1) ASTM method D412 tensile tester grip separation speed 10 in./min.
(2) Typical properties determined on film cast from toluene solution.
(3) Typical values on polymer compression molded at 177 C
(4) Neat Polymer concentration in toluene Table 2 SBS Elastomeric Polymers*
Property (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) Di- Linear Linear Radial Diblock Linear Linear Linear block Tensile Strength, MPa1*2 2 32 32 32 2 21 32 28 300% Modulus, MPa1*2 1.0 2.8 2.8 2.4 1.2 2.1 2.8 2.9 Elongation at Break, 880 880 900 600 800 900 800 % 1.2 Set at Break, %1.2 10 10 10 40 20 10 Hardness, Shore A (10 70 69 66 63 64 74 66 70 sec.)3 Specific Gravity 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.96 Brookfield Viscosity, cps at 315 4,000 1,100 9,000 630 4,800 1,000 1,650 25 C (25%w) Brookfield Viscosity, cps at 2,500 420 25 C (15%w) Melt Index g/10 min. 20 <1 14 <1 10 <1 8 3 (200 C/5kg) Styrene/
Rubber Ratio 33/67 31/69 28/72 23/77 33/67 36/64 Physical Form Porous Porous Porous Porous Porous Porous Porous Porous Pellet Pellet Pellet Pellet Pellet Pellet Pellet Pellet Powder Powder Powder Powder Diblock, % 75 16 17 16 78 34 15 <1 *polymers recited in this table supplied by KRATON
(1) ASTM method D412 grip separation speed 10 in./min.
(2) Typical properties determined on film cast from toluene solution (3) Typical values on polymer compression molded at 177 C
(4) Neat polymer concentration in toluene Table 2 (continued) SBS Elastomeric Polymers*
Property (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) Linear Radial Radial Radial Radial Linear Linear Tensile Strength, MPa1*2 28 28 25 300% Modulus, MPal* -2 2.9 5.5 3 - --Elongation at Break, 800 820 800 - - --% 1.2 Set at Break, %1.2 --Hardness, Shore A (10 sec.)3 87 68 74 68 68 66 Specific Gravity 0.94 0.94 0.94 0.94 0.94 0.94 0.94 Brookfield Viscosity, cps at 600 >20,000 TBD5 >20,000 1,500v 25 C (25%w) Brookfield Viscosity, cps at - 1,100 1,200 TBD 1,100 2,000 (15%w) Melt Index g/10 min. 14 <1 <1 <1 <1 <1 (200 C/5kg) Styrene/
Rubber Ratio 40/60 31/69 30/70 31/69 33/69 30/70 Physical Form Porous Porous Porous Porous Porous Porous Porous Pellet Pellet Pellet Pellet Pellet Pellet Pellet Powder Powder Powder Powder Powder Diblock, % <1 16 10 16 18 <1 <1 *polymers recited in this table supplied by KRATON
(1) ASTM method D412 grip separation speed 10 in./min.
(2) Typical properties determined on film cast from toluene solution (3) Typical values on polymer compression molded at 177 C
(4) Neat polymer concentration in toluene (5) TBD - To Be Determined In another embodiment the elastomers employed as binders may be maleated styrene-ethylene/butylene-styrene (SEBS) elastomeric polymers. Such maleated SEBS
elastomers comprise about 65% to about 90% (e.g., about 70% or about 87%) rubber midblocks by weight, 5 and have an elongation at break of 500 to 750% using ASTM D412 on films cast from toluene solution with the grip separation speed set at 10 inches per minute. Maleated SEBS polymers typically have from about 0.8% to about 2.2% (e.g., 0.9% to 2.1% or 1% to 1.7%) of substitution. Some properties of KRATON styrene-ethylene/butylene-styrene (SEBS) elastomeric polymers (KRATON FG Polymers) are detailed in Table 3.
Table 3 Maleated SEBS Polymers FG Polymer Grades*
FG1901 (SEBS) FG1924 (SEBS) Property Linear Linear Tensile Strength, MPal 34 23 300% Modulus, MPal Elongation at Break, %1 500 750 Hardness, Shore A (10 sec)2 71 49 Specific Gravity 0.91 0.89 Brookfield Viscosity, 25%w 5,000 19,000 (toluene solutions) cps at 25 C 110 270 10%w Melt Index g/10 mm (5kg) Styrene/Rubber Ratio 30/70 13/87 Physical Form Dense Pellet Dense Pellet FDA3 1.0% bound Comments 1.7% bound functionality functionality *polymers recited in this table supplied by KRATON
(1) ASTM method D412-tensile tester grip separation speed 10 in./min.
(2) Typical values on polymer compression molded at 177 C
In one embodiment the elastomeric binder comprises triblock copolymers of styrene and ethylene/butylene with a polystyrene content of: about 8% to about 14%, about 12% to about 20%, about 18% to about 28%, about 22% to about 32%, about 26% to about 36%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 16%, about 18%, about 19%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, about 36% or mixtures of any two or more, three or more, or four or more of such triblock copolymers. Any one or more of such triblock copolymers may optionally comprise 1%
to 3%, 1.4% to 2.0%, 1% to 1.4%, 1.6% to 3%, or 2% to 3% of bound maleic anhydride (maleated copolymers) and may be linear triblock copolymers. In one such embodiment the binder comprises two different maleated triblock copolymers of styrene and ethylene/butylene with a polystyrene: a first triblock copolymer of styrene and ethylene/butylene with a polystyrene having 0.4% to 1.6% (e.g., 0.5% to 1.5%, 0.6% to 1.4,% or 0.7% to 1.3%) substitution by maleic anhydride by weight of the first triblock copolymer (and optionally less than 0.3% maleic anhydride free); and a second triblock copolymer of styrene and ethylene/butylene with a polystyrene having 1.1% to 2.5% (e.g., 1.3 to 2.3 or 1.4 to 2.4%) substitution by maleic anhydride by weight of the second triblock copolymer.
In such an embodiment the first and/or second triblock copolymers may be linear or branched copolymers(e.g., arborols or dendrimers) , and the second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1 (e.g., the first copolymer to second copolymer ratio is about 4:1 to about 5.5:1, about 5:1 to about 6:1, or about 5.5:1 to about 6.5:1).
Persons skilled in the art will also recognize other elastomeric binders that may be used in place of or in addition to the elastomeric binders described in this disclosure.
In addition to comprising elastomeric polymers (e.g., SBCs), first particles and solvents, elastomeric binder systems that serve as first components optionally comprise a tackifier.
Tackifiers may be present in any suitable amount, including in a range selected from about or from about 0.5% to about 30%; 1% to about 5%, from about 2% to about 8%, from about 3% to about 7%, from about 5% to about 10%, from about 10% to about 15%, from about 15% to about 20%, from about 20% to about 25%, or from about 25% to about 30%. Some suitable tackifiers, including totally synthetic (e.g., members of the Regalrez family from Eastman Chemical) or modified resins or rosins are set forth in the section describing primers that follows.
First components, and primers discussed below, may further comprise light stabilizers and UV absorbers (UV stabilizers), fire retardants, and/or antioxidants. For example, Tinuvin light stabilizing products (e.g., Tinuvin 328 and/or Tinuvin 770DF) produced by BASF , and/or IRGANOX antioxidant products (e.g., phenolic or hindered phenolic antioxidants such as IRGANOX 1520 or IRGANOX 150L) produced by BASF may be included in the first component binder composition used to set down the base coat or in a primer.
Where light/UV
stabilizers, UV absorbers, fire retardants, and/or antioxidants are added to either or both of the first component or the primer, they are generally added in an amount less than 2% by weight (e.g., about 1%, 0.75%, 0.5%, 0.4%, 0.3%, 0.2% 0.1%, 0.075%, 0.06%, or 0.05%, or in a range selected from about 0.01% to about 2%, from about 0.05% to about 1.0%, or from about 0.75%
to about 0.5% by weight), and take the place of a corresponding weight of any solvents that may be present.
In addition to the ease of application, elastomer based coatings that do not contain a colorant or significant amounts of opaque particles are nearly transparent to visible light.
Typical light transmission (Total Luminous Transmittance or "TLT") of an elastomeric binder coating prepared using SBCs having 15 micron thickness is approximately 90%
(about 85% to about 92%) with a haze of about 61% (about 55% to about 65%). HP/OP coatings without added colorants that are about 25 microns thick prepared with clear first particles (e.g., EXPANCEL particles or other plastic or glass particles or hollow spheres) and fumed silica second particles treated with a silane (silanizing agent) can be nearly transparent. Such HP/OP
coatings typically have a TLT of about 80% (about 75% to about 85%) with a haze of about 90% (about 85% to about 90%) as measure by ASTM D1003-11. For the measurements the instrument was calibrated against air and glass sample blanks and given a TLT
of about 90% to about 91% and a haze of about 0.2%. Excluding or removing fine particulate materials such as talc used to increase the properties of commercially available elastomer compositions (e.g., flowability of bulk particulates) may increase TLT and haze values. Such fine particulates used in bulk elastomers may be removed by washing with a suitable solvent or by omitting the material from the elastomer compositions when they are prepared.
A variety of solvents may be employed to dissolve elastomeric binders for the preparation of coating compositions used to prepare the base coat of HP/OP
coatings described herein. In some embodiments, the copolymers are dissolved in solvents selected from: methyl ethyl ketone (MEK), ethyl acetate, toluene, 1-chloro-4-(trifluoromethyl)-benzene, xylene or mixed xylenes (including technical grade xylenes), isopropyl acetate, 1,1,1,-trichloroethane, methyl isobutyl ketone (MIBK), tertbutyl acetate (t-butyl acetate), cyclohexane, methyl-cyclohexane, or mixtures comprising any two, three, four or more thereof. In one embodiment the solvent(s) are selected from those found in the solubility chart shown in Figure 3, or mixtures of any two, three, four or more thereof. In another embodiment, the solvent comprises greater than 50%, 60%, 70%, 80%, 90%, 95%, 98% or 99% of a xylene (1,2-xylene, 1,3-xylene, or 1,4-xylene) or a mixture of any two or all three xylenes and optionally ethyl benzene (e.g., a technical grade of xylene comprising 34%-47% 1,3-xylene, 9%-21% 1,4-xylene, 4%-16% 1,2-xylene, 9%-10% ethylbenzene, 0%4% toluene, and 0%-1 % benzene).
In any of the foregoing embodiments, particularly where coatings are to be nearly transparent, the elastomeric binder components comprise at most insubstantial amounts (e.g., less than about 0.5% by weight of the polymers present in the binder) of colorants or particulates that are insoluble in solvents that dissolve the elastomeric polymers and/or that would block the transmission of visible light. One source of such particulates is materials added for the flowability of bulk polymers in the form of powders, pellets, or flakes (e.g., talc added to bulk SBCs).
3.0 Particles Employed in HP/OP Oleophobic Coatings:
3.1 First Particles Embodiments of the coatings disclosed herein may comprise particles that are added to the binder compositions to improve the mechanical properties of the coating, e.g., the durability of the HP/OP coatings. A wide variety of such particles, which are also known as extenders or fillers, may be added to the binders. Those particles are denoted herein as "first particles"
because the coatings described herein may have one or more additional types of particles. Such first particles that can be employed in the HP/OP coatings described herein include, but are not limited to, particles comprising: wood (e.g., wood dust), glass, metals (e.g., iron, titanium, nickel, zinc, tin), alloys of metals, metal oxides, metalloid oxides (e.g., silica), plastics (e.g., thermoplastics), carbides, nitrides, borides, spinels, diamonds, and fibers (e.g., glass fibers).
Numerous variables may be considered in the selection of first particles.
These variables include, but are not limited to, the effect the first particles have on the resulting coatings, their size, their hardness, their compatibility with the binder, the resistance of the first particles to the environment in which the coatings will be employed, and the environment the first particles must endure in the coating and/or curing process, including resistance to temperature and solvent conditions. In addition, if light is used for curing the coatings or they are intended for extended exposure to sunlight, the particles must be resistant to the required light exposure conditions (e.g., resistant to UV light employed in curing or sunlight).
In embodiments described herein, first particles have an average size in a range selected from about 1 micron (pm) to about 300 m or from about 30 m to about 225 m.
Within the broader ranges, embodiments include ranges of first particles having an average size of from about 1 pm to about 5 pm, from about 5 pm to about 10 pm, from about 10 pm to about 15 pm, from about 15 pm to about 20 pm, from about 20 pm to about 25 pm, from about 1 pm to about 25 pm, from about 5 pm to about 25 pm, from about 25 pm to about 50 pm, from about 50 pm to about 75 pm, from about 75 pm to about 100 pm, from about 100 pm to about 125 pm, from about 125 pm to about 150 pm, from about 150 pm to about 175 pm, from about 175 pm to about 200 pm, from about 200 pm to about 225 [tm, and from about 225 pm to about 250 pm.
Also included within this broad range are embodiments employing particles in ranges from about 10 m to about 100 m, from about 10 m to about 200 m, from about 20 m to about 200 m, from about 30 m to about 50 m, from about 30 m to about 100 m, from about 30 m to about 200 m, from about 30 m to about 225 m, from about 50 m to about 100 m, from about 50 m to about 200 m, from about 75 m to about 150 m, from about 75 m to about 200 m, from about 100 m to about 225 m, from about 100 m to about 250 m, from about 125 p.m to about 225 pm, from about 125 p.m to about 250 pm, from about 150 p.m to about 200 pm, from about 150 p.m to about 250 pm, from about 175 p.m to about 250 pm, from about 200 p.m to about 250 pm, from about 225 p.m to about 275 pm, or from about 250 p.m to about 300 p.m.
First particles may be incorporated into the elastomer binders at various ratios depending on the binder composition and the first particle's properties. In some embodiments, the first particles may have a content range selected from about 0.01% to about 60% or more by weight.
Included within this broad range are embodiments in which the first particles are present, by weight, in ranges from about 0.02% to about 0.2%, from about 0.05% to about 0.5%, from about 0.075% to about 0.75%, from about 0.1% to about 1%, from about 0.5% to about 2.5%, from about 2% to about 5%, from about 5% to about 10%, from about 10% to about 15%, from about 15% to about 20%, from about 20% to about 25%, from about 25% to about 30%, from about 30% to about 35%, from about 35% to about 40%, from about 40% to about 45%, from about 45% to about 50%, from about 50% to about 55%, from about 55% to about 60%, and greater than 60%. Also included within this broad range are embodiments in which the first particles are present, by weight, in ranges from about 4% to about 30%, from about 5% to about 25%, from about 5% to about 35%, from about 10% to about 25%, from about 10% to about 30%, from about 10% to about 40%, from about 10% to about 45%, from about 15% to about 25%, from about 15% to about 35%, from about 15% to about 45%, from about 20% to about 30%, from about 20% to about 35%, from about 20% to about 40%, from about 20% to about 45%, from about 20% to about 55%, from about 25% to about 40%, from about 25% to about 45%, from about 25% to about 55%, from about 30% to about 40%, from about 30% to about 45%, from about 30% to about 55%, from about 30% to about 60%, from about 35% to about 45%, from about 35% to about 50%, from about 35% to about 60%, from about 40% to about 60%, from about 0.01% to about 5%, from about 0.03% to about 1%, from about 0.05%
to about 0.15%, from about 0.1% to about 2.5%, from about 0.2% to about 5%, from about 0.05% to about 10%, from about 0.1% to about 10%, from about 0.05% to about 15%, or from about 0.05% to about 20%, on a weight basis.
In those embodiments where it is desirable to have coatings that are transparent, substantially transparent, or colored but transparent, it is generally desirable to employ particles that are transparent. In one set of embodiments, plastic (e.g., thermoplastic) microspheres are employed in the binder systems to develop surface texture. In another set of embodiments, glass microspheres are employed in the binder systems to develop surface texture.
In one embodiment, substantially spherical thermoplastic particles are added to the elastomeric binder composition to develop surface texture (e.g., EXPANCEL
microspheres or EXPANCEL particles). Such microspheres consist of a polymer shell encapsulating a gas. The average diameter of these hollow spheres typically ranges from 6 to 45 i.tm and have a density of 1000 to 1300 kg/m3 (8.3-10.8 lbs/US Gallon). Upon heating, the microspheres expand and the volume of the microspheres can increase more than 40 times (with the diameter changing, for example, from 10 to 40 i.tm), resulting in a density below 30 kg/m3 (0.25 lbs/US Gallon).
Typical expansion temperatures range from 80 to 190 C (176-374 F). When heating the microspheres the pressure of the gas inside the shell increases and the thermoplastic shell softens, resulting in a dramatic increase of the volume of the microspheres.
Cooling the microspheres results in the shell stiffening again and produces lighter (lower density) expanded microspheres. Some thermoplastic microspheres produced under the EXPANCEL
brand (AkzoNobel, distributed by Eka Chemicals, Inc., 2240 Northmont Parkway, Duluth, GA 30096, USA) are suitable for use in preparing HP/OP, particularly those that are substantially transparent. See Table 4.
Table 4 EXPANCEL particles and properties Main types Varieties Description Solid con-Density of tent riej EXPANCEL
Unexpended EXPANCEL WU :Wdatnexpanded:tbitmi:
mic rospheres spneres EXPANCEL WUF Wet, unexpended micro- 60-30 1000-1300 spheres EXPANCEL DU DiV, unexpanueu spheres EXPANCEL OUT Dry, treated. unexpended rni- >99 -1000 crospheres EXPANCEL SL Wet, satted. unexpended *ttlk crospheres EXPANCEL SW Wet, unexpended micro- 44 1200 spheres EXPANCELMB expended micro- 65 spheres mixed :vith a ntatrix, iEXPANCEL) e d. EVA
Expanded mi- EXPANCEL WE 'net, expanded rncrospheres 15 30 crospheres EXPANCEL DE Dry. expander,' microspheres >99 25-70 EXPANCEL DET Dry treated, expanded micro- >99 25 spheres Where HP/OP coatings capable of withstanding higher temperatures are desired, and particularly coatings that are substantially transparent, glass microspheres may be employed in place of thermoplastic microspheres. Such glass microspheres include those produced by 3MTm (St. Paul, MN) or Sphere One, Inc. (Chattanooga, TN).
3.1.1 Exemplary Sources of First Particles First particles may be prepared from the diverse materials described above.
Alternatively, first particles may be purchased from a variety of suppliers.
Some commercially available first particles that may be employed in the formation of the HP/OP
coatings described herein include those in Table 5.
Table 5 First Particles First First Particle First Particle First (g/cc) Particle Color Crush Source part- (Filler) Type Particle Size Strength Location icle ID Details Range (psi) No. (pm) 1 K1 Glass Bubbles GPSa 0.125 30-120 White 250 3mTm 2 K15 Glass Bubbles GPSa 0.15 30-115 White 300 3mTm 3 S15 Glass Bubbles GPSa 0.15 25-95 White 300 3mTm 4 S22 Glass Bubbles GPSa 0.22 20-75 White 400 3mTm 5 K20 Glass Bubbles GPSa 0.2 20-125 White 500 3mTm 6 K25 Glass Bubbles GPSa 0.25 25-105 White 750 3mTm 7 S32 Glass Bubbles GPSa 0.32 20-80 White 2000 3mTm 8 S35 Glass Bubbles GPSa 0.35 10-85 White 3000 3mTm 9 K37 Glass Bubbles GPSa 0.37 20-85 White 3000 3mTm S38 Glass Bubbles GPSa 0.38 15-85 White 4000 3mTm
230 C <1 <1 <1 5 <1 22 <1 <100 Styrene/Rubber 30/70 30/70 30/70 30/70 33/67 13/87 31/69 30/70 Ratio Fluffy Powder/ Powder/ Powder/ Powder/ Dense Powder Dense Physical Form Crumb Fluffy Fluffy Fluffy Fluffy Pellet Pellet Crumb Crumb Crumb Crumb Diblock, % <1 <1 <1 <1 29 Property (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) (SEBS) Linear Linear Linear Linear Linear Linear Linear Linear Comments FDA FDA FDA FDA FDA FDA FDA FDA
*polymers recited in this table supplied by KRATONC) (1) ASTM method D412 tensile tester grip separation speed 10 in./min.
(2) Typical properties determined on film cast from toluene solution.
(3) Typical values on polymer compression molded at 177 C
(4) Neat Polymer concentration in toluene Table 2 SBS Elastomeric Polymers*
Property (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) Di- Linear Linear Radial Diblock Linear Linear Linear block Tensile Strength, MPa1*2 2 32 32 32 2 21 32 28 300% Modulus, MPa1*2 1.0 2.8 2.8 2.4 1.2 2.1 2.8 2.9 Elongation at Break, 880 880 900 600 800 900 800 % 1.2 Set at Break, %1.2 10 10 10 40 20 10 Hardness, Shore A (10 70 69 66 63 64 74 66 70 sec.)3 Specific Gravity 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.96 Brookfield Viscosity, cps at 315 4,000 1,100 9,000 630 4,800 1,000 1,650 25 C (25%w) Brookfield Viscosity, cps at 2,500 420 25 C (15%w) Melt Index g/10 min. 20 <1 14 <1 10 <1 8 3 (200 C/5kg) Styrene/
Rubber Ratio 33/67 31/69 28/72 23/77 33/67 36/64 Physical Form Porous Porous Porous Porous Porous Porous Porous Porous Pellet Pellet Pellet Pellet Pellet Pellet Pellet Pellet Powder Powder Powder Powder Diblock, % 75 16 17 16 78 34 15 <1 *polymers recited in this table supplied by KRATON
(1) ASTM method D412 grip separation speed 10 in./min.
(2) Typical properties determined on film cast from toluene solution (3) Typical values on polymer compression molded at 177 C
(4) Neat polymer concentration in toluene Table 2 (continued) SBS Elastomeric Polymers*
Property (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) (SBS) Linear Radial Radial Radial Radial Linear Linear Tensile Strength, MPa1*2 28 28 25 300% Modulus, MPal* -2 2.9 5.5 3 - --Elongation at Break, 800 820 800 - - --% 1.2 Set at Break, %1.2 --Hardness, Shore A (10 sec.)3 87 68 74 68 68 66 Specific Gravity 0.94 0.94 0.94 0.94 0.94 0.94 0.94 Brookfield Viscosity, cps at 600 >20,000 TBD5 >20,000 1,500v 25 C (25%w) Brookfield Viscosity, cps at - 1,100 1,200 TBD 1,100 2,000 (15%w) Melt Index g/10 min. 14 <1 <1 <1 <1 <1 (200 C/5kg) Styrene/
Rubber Ratio 40/60 31/69 30/70 31/69 33/69 30/70 Physical Form Porous Porous Porous Porous Porous Porous Porous Pellet Pellet Pellet Pellet Pellet Pellet Pellet Powder Powder Powder Powder Powder Diblock, % <1 16 10 16 18 <1 <1 *polymers recited in this table supplied by KRATON
(1) ASTM method D412 grip separation speed 10 in./min.
(2) Typical properties determined on film cast from toluene solution (3) Typical values on polymer compression molded at 177 C
(4) Neat polymer concentration in toluene (5) TBD - To Be Determined In another embodiment the elastomers employed as binders may be maleated styrene-ethylene/butylene-styrene (SEBS) elastomeric polymers. Such maleated SEBS
elastomers comprise about 65% to about 90% (e.g., about 70% or about 87%) rubber midblocks by weight, 5 and have an elongation at break of 500 to 750% using ASTM D412 on films cast from toluene solution with the grip separation speed set at 10 inches per minute. Maleated SEBS polymers typically have from about 0.8% to about 2.2% (e.g., 0.9% to 2.1% or 1% to 1.7%) of substitution. Some properties of KRATON styrene-ethylene/butylene-styrene (SEBS) elastomeric polymers (KRATON FG Polymers) are detailed in Table 3.
Table 3 Maleated SEBS Polymers FG Polymer Grades*
FG1901 (SEBS) FG1924 (SEBS) Property Linear Linear Tensile Strength, MPal 34 23 300% Modulus, MPal Elongation at Break, %1 500 750 Hardness, Shore A (10 sec)2 71 49 Specific Gravity 0.91 0.89 Brookfield Viscosity, 25%w 5,000 19,000 (toluene solutions) cps at 25 C 110 270 10%w Melt Index g/10 mm (5kg) Styrene/Rubber Ratio 30/70 13/87 Physical Form Dense Pellet Dense Pellet FDA3 1.0% bound Comments 1.7% bound functionality functionality *polymers recited in this table supplied by KRATON
(1) ASTM method D412-tensile tester grip separation speed 10 in./min.
(2) Typical values on polymer compression molded at 177 C
In one embodiment the elastomeric binder comprises triblock copolymers of styrene and ethylene/butylene with a polystyrene content of: about 8% to about 14%, about 12% to about 20%, about 18% to about 28%, about 22% to about 32%, about 26% to about 36%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 16%, about 18%, about 19%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, about 36% or mixtures of any two or more, three or more, or four or more of such triblock copolymers. Any one or more of such triblock copolymers may optionally comprise 1%
to 3%, 1.4% to 2.0%, 1% to 1.4%, 1.6% to 3%, or 2% to 3% of bound maleic anhydride (maleated copolymers) and may be linear triblock copolymers. In one such embodiment the binder comprises two different maleated triblock copolymers of styrene and ethylene/butylene with a polystyrene: a first triblock copolymer of styrene and ethylene/butylene with a polystyrene having 0.4% to 1.6% (e.g., 0.5% to 1.5%, 0.6% to 1.4,% or 0.7% to 1.3%) substitution by maleic anhydride by weight of the first triblock copolymer (and optionally less than 0.3% maleic anhydride free); and a second triblock copolymer of styrene and ethylene/butylene with a polystyrene having 1.1% to 2.5% (e.g., 1.3 to 2.3 or 1.4 to 2.4%) substitution by maleic anhydride by weight of the second triblock copolymer.
In such an embodiment the first and/or second triblock copolymers may be linear or branched copolymers(e.g., arborols or dendrimers) , and the second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1 (e.g., the first copolymer to second copolymer ratio is about 4:1 to about 5.5:1, about 5:1 to about 6:1, or about 5.5:1 to about 6.5:1).
Persons skilled in the art will also recognize other elastomeric binders that may be used in place of or in addition to the elastomeric binders described in this disclosure.
In addition to comprising elastomeric polymers (e.g., SBCs), first particles and solvents, elastomeric binder systems that serve as first components optionally comprise a tackifier.
Tackifiers may be present in any suitable amount, including in a range selected from about or from about 0.5% to about 30%; 1% to about 5%, from about 2% to about 8%, from about 3% to about 7%, from about 5% to about 10%, from about 10% to about 15%, from about 15% to about 20%, from about 20% to about 25%, or from about 25% to about 30%. Some suitable tackifiers, including totally synthetic (e.g., members of the Regalrez family from Eastman Chemical) or modified resins or rosins are set forth in the section describing primers that follows.
First components, and primers discussed below, may further comprise light stabilizers and UV absorbers (UV stabilizers), fire retardants, and/or antioxidants. For example, Tinuvin light stabilizing products (e.g., Tinuvin 328 and/or Tinuvin 770DF) produced by BASF , and/or IRGANOX antioxidant products (e.g., phenolic or hindered phenolic antioxidants such as IRGANOX 1520 or IRGANOX 150L) produced by BASF may be included in the first component binder composition used to set down the base coat or in a primer.
Where light/UV
stabilizers, UV absorbers, fire retardants, and/or antioxidants are added to either or both of the first component or the primer, they are generally added in an amount less than 2% by weight (e.g., about 1%, 0.75%, 0.5%, 0.4%, 0.3%, 0.2% 0.1%, 0.075%, 0.06%, or 0.05%, or in a range selected from about 0.01% to about 2%, from about 0.05% to about 1.0%, or from about 0.75%
to about 0.5% by weight), and take the place of a corresponding weight of any solvents that may be present.
In addition to the ease of application, elastomer based coatings that do not contain a colorant or significant amounts of opaque particles are nearly transparent to visible light.
Typical light transmission (Total Luminous Transmittance or "TLT") of an elastomeric binder coating prepared using SBCs having 15 micron thickness is approximately 90%
(about 85% to about 92%) with a haze of about 61% (about 55% to about 65%). HP/OP coatings without added colorants that are about 25 microns thick prepared with clear first particles (e.g., EXPANCEL particles or other plastic or glass particles or hollow spheres) and fumed silica second particles treated with a silane (silanizing agent) can be nearly transparent. Such HP/OP
coatings typically have a TLT of about 80% (about 75% to about 85%) with a haze of about 90% (about 85% to about 90%) as measure by ASTM D1003-11. For the measurements the instrument was calibrated against air and glass sample blanks and given a TLT
of about 90% to about 91% and a haze of about 0.2%. Excluding or removing fine particulate materials such as talc used to increase the properties of commercially available elastomer compositions (e.g., flowability of bulk particulates) may increase TLT and haze values. Such fine particulates used in bulk elastomers may be removed by washing with a suitable solvent or by omitting the material from the elastomer compositions when they are prepared.
A variety of solvents may be employed to dissolve elastomeric binders for the preparation of coating compositions used to prepare the base coat of HP/OP
coatings described herein. In some embodiments, the copolymers are dissolved in solvents selected from: methyl ethyl ketone (MEK), ethyl acetate, toluene, 1-chloro-4-(trifluoromethyl)-benzene, xylene or mixed xylenes (including technical grade xylenes), isopropyl acetate, 1,1,1,-trichloroethane, methyl isobutyl ketone (MIBK), tertbutyl acetate (t-butyl acetate), cyclohexane, methyl-cyclohexane, or mixtures comprising any two, three, four or more thereof. In one embodiment the solvent(s) are selected from those found in the solubility chart shown in Figure 3, or mixtures of any two, three, four or more thereof. In another embodiment, the solvent comprises greater than 50%, 60%, 70%, 80%, 90%, 95%, 98% or 99% of a xylene (1,2-xylene, 1,3-xylene, or 1,4-xylene) or a mixture of any two or all three xylenes and optionally ethyl benzene (e.g., a technical grade of xylene comprising 34%-47% 1,3-xylene, 9%-21% 1,4-xylene, 4%-16% 1,2-xylene, 9%-10% ethylbenzene, 0%4% toluene, and 0%-1 % benzene).
In any of the foregoing embodiments, particularly where coatings are to be nearly transparent, the elastomeric binder components comprise at most insubstantial amounts (e.g., less than about 0.5% by weight of the polymers present in the binder) of colorants or particulates that are insoluble in solvents that dissolve the elastomeric polymers and/or that would block the transmission of visible light. One source of such particulates is materials added for the flowability of bulk polymers in the form of powders, pellets, or flakes (e.g., talc added to bulk SBCs).
3.0 Particles Employed in HP/OP Oleophobic Coatings:
3.1 First Particles Embodiments of the coatings disclosed herein may comprise particles that are added to the binder compositions to improve the mechanical properties of the coating, e.g., the durability of the HP/OP coatings. A wide variety of such particles, which are also known as extenders or fillers, may be added to the binders. Those particles are denoted herein as "first particles"
because the coatings described herein may have one or more additional types of particles. Such first particles that can be employed in the HP/OP coatings described herein include, but are not limited to, particles comprising: wood (e.g., wood dust), glass, metals (e.g., iron, titanium, nickel, zinc, tin), alloys of metals, metal oxides, metalloid oxides (e.g., silica), plastics (e.g., thermoplastics), carbides, nitrides, borides, spinels, diamonds, and fibers (e.g., glass fibers).
Numerous variables may be considered in the selection of first particles.
These variables include, but are not limited to, the effect the first particles have on the resulting coatings, their size, their hardness, their compatibility with the binder, the resistance of the first particles to the environment in which the coatings will be employed, and the environment the first particles must endure in the coating and/or curing process, including resistance to temperature and solvent conditions. In addition, if light is used for curing the coatings or they are intended for extended exposure to sunlight, the particles must be resistant to the required light exposure conditions (e.g., resistant to UV light employed in curing or sunlight).
In embodiments described herein, first particles have an average size in a range selected from about 1 micron (pm) to about 300 m or from about 30 m to about 225 m.
Within the broader ranges, embodiments include ranges of first particles having an average size of from about 1 pm to about 5 pm, from about 5 pm to about 10 pm, from about 10 pm to about 15 pm, from about 15 pm to about 20 pm, from about 20 pm to about 25 pm, from about 1 pm to about 25 pm, from about 5 pm to about 25 pm, from about 25 pm to about 50 pm, from about 50 pm to about 75 pm, from about 75 pm to about 100 pm, from about 100 pm to about 125 pm, from about 125 pm to about 150 pm, from about 150 pm to about 175 pm, from about 175 pm to about 200 pm, from about 200 pm to about 225 [tm, and from about 225 pm to about 250 pm.
Also included within this broad range are embodiments employing particles in ranges from about 10 m to about 100 m, from about 10 m to about 200 m, from about 20 m to about 200 m, from about 30 m to about 50 m, from about 30 m to about 100 m, from about 30 m to about 200 m, from about 30 m to about 225 m, from about 50 m to about 100 m, from about 50 m to about 200 m, from about 75 m to about 150 m, from about 75 m to about 200 m, from about 100 m to about 225 m, from about 100 m to about 250 m, from about 125 p.m to about 225 pm, from about 125 p.m to about 250 pm, from about 150 p.m to about 200 pm, from about 150 p.m to about 250 pm, from about 175 p.m to about 250 pm, from about 200 p.m to about 250 pm, from about 225 p.m to about 275 pm, or from about 250 p.m to about 300 p.m.
First particles may be incorporated into the elastomer binders at various ratios depending on the binder composition and the first particle's properties. In some embodiments, the first particles may have a content range selected from about 0.01% to about 60% or more by weight.
Included within this broad range are embodiments in which the first particles are present, by weight, in ranges from about 0.02% to about 0.2%, from about 0.05% to about 0.5%, from about 0.075% to about 0.75%, from about 0.1% to about 1%, from about 0.5% to about 2.5%, from about 2% to about 5%, from about 5% to about 10%, from about 10% to about 15%, from about 15% to about 20%, from about 20% to about 25%, from about 25% to about 30%, from about 30% to about 35%, from about 35% to about 40%, from about 40% to about 45%, from about 45% to about 50%, from about 50% to about 55%, from about 55% to about 60%, and greater than 60%. Also included within this broad range are embodiments in which the first particles are present, by weight, in ranges from about 4% to about 30%, from about 5% to about 25%, from about 5% to about 35%, from about 10% to about 25%, from about 10% to about 30%, from about 10% to about 40%, from about 10% to about 45%, from about 15% to about 25%, from about 15% to about 35%, from about 15% to about 45%, from about 20% to about 30%, from about 20% to about 35%, from about 20% to about 40%, from about 20% to about 45%, from about 20% to about 55%, from about 25% to about 40%, from about 25% to about 45%, from about 25% to about 55%, from about 30% to about 40%, from about 30% to about 45%, from about 30% to about 55%, from about 30% to about 60%, from about 35% to about 45%, from about 35% to about 50%, from about 35% to about 60%, from about 40% to about 60%, from about 0.01% to about 5%, from about 0.03% to about 1%, from about 0.05%
to about 0.15%, from about 0.1% to about 2.5%, from about 0.2% to about 5%, from about 0.05% to about 10%, from about 0.1% to about 10%, from about 0.05% to about 15%, or from about 0.05% to about 20%, on a weight basis.
In those embodiments where it is desirable to have coatings that are transparent, substantially transparent, or colored but transparent, it is generally desirable to employ particles that are transparent. In one set of embodiments, plastic (e.g., thermoplastic) microspheres are employed in the binder systems to develop surface texture. In another set of embodiments, glass microspheres are employed in the binder systems to develop surface texture.
In one embodiment, substantially spherical thermoplastic particles are added to the elastomeric binder composition to develop surface texture (e.g., EXPANCEL
microspheres or EXPANCEL particles). Such microspheres consist of a polymer shell encapsulating a gas. The average diameter of these hollow spheres typically ranges from 6 to 45 i.tm and have a density of 1000 to 1300 kg/m3 (8.3-10.8 lbs/US Gallon). Upon heating, the microspheres expand and the volume of the microspheres can increase more than 40 times (with the diameter changing, for example, from 10 to 40 i.tm), resulting in a density below 30 kg/m3 (0.25 lbs/US Gallon).
Typical expansion temperatures range from 80 to 190 C (176-374 F). When heating the microspheres the pressure of the gas inside the shell increases and the thermoplastic shell softens, resulting in a dramatic increase of the volume of the microspheres.
Cooling the microspheres results in the shell stiffening again and produces lighter (lower density) expanded microspheres. Some thermoplastic microspheres produced under the EXPANCEL
brand (AkzoNobel, distributed by Eka Chemicals, Inc., 2240 Northmont Parkway, Duluth, GA 30096, USA) are suitable for use in preparing HP/OP, particularly those that are substantially transparent. See Table 4.
Table 4 EXPANCEL particles and properties Main types Varieties Description Solid con-Density of tent riej EXPANCEL
Unexpended EXPANCEL WU :Wdatnexpanded:tbitmi:
mic rospheres spneres EXPANCEL WUF Wet, unexpended micro- 60-30 1000-1300 spheres EXPANCEL DU DiV, unexpanueu spheres EXPANCEL OUT Dry, treated. unexpended rni- >99 -1000 crospheres EXPANCEL SL Wet, satted. unexpended *ttlk crospheres EXPANCEL SW Wet, unexpended micro- 44 1200 spheres EXPANCELMB expended micro- 65 spheres mixed :vith a ntatrix, iEXPANCEL) e d. EVA
Expanded mi- EXPANCEL WE 'net, expanded rncrospheres 15 30 crospheres EXPANCEL DE Dry. expander,' microspheres >99 25-70 EXPANCEL DET Dry treated, expanded micro- >99 25 spheres Where HP/OP coatings capable of withstanding higher temperatures are desired, and particularly coatings that are substantially transparent, glass microspheres may be employed in place of thermoplastic microspheres. Such glass microspheres include those produced by 3MTm (St. Paul, MN) or Sphere One, Inc. (Chattanooga, TN).
3.1.1 Exemplary Sources of First Particles First particles may be prepared from the diverse materials described above.
Alternatively, first particles may be purchased from a variety of suppliers.
Some commercially available first particles that may be employed in the formation of the HP/OP
coatings described herein include those in Table 5.
Table 5 First Particles First First Particle First Particle First (g/cc) Particle Color Crush Source part- (Filler) Type Particle Size Strength Location icle ID Details Range (psi) No. (pm) 1 K1 Glass Bubbles GPSa 0.125 30-120 White 250 3mTm 2 K15 Glass Bubbles GPSa 0.15 30-115 White 300 3mTm 3 S15 Glass Bubbles GPSa 0.15 25-95 White 300 3mTm 4 S22 Glass Bubbles GPSa 0.22 20-75 White 400 3mTm 5 K20 Glass Bubbles GPSa 0.2 20-125 White 500 3mTm 6 K25 Glass Bubbles GPSa 0.25 25-105 White 750 3mTm 7 S32 Glass Bubbles GPSa 0.32 20-80 White 2000 3mTm 8 S35 Glass Bubbles GPSa 0.35 10-85 White 3000 3mTm 9 K37 Glass Bubbles GPSa 0.37 20-85 White 3000 3mTm S38 Glass Bubbles GPSa 0.38 15-85 White 4000 3mTm
11 S38HS Glass Bubbles GPSa 0.38 15-85 White 5500 3mTm
12 K46 Glass Bubbles GPSa 0.46 15-80 White 6000 3mTm
13 S60 Glass Bubbles GPSa 0.6 15-65 White 10000 3mTm
14 S60/HS Glass Bubbles GPSa 0.6 11-60 White 18000 3mTm A16/ Glass Bubbles Floated 0.16 35-135 White 500 3mTm 500 Series 16 A20/ Glass Bubbles Floated 0.2 30-120 White 1000 3mTm 1000 Series 17 H20/ Glass Bubbles Floated 0.2 25-110 White 1000 3mTm 1000 Series First First Particle First Particle First (g/cc) Particle Color Crush Source part- (Filler) Type Particle Size Strength Location icle ID Details Range (psi) No. (pm) 18 D32/ Glass Bubbles Floated 0.32 20-85 White 4500 3mTm 4500 Series j 19 Expancel 551 Plastic Micro Dry 0.042 30-50 AkzoNobel DE -spheres Expanded 0.004 i 40 d42 20 Expancel 551 Plastic Micro Dry 0.042 30-50 AkzoNobel DE 40 d42 2 -spheres Expanded 0.002 i 21 Expancel 461 Plastic Micro Dry 0.07
15-25 AkzoNobel DE 20 d70 -spheres Expanded 0.006 i 22 Expancel 461 Plastic Micro Dry 0.06 20-40 AkzoNobel DE 40 d60 -spheres Expanded 0.005 i 23 Expancel 461 Plastic Micro Dry 0.025 35-55 AkzoNobel DET 40 d25 -spheres Expanded 0.003 i 24 Expancel 461 Plastic Micro Dry 0.025 60-90 AkzoNobel DET 80 d25 -spheres Expanded 0.003 i 25 Expancel 920 Plastic Micro Dry 0.030 35-55 AkzoNobel DE 40 d30 -spheres Expanded 0.003 i 26 Expancel 920 Plastic Micro Dry 0.025 35-55 AkzoNobel DET 40 d25 -spheres Expanded 0.003 i 27 Expancel 920 Plastic Micro Dry 0.030 55-85 AkzoNobel DE 80 d30 -spheres Expanded 0.003 i 28 H50/ 10000 Glass Bubbles Floated 0.5 20-60 White 10000 3mTm EPX Series j 29 iMK Glass Bubbles Floated 0.6 8.6-26.7 White 28000 3mTm Series j 30 G-3125 Z-Light CMb 0.7 50-125 Gray 2000 3mTm SpheresTM j 31 G-3150 Z-Light CMb 0.7 55-145 Gray 2000 3mTm SpheresTM j 32 G-3500 Z-Light CMb 0.7 55-220 Gray 2000 3mTm SpheresTM j 33 G-600 Zeeo- CMb 2.3 1-40 Gray >60000 3MTm spheresTM j 34 G-800 Zeeo- CMb 2.2 2-200 Gray >60000 3MTm spheresTM j 35 G-850 Zeeo- CMb 2.1 12-200 Gray >60000 3MTm spheresTM j 36 W-610 Zeeo- CMb 2.4 1-40 White >60000 3MTm spheresTM j 37 SG Extendo- HS' 0.72 30-140 Gray 2500 Sphere One sphereTM f 38 DSG Extendo- HS' 0.72 30-140 Gray 2500 Sphere One sphereTM f 39 SGT Extendo- HS' 0.72 30-160 Gray 2500 Sphere One sphereTM f 40 TG Extendo- HS' 0.72 8-75 Gray 2500 Sphere One sphereTM f 41 SLG Extendo- HS' 0.7 10-149 Off 3000 Sphere One sphereTM White f First First Particle First Particle First (g/cc) Particle Color Crush Source part- (Filler) Type Particle Size Strength Location icle ID Details Range (psi) No. (pm) 42 SLT Extendo- HS' 0.4 10-90 Off 3000 Sphere One sphereTM White f 43 SL-150 Extendo- HS' 0.62 70 Cream 3000 Sphere One sphereTM f 44 SLW-150 Extendo- HS' 0.68 8-80 White 3000 Sphere One sphereTM f 45 HAT Extendo- HS' 0.68 10-165 Gray 2500 Sphere One sphereTM f 46 HT-150 Extendo- HS' 0.68 8-85 Gray 3000 Sphere One sphereTM f 47 KLS-90 Extendo- HS' 0.56 4-05 Light 1200 Sphere One sphereTM Gray f 48 KLS-125 Extendo- HS' 0.56 4-55 Light 1200 Sphere One sphereTM Gray f 49 KLS-150 Extendo- HS' 0.56 4-55 Light 1200 Sphere One sphereTM Gray f 50 KLS-300 Extendo- HS' 0.56 4-55 Light 1200 Sphere One sphereTM Gray f 51 HA-300 Extendo- HS' 0.68 10-146 Gray 2500 Sphere One sphereTM f 52 XIOM 512 Thermo- MPRd 0.96 10-100 White 508 XIOM
plastic Corp.
k 53 XIOM 512 Thermo- MPRd 0.96 10-100 Black 508 XIOM
plastic Corp.
k 54 CORVELTm Nylon 1.09 44-74 ROHM &
Black 78-7001 Thermo- Powder Black HASS
plastic Coating g 55 Micro-glass Fibers MMEGFe 1.05 16X120 White Fibertec 3082 h 56 Micro-glass Fibers MMEGFe 0.53 10X150 White Fibertec 9007D Silane- h Treated 57 Tiger Drylac Polyester Tiger Series 49 crosslinked Drylac with TGIC USA, Inc.
(triglycidyl /
isocyanurate) 58 Soft- Rubber based 90, 180, or Van-SoftPoint Sand 300 ous Indust.
colors Copley, OH
a ¨GPS - general purpose series g ¨ Philadelphia, PA
b ¨ ceramic microspheres h ¨ Bridgewater, MA
c ¨ hollow spheres i ¨ Distributed by Eka Chem., Inc., Duluth, GA
d ¨ modified polyethylene resins j ¨ St. Paul, MN
e ¨ microglass milled E-glass filaments k ¨ West Babylon, NY
f¨ Chattanooga, TN 1¨ St. Charles, IL
3.2 Second Particles The coatings disclosed herein employ second particles (e.g., nanoparticles), which are particles that bear, or are associated with, hydrophobic and/or oleophobic compounds or moieties (i.e., moieties that are covalently or non-covalently bound). The hydrophobic moieties can be introduced by treating the particles to include moieties such as siloxanes, fluorinated hydrocarbons (e.g., partly or fully fluorinated hydrocarbons) or nonfluorinated hydrocarbons. In an embodiment, second particles suitable for the preparation of elastomer-based HP/OP coatings have a size from about 1 nanometer (nm) to about 25 p.m and are capable of binding covalently to one or more chemical moieties (groups or components) that provide the second particles, and the coatings into which they are incorporated, hydrophobicity, and when selected to include fluoroalkyl groups, hydrophobicity and oleophobicity.
In one embodiment the second particles have a surface area over 100, 150, 200, 250, or 300 square meters per gram (m2/g) of particulate. In another embodiment, where the particles are fumed silica, the surface area can be about or greater than 150, 175, 200, 225 or 250 m2/g.
Second particles having a wide variety of compositions may be employed in the durable HP/OP coatings described and employed herein. In some embodiments the second particles will be particles comprising metal oxides (e.g., aluminum oxides such as alumina, zinc oxides, nickel oxides, zirconium oxides, iron oxides, or titanium dioxides), or oxides of metalloids (e.g., metalloid oxides such as oxides of B, Si, Sb, Te and Ge) such as glass, silica (e.g., fumed silica), silicates, aluminosilicates, or particles comprising combinations thereof.
In some embodiments, the second particles may have an average size in a range selected from about 1 nm up to about 25 p.m or more. Included within this broad range are embodiments in which the second particles have an average size in a range selected from:
about 1 nm to about 10 nm, from about 10 nm to about 25 nm, from about 25 nm to about 50 nm, from about 50 nm to about 100 nm, from about 100 nm to about 250 nm, from about 250 nm to about 500 nm, from about 500 nm to about 750 nm, from about 750 nm to about 1 pm, from about 1 p.m to about 5 pm, from about 5 p.m to about 10 pm, from about 10 p.m to about 15 pm, from about 15 p.m to about 20 pm, from about 20 p.m to about 25 pm, from about 1 nm to about 100 nm, from about 2 nm to about 200 nm, from about 10 nm to about 200 nm, from about 20 nm to about 400 nm, from about 10 nm to about 500 nm; from about 40 nm to about 800 nm, from about 100 nm to about 1 pm, from about 200 nm to about 1.5 pm, from about 500 nm to about 2 pm, from about 500 nm to about 2.5 pm, from about 1 p.m to about 10 pm, from about 2 p.m to about 20 pm, from about 2.5 p.m to about 25 pm, from about 500 nm to about 25 lam, from about 400 nm to about 20 pm, from about 100 nm to about 15 lam, from about 1 nm to about 50 nm, from about 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nm to about 120 nm, from about 5 nm to about 100 nm, from about 5 nm to about 200 nm; from about 5 nm to about 400 nm; from about 10 nm to about 300 nm; or from about 20 nm to about 400 nm.
In the above-mentioned embodiments, the lower size of second particles may be limited to particles greater than about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, or about 60 nm; and the upper size of second particles may be limited to particles less than about 20 lam, about 10 lam, about 5 lam, about 1 lam, about 0.8 lam, about 0.6 lam, about 0.5 lam, about 0.4 lam, about 0.3 lam, about 0.2 lam, or about 100 nm.
Any combination of particle size, particle composition, surface area, and/or percent composition in the coatings recited herein may be employed in preparing elastomer-based HP/OP coatings. Limitations on the upper and lower size of second particles may be used alone or in combination with any of the above-recited size limits on particle composition, surface area, percent composition in the coatings, and the like.
In some embodiments, the coatings may contain first particles in any of the above-mentioned ranges subject to either the proviso that the coatings do not contain only particles (e.g., first or second particles) with a size of 25 lam or less, or the proviso that the coatings do not contain more than an insubstantial amount of second particles with a size of 25 lam or less (recognizing that separation processes for particles greater than 25 lam may ultimately provide an unintended, insubstantial amount of particles that are 25 lam or less). An insubstantial amount of particles is less than 3% by weight or number of those particles, but it can also be less than 0.5%, 1%, or 2% wherever recited.
In other embodiments, second particles have an average size greater than 30 lam and less than 250 lam, and coatings comprising those particles do not contain more than insubstantial amounts of particles (e.g., first and second particles) with a size of 30 lam or less. In yet other embodiments, the coatings do not contain only particles (e.g., first and second particles) with a size of 40 lam or less, or particles with a size of 40 lam or less in substantial amounts. In addition, in still other embodiments, the coatings do not contain only particles (e.g., first and second particles) with a size of 50 lam or less, or particles with a size of 50 lam or less in substantial amounts.
In other embodiments, such as where the second particles are prepared by fuming (e.g., fumed silica or fumed zinc oxide), the second particles may have an average size in a range selected from about 1 nm to about 50 nm, from about 1 nm to about 100 nm, from about 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nm to about 120 nm, from about 5 nm to about 100 nm, from about 5 nm to about 200 nm, from about 25 nm to about 100 nm, from about 30 nm to about 200 nm, from about 5 nm to about 400 nm, from about 10 nm to about 300 nm, from about 20 nm to about 400 nm, or from about 50 nm to about 400 nm.
As indicated above, second particles are treated to introduce one or more moieties (e.g., groups or components) that impart HP/OP properties to the particles, either prior to incorporation into the compositions that will be used to apply coatings or after incorporation into the coatings. In some embodiments, the second particles are treated with a silanizing agent, a silane, a siloxane or a silazane, to introduce hydrophobic/superhydrophobic and/or oleophobic/superoleophobic properties to the particles (in addition to any such properties already possessed by the particles).
In one embodiment, second particles are silica, silicates, alumina (e.g., A1203), titanium oxide, or zinc oxide that are treated with one or more silanizing agents, e.g., compounds of formula (I) (below). In other embodiments, second particles are comprised of silica, silicates, alumina (e.g., A1203), titanium oxide, or zinc oxide that are treated with a siloxane. In another embodiment, the second particles are silica, silicates, glass, alumina (e.g., A1203), titanium oxide, or zinc oxide, treated with a silanizing agent, a siloxane or a silazane. In another embodiment, the second particles may be a fumed metal or metalloid (e.g., particles of fumed silica or fumed zinc oxide).
In embodiments where a silanizing agent is employed, the silanizing agent may be a compound of the formula (I):
R4_nSi-Xn (I) where n is an integer from 1 to 3;
each R is independently selected from (i) alkyl or cycloalkyl group optionally substituted with one or more fluorine atoms, (ii) C1 to 20 alkyl optionally substituted with one or more substituents independently selected from fluorine atoms and C60 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, Ci to 10 haloalkyl, Ci to 10 alkoxy, or Ci to 10 haloalkoxy substituents, (iii) C2 to 8 or C6 to 20 alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, C1 to 10 haloalkyl, C1 to 10 alkoxy, or C1 to 10 haloalkoxy substituents, (iv) C60 14 aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents, (V) C4 to 20 alkenyl or C4 to 20 alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy, and (vi) ¨Z-((CF2)q(CF3))r, wherein Z is a C1 to 12 or a C2 to 8 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4;
each X is independently selected from -H, -Cl, -I, -Br, -OH, -0R2, -NHR3, or -N(R3)2 group;
each R2 is an independently selected C1 to 4 alkyl or haloalkyl group; and each R3 is an independently selected H, C1 to 4 alkyl, or haloalkyl group.
In some embodiments, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms.
In other embodiments, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms.
In other embodiments, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms.
In other embodiments, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms and n is 3.
In other embodiments, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms and n is 3.
In other embodiments, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms and n is 3.
In other embodiments, R has the form ¨Z-((CF2)q(CF3)),, wherein Z is a C1 to 12 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4.
In any of the previously mentioned embodiments of compounds of formula (I), the value of n may be varied such that 1, 2 or 3 independently selected terminal functionalities are present.
Thus, in some embodiments, n is 3. In other embodiments, n is 2. In still other embodiments, n is 1.
In any of the previously mentioned embodiments of compounds of formula (I), all halogen atoms present in any one or more R groups may be fluorine.
In any of the previously mentioned embodiments of compounds of formula (I), X
may be independently selected from H, Cl, -0R2, -NHR3, -N(R3)2, or combinations thereof. In other embodiments, X may be selected from Cl, -0R2, -NHR3, -N(R3)2, or combinations thereof. In still other embodiments, X may be selected from -Cl, -NHR3, -N(R3)2 or combinations thereof.
Any coating described herein may be prepared with one, two, three, four or more compounds of formula (I) employed alone or in combination to modify the nano-particles, and/or other components of the coating including filler-particles. The use of silanizing agents of formula (I) to modify nano-particles, or any of the other components of the coatings, will introduce one or more R3_11X11Si- groups (e.g., R3Si-, R2X1Si-, or RX2Si-groups) where R and X
are as defined for a compound of formula (I). The value of n is 0, 1, or 2, due to the displacement of at least one "X" substituent and formation of at least one bond between a nano-particle and the Si atom (the bond between the nano-particle and the silicon atom is indicated by a dash "-" (e.g., R35i- R2X1Si-, or RX2Si- groups).
In other embodiments, suitable silanizing agents for modifying the nano-particles used in the coating compositions generally comprise those with fluorinated or polyfluorinated alkyl groups (e.g., fluoroalkyl groups) or alkyl groups (hydrocarbon containing groups) including, but not limited to:
(tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0);
(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0);
(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0);
(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0);
(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane (51H5 840.5);
(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane (51H5 841.7);
n-octadecyltrimethoxysilane (SI06645.0); n-octyltriethoxysilane (SI06715.0);
and 3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)silane (51N6597 .4) where the designations given in parentheses are the product numbers from Gelest, Inc., Morrisville, PA..
Another group of reagents that can be employed to prepare first or second particles with hydrophobic and/or oleophobic properties include (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane;
(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane;
nonafluorohexyldimethylchlorosilane;
(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane;
3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)-silane:
nonafluorohexylmethyldichlorosilane;
nonafluorohexyltrichlorosilane;
nonafluorohexyltriethoxysilane; and nonafluorohexyltrimethoxysilane.
In one embodiment, the coating compositions set forth herein comprise silica second particles treated with non afl uorohexyi trichiorosilane.
In addition to the silanizing agents recited above, a variety of other silanizing agents can be used to alter the properties of second particles and to provide hydrophobic and/or oleophobic properties. In some embodiments, second particles may be treated with an agent selected from dimethyldichlorosilane, hexamethyldisilazane, octyltrimethoxysilane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane. In such embodiments, the second particles may be silica. Silica second particles treated with such agents may have an average size in a range selected from about 1 nm to about 50 nm, from about 1 nm to about 100 nm, from about 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nm to about 120 nm, from about 5 nm to about 150 nm, from about 5 nm to about 400 nm, from about 10 nm to about 300 nm, from about 20 nm to about 400 nm, or from about 50 nm to about 250 nm.
Other agents can be used to modify second particles, including, but not limited to, one or more of: polydimethylsiloxane, gamma-aminopropyltriethoxysilane, Dynasylan A
(tetraethylorthosilicate), hexamethyldisilazane, and Dynasylan F 8263 (fluoroalkylsilane), any one or more of which may be used alone or in combination with the silanizing agents recited herein.
Two attributes of silanizing agents that may be considered for the purposes of their reaction with second particles and the introduction of hydrophobic or oleophobic moieties are the leaving group (e.g., X groups of compounds of the formula (I)) and the terminal functionality (e.g., R groups of compounds of the formula (I)). A silanizing agent's leaving group(s) can determine the reactivity of the agent with the first or second particle(s), or other components of the coating, if applied after a coating has been applied. Where the first or second particles are a silicate or silica (e.g., fumed silica) the leaving group can be displaced to form Si-0-Si bonds. Leaving group effectiveness is ranked in the decreasing order as chloro > methoxy > hydro (H) > ethoxy (measured as trichloro > trimethoxy > trihydro >
triethoxy). This ranking of the leaving groups is consistent with their bond dissociation energy. The terminal functionality determines the level of hydrophobicity that results from application of the silane to the surface.
3.2.1 Some Sources of Second Particles Second particles such as those comprising fumed silica may be purchased from a variety of suppliers including, but not limited to, Cabot Corp., Billerica, MA (e.g., Nanogel TLD201, CAB-0-SIL TS-720 (silica, pretreated with polydimethylsiloxane), and M5 (untreated silica)) and Evonik Industries, Essen, Germany (e.g., ACEMATT silica such as untreated HK400, AEROXIDE silica, AEROXIDE TiO2 titanium dioxide, and AEROXIDE Alu alumina).
Some commercially available second particles are set forth in Table 6 along with their surface treatment by a silanizing agent or polydimethyl siloxane.
Table 6 Some commercially available second particles Nominal BET
Product Surface Level of Surface Area Particle Product Name Treatment Treatment of Base Size (nm) Source Product (m2/g) M-5 None None 200 --- Cab-O-Sil Aerosil0 None None 200 12 Evonik Aerosil0 None None 255 --- Evonik Aerosil0 None None 300 7 Evonik Aerosil0 None None 380 7 Evonik HP-60 None None 200 --- Cab-O-Sil PTG None None 200 --- Cab-O-Sil H-5 None None 300 --- Cab-O-Sil HS-5 None None 325 --- Cab-O-Sil EH-5 None None 385 --- Cab-O-Sil TS-610 Dimethyldichlorosila Intermediate 130 --- Cab-O-Sil ne TS-530 Hexamethyldisilazane High 320 --- Cab-O-Sil TS-382 Octyltrimethoxysilan High 200 --- Cab-O-Sil e TS-720 Polydimethylsiloxane High 200 --- Cab-O-Sil Aerosil0 Polydimethylsiloxane --- 100 14 Evonik Aerosil0 Hexamethyldisilazane --- 125-175 --- Evonik R504 (HMDS) and aminosilane Aerosil0 HMDS based on --- 220 --- Evonik R812S Aerosil0 300 BET Surface Area is Brunauer, Emmett and Teller surface area HexamOthyldisilazane Dimethyldichlorosilane I hi .--si si i CI "-I I
Polyclimethylsiloxane ,Octyitrimethoxysilane dAi--D( ¨0 µ
I
I iI C ssõ, r b¨
n As purchased, the particles may be untreated (e.g., M5 silica) and may not possess any HP/OP properties. Such untreated particles can be treated to covalently attach one or more groups or moieties to the particles that give them HP/OP properties, for example, by treatment with the silanizing agents discussed above.
3.2.2 Dispersants for Second Particles Second particles can be applied to a base coating of elastomeric binder after it has been applied to the surface of an object (or a part thereof) in the form of a second component having a composition comprising one or more independently selected second particles as described above (e.g., second particles having a size of about 1 nanometer (nm) to about 25 microns ([tm) wherein said particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles; wherein said second component optionally comprises one or more solvents (liquid dispersants).
If the elastomeric coating has not dried, or has been subjected to a solvent that dissolves at least the outermost portion of the binder (e.g., renders it sufficiently tacky), second particles may be applied directly to the elastomeric binder by contacting the second particles with the binder. Second particles may be contacted with the surface by any suitable means, including spraying them on the surface using a stream of gas (e.g., air, nitrogen, or an inert gas), exposing the binder coating to particles suspended in a gas, or contacting the base coat of elastomeric binder with a fluidized bed of second particles.
Second particles can also be applied to a base coating of elastomeric binder in a second coating component that, in addition to the second particles, contains a solvent (dispersant) that dissolves, expands or swells the outermost portion of the binder sufficiently (e.g., renders it tacky) to permit the second particles to become bound in at least the outermost portion of the binder base coat. Where second components of the coating composition comprise a solvent, the second particles are dispersed in the solvent for application. Second particles, and particularly smaller second particles (e.g., 1-50 nm or 1-100 nm), may form aggregates in solvents used as dispersants.
Suitable solvents include those with a surface energy lower than water including, but not limited to: alcohols, ketones, acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene, xylene, isopropyl acetate, 1,1,1,-trichloroethane, methyl isobutyl ketone (MIBK), tertbutyl acetate (t-butyl acetate), cyclohexane, methyl-cyclohexane, or mixtures comprising any two, three, four or more thereof. In an embodiment, the solvents are non-aqueous (e.g., they contain less than 10%, 5%, 4%, 3%, 2%, 1%, or 0.5 % of water by weight or they contain only insubstantial amounts of water). Solvents that are miscible with water are employed in the second coating component in another embodiment. In another embodiment, the solvent comprises a non-aqueous water miscible solvent. In one embodiment, the solvent employed in the second coating component is acetone or is comprised of acetone. In another embodiment the solvent employed in the second coating component is NMP (N-methylpyrrolidone) or is comprised of NMP. In other embodiments, the solvent employed in the second coating composition comprises a mixture of acetone or NMP with water, particularly a minor proportion of water (e.g., less than about 5%, less than about 4%, less than about 2%, less than about 1%, or less than about 0.5% water).
In one embodiment, the second component of the coating composition (i.e., the top coat) comprises:
i) one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles; and ii) optionally, one or more independently selected solvents, wherein when said one or more solvents are present, said second particles may be present in a weight percent range selected from (0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) based on the weight of the one or more solvents and second particles.
In another embodiment, the second component of the coating composition (i.e., the top coat) comprises:
(i) 0.1 to 3.5 parts by weight (e.g., 0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) of second particles that comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with the second particles;
(ii) a fluorinated polyolefin, (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV); and/or a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer; and (iii) a solvent for a the remainder of a total of 100 parts by weight.
In another embodiment, the fluorinated polyolefin (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV), if present, comprises from 0.1 to 1.0 parts by weight (e.g., 0.1-0.5, 0.5-1.0, or 0.3 -0.7 parts) of the composition.
In another embodiment, the Fluoroethylene-Alkyl Vinyl Ether (e.g., the constituent polymer found in Lumiflon TM), if present, comprises 0.06 to 0.6 parts by weight (e.g., 0.06-0Ø1, 0.1-0.2, 0.2 -0.4, or 0.4-0.6 parts ) of the composition. In such an embodiment the FEVE
may have an average molecular weight of about 1,000 to 3,000 (e.g., about 1,000 - 2,000, 2,000 -3,000, 1,500- 2,500, or about 1,000, about 1,500, about 2,000, about 2,500, or about 3,000 Dalton). Accordingly, one embodiment of the second component comprises per 100 parts by weight:
i) 0.1 to 3.5 parts by weight (e.g., 0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) of one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with said second particles;
ii) 0.1 to 1.0 parts by weight (e.g., 0.1-0.5, 0.5-1.0, or 0.3 -0.7 parts) of a fluorinated polyolefin, (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV); and/or 0.06 to 0.6 parts by weight (e.g., 0.06-0Ø1, 0.1-0.2, 0.2 -0.4, or 0.4-0.6 parts) of a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, having an average molecular weight of about 1,000 to 3,000 (e.g., about 1,000 - 2,000, 2,000 -3,000, 1,500-2,500, or about 1,000, 1,500, 2,000, 2,500, or 3,000 Da);
and (iii) one or more solvent for a the remainder of a total of 100 parts by weight.
Where the solvent employed in second coating compositions dissolves or renders at least the outermost layer of the elastomeric binder "tacky," second particles can be introduced into completely dried and cured base coats of elastomeric binder. That permits the repair of worn or abraded coatings that have lost HP/OP behavior over all or part of their surface.
4.0 Surface Preparation and Priming To improve the adherence and performance of the coatings described herein the surface to be coated, in whole or in part, should be clean, free of contaminants and capable of supporting the coatings (e.g., not friable).
Performance of the coatings in terms of their durability can be significantly improved by the application of a primer. Any primer compatible with both the surface of the object and the elastomeric coating can be employed.
A variety of primer compositions may be employed. In one embodiment the primers comprise one or more polymers that are elastic (i.e., have viscoelasticity), such as those that comprise the binder used in the first component of the coating compositions described herein (e.g., SBCs). In one embodiment, the primer comprises one or more polymers that are elastic (i.e., have viscoelasticity, e.g., SBCs) and a tackifier. In one embodiment, the primer is a Plasti Dip Tm metal primer f938 hp.
In one embodiment, when a tackifier is employed, it may be selected from resins (e.g.
rosins and their derivates; terpenes and modified terpenes; aliphatic, cycloaliphatic and aromatic resins (C5 aliphatic resins, C9 aromatic resins, and C5/C9 aliphatic/aromatic resins);
hydrogenated hydrocarbon resins (e.g., RegalrezTM 1094, Eastman Chemical Co., Kingsport TN), and mixtures thereof and/or terpene-phenol resins). In one embodiment the tackifier is an ester of hydrogenated rosin (e.g., FORALTM 105-E ester of hydrogenated rosin).
In other embodiments the primer is an elastomeric primer comprising triblock copolymers of styrene and ethylene/butylene and an ester of a hydrogenated thermoplastic rosin (e.g., FORALTM 105-E, Eastman Chemical). The polystyrene content of the triblock copolymers will typically be from about 8% to about 14%, from about 12% to about 20%, from about 18% to about 28%, from about 22% to about 32%, from about 26% to about 36%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about
plastic Corp.
k 53 XIOM 512 Thermo- MPRd 0.96 10-100 Black 508 XIOM
plastic Corp.
k 54 CORVELTm Nylon 1.09 44-74 ROHM &
Black 78-7001 Thermo- Powder Black HASS
plastic Coating g 55 Micro-glass Fibers MMEGFe 1.05 16X120 White Fibertec 3082 h 56 Micro-glass Fibers MMEGFe 0.53 10X150 White Fibertec 9007D Silane- h Treated 57 Tiger Drylac Polyester Tiger Series 49 crosslinked Drylac with TGIC USA, Inc.
(triglycidyl /
isocyanurate) 58 Soft- Rubber based 90, 180, or Van-SoftPoint Sand 300 ous Indust.
colors Copley, OH
a ¨GPS - general purpose series g ¨ Philadelphia, PA
b ¨ ceramic microspheres h ¨ Bridgewater, MA
c ¨ hollow spheres i ¨ Distributed by Eka Chem., Inc., Duluth, GA
d ¨ modified polyethylene resins j ¨ St. Paul, MN
e ¨ microglass milled E-glass filaments k ¨ West Babylon, NY
f¨ Chattanooga, TN 1¨ St. Charles, IL
3.2 Second Particles The coatings disclosed herein employ second particles (e.g., nanoparticles), which are particles that bear, or are associated with, hydrophobic and/or oleophobic compounds or moieties (i.e., moieties that are covalently or non-covalently bound). The hydrophobic moieties can be introduced by treating the particles to include moieties such as siloxanes, fluorinated hydrocarbons (e.g., partly or fully fluorinated hydrocarbons) or nonfluorinated hydrocarbons. In an embodiment, second particles suitable for the preparation of elastomer-based HP/OP coatings have a size from about 1 nanometer (nm) to about 25 p.m and are capable of binding covalently to one or more chemical moieties (groups or components) that provide the second particles, and the coatings into which they are incorporated, hydrophobicity, and when selected to include fluoroalkyl groups, hydrophobicity and oleophobicity.
In one embodiment the second particles have a surface area over 100, 150, 200, 250, or 300 square meters per gram (m2/g) of particulate. In another embodiment, where the particles are fumed silica, the surface area can be about or greater than 150, 175, 200, 225 or 250 m2/g.
Second particles having a wide variety of compositions may be employed in the durable HP/OP coatings described and employed herein. In some embodiments the second particles will be particles comprising metal oxides (e.g., aluminum oxides such as alumina, zinc oxides, nickel oxides, zirconium oxides, iron oxides, or titanium dioxides), or oxides of metalloids (e.g., metalloid oxides such as oxides of B, Si, Sb, Te and Ge) such as glass, silica (e.g., fumed silica), silicates, aluminosilicates, or particles comprising combinations thereof.
In some embodiments, the second particles may have an average size in a range selected from about 1 nm up to about 25 p.m or more. Included within this broad range are embodiments in which the second particles have an average size in a range selected from:
about 1 nm to about 10 nm, from about 10 nm to about 25 nm, from about 25 nm to about 50 nm, from about 50 nm to about 100 nm, from about 100 nm to about 250 nm, from about 250 nm to about 500 nm, from about 500 nm to about 750 nm, from about 750 nm to about 1 pm, from about 1 p.m to about 5 pm, from about 5 p.m to about 10 pm, from about 10 p.m to about 15 pm, from about 15 p.m to about 20 pm, from about 20 p.m to about 25 pm, from about 1 nm to about 100 nm, from about 2 nm to about 200 nm, from about 10 nm to about 200 nm, from about 20 nm to about 400 nm, from about 10 nm to about 500 nm; from about 40 nm to about 800 nm, from about 100 nm to about 1 pm, from about 200 nm to about 1.5 pm, from about 500 nm to about 2 pm, from about 500 nm to about 2.5 pm, from about 1 p.m to about 10 pm, from about 2 p.m to about 20 pm, from about 2.5 p.m to about 25 pm, from about 500 nm to about 25 lam, from about 400 nm to about 20 pm, from about 100 nm to about 15 lam, from about 1 nm to about 50 nm, from about 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nm to about 120 nm, from about 5 nm to about 100 nm, from about 5 nm to about 200 nm; from about 5 nm to about 400 nm; from about 10 nm to about 300 nm; or from about 20 nm to about 400 nm.
In the above-mentioned embodiments, the lower size of second particles may be limited to particles greater than about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, or about 60 nm; and the upper size of second particles may be limited to particles less than about 20 lam, about 10 lam, about 5 lam, about 1 lam, about 0.8 lam, about 0.6 lam, about 0.5 lam, about 0.4 lam, about 0.3 lam, about 0.2 lam, or about 100 nm.
Any combination of particle size, particle composition, surface area, and/or percent composition in the coatings recited herein may be employed in preparing elastomer-based HP/OP coatings. Limitations on the upper and lower size of second particles may be used alone or in combination with any of the above-recited size limits on particle composition, surface area, percent composition in the coatings, and the like.
In some embodiments, the coatings may contain first particles in any of the above-mentioned ranges subject to either the proviso that the coatings do not contain only particles (e.g., first or second particles) with a size of 25 lam or less, or the proviso that the coatings do not contain more than an insubstantial amount of second particles with a size of 25 lam or less (recognizing that separation processes for particles greater than 25 lam may ultimately provide an unintended, insubstantial amount of particles that are 25 lam or less). An insubstantial amount of particles is less than 3% by weight or number of those particles, but it can also be less than 0.5%, 1%, or 2% wherever recited.
In other embodiments, second particles have an average size greater than 30 lam and less than 250 lam, and coatings comprising those particles do not contain more than insubstantial amounts of particles (e.g., first and second particles) with a size of 30 lam or less. In yet other embodiments, the coatings do not contain only particles (e.g., first and second particles) with a size of 40 lam or less, or particles with a size of 40 lam or less in substantial amounts. In addition, in still other embodiments, the coatings do not contain only particles (e.g., first and second particles) with a size of 50 lam or less, or particles with a size of 50 lam or less in substantial amounts.
In other embodiments, such as where the second particles are prepared by fuming (e.g., fumed silica or fumed zinc oxide), the second particles may have an average size in a range selected from about 1 nm to about 50 nm, from about 1 nm to about 100 nm, from about 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nm to about 120 nm, from about 5 nm to about 100 nm, from about 5 nm to about 200 nm, from about 25 nm to about 100 nm, from about 30 nm to about 200 nm, from about 5 nm to about 400 nm, from about 10 nm to about 300 nm, from about 20 nm to about 400 nm, or from about 50 nm to about 400 nm.
As indicated above, second particles are treated to introduce one or more moieties (e.g., groups or components) that impart HP/OP properties to the particles, either prior to incorporation into the compositions that will be used to apply coatings or after incorporation into the coatings. In some embodiments, the second particles are treated with a silanizing agent, a silane, a siloxane or a silazane, to introduce hydrophobic/superhydrophobic and/or oleophobic/superoleophobic properties to the particles (in addition to any such properties already possessed by the particles).
In one embodiment, second particles are silica, silicates, alumina (e.g., A1203), titanium oxide, or zinc oxide that are treated with one or more silanizing agents, e.g., compounds of formula (I) (below). In other embodiments, second particles are comprised of silica, silicates, alumina (e.g., A1203), titanium oxide, or zinc oxide that are treated with a siloxane. In another embodiment, the second particles are silica, silicates, glass, alumina (e.g., A1203), titanium oxide, or zinc oxide, treated with a silanizing agent, a siloxane or a silazane. In another embodiment, the second particles may be a fumed metal or metalloid (e.g., particles of fumed silica or fumed zinc oxide).
In embodiments where a silanizing agent is employed, the silanizing agent may be a compound of the formula (I):
R4_nSi-Xn (I) where n is an integer from 1 to 3;
each R is independently selected from (i) alkyl or cycloalkyl group optionally substituted with one or more fluorine atoms, (ii) C1 to 20 alkyl optionally substituted with one or more substituents independently selected from fluorine atoms and C60 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, Ci to 10 haloalkyl, Ci to 10 alkoxy, or Ci to 10 haloalkoxy substituents, (iii) C2 to 8 or C6 to 20 alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, C1 to 10 haloalkyl, C1 to 10 alkoxy, or C1 to 10 haloalkoxy substituents, (iv) C60 14 aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents, (V) C4 to 20 alkenyl or C4 to 20 alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy, and (vi) ¨Z-((CF2)q(CF3))r, wherein Z is a C1 to 12 or a C2 to 8 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4;
each X is independently selected from -H, -Cl, -I, -Br, -OH, -0R2, -NHR3, or -N(R3)2 group;
each R2 is an independently selected C1 to 4 alkyl or haloalkyl group; and each R3 is an independently selected H, C1 to 4 alkyl, or haloalkyl group.
In some embodiments, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms.
In other embodiments, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms.
In other embodiments, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms.
In other embodiments, R is an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms and n is 3.
In other embodiments, R is an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms and n is 3.
In other embodiments, R is an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms and n is 3.
In other embodiments, R has the form ¨Z-((CF2)q(CF3)),, wherein Z is a C1 to 12 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4.
In any of the previously mentioned embodiments of compounds of formula (I), the value of n may be varied such that 1, 2 or 3 independently selected terminal functionalities are present.
Thus, in some embodiments, n is 3. In other embodiments, n is 2. In still other embodiments, n is 1.
In any of the previously mentioned embodiments of compounds of formula (I), all halogen atoms present in any one or more R groups may be fluorine.
In any of the previously mentioned embodiments of compounds of formula (I), X
may be independently selected from H, Cl, -0R2, -NHR3, -N(R3)2, or combinations thereof. In other embodiments, X may be selected from Cl, -0R2, -NHR3, -N(R3)2, or combinations thereof. In still other embodiments, X may be selected from -Cl, -NHR3, -N(R3)2 or combinations thereof.
Any coating described herein may be prepared with one, two, three, four or more compounds of formula (I) employed alone or in combination to modify the nano-particles, and/or other components of the coating including filler-particles. The use of silanizing agents of formula (I) to modify nano-particles, or any of the other components of the coatings, will introduce one or more R3_11X11Si- groups (e.g., R3Si-, R2X1Si-, or RX2Si-groups) where R and X
are as defined for a compound of formula (I). The value of n is 0, 1, or 2, due to the displacement of at least one "X" substituent and formation of at least one bond between a nano-particle and the Si atom (the bond between the nano-particle and the silicon atom is indicated by a dash "-" (e.g., R35i- R2X1Si-, or RX2Si- groups).
In other embodiments, suitable silanizing agents for modifying the nano-particles used in the coating compositions generally comprise those with fluorinated or polyfluorinated alkyl groups (e.g., fluoroalkyl groups) or alkyl groups (hydrocarbon containing groups) including, but not limited to:
(tridecafluoro-1,1,2,2-tetrahydrooctyl)silane (SIT8173.0);
(tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane (SIT8174.0);
(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (SIT8175.0);
(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane (SIT8176.0);
(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane (51H5 840.5);
(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane (51H5 841.7);
n-octadecyltrimethoxysilane (SI06645.0); n-octyltriethoxysilane (SI06715.0);
and 3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)silane (51N6597 .4) where the designations given in parentheses are the product numbers from Gelest, Inc., Morrisville, PA..
Another group of reagents that can be employed to prepare first or second particles with hydrophobic and/or oleophobic properties include (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane;
(tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane;
nonafluorohexyldimethylchlorosilane;
(tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane;
3,3,4,4,5,5,6,6,6-nonafluorohexyldimethyl(dimethylamino)-silane:
nonafluorohexylmethyldichlorosilane;
nonafluorohexyltrichlorosilane;
nonafluorohexyltriethoxysilane; and nonafluorohexyltrimethoxysilane.
In one embodiment, the coating compositions set forth herein comprise silica second particles treated with non afl uorohexyi trichiorosilane.
In addition to the silanizing agents recited above, a variety of other silanizing agents can be used to alter the properties of second particles and to provide hydrophobic and/or oleophobic properties. In some embodiments, second particles may be treated with an agent selected from dimethyldichlorosilane, hexamethyldisilazane, octyltrimethoxysilane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane. In such embodiments, the second particles may be silica. Silica second particles treated with such agents may have an average size in a range selected from about 1 nm to about 50 nm, from about 1 nm to about 100 nm, from about 1 nm to about 400 nm, from about 1 nm to about 500 nm, from about 2 nm to about 120 nm, from about 5 nm to about 150 nm, from about 5 nm to about 400 nm, from about 10 nm to about 300 nm, from about 20 nm to about 400 nm, or from about 50 nm to about 250 nm.
Other agents can be used to modify second particles, including, but not limited to, one or more of: polydimethylsiloxane, gamma-aminopropyltriethoxysilane, Dynasylan A
(tetraethylorthosilicate), hexamethyldisilazane, and Dynasylan F 8263 (fluoroalkylsilane), any one or more of which may be used alone or in combination with the silanizing agents recited herein.
Two attributes of silanizing agents that may be considered for the purposes of their reaction with second particles and the introduction of hydrophobic or oleophobic moieties are the leaving group (e.g., X groups of compounds of the formula (I)) and the terminal functionality (e.g., R groups of compounds of the formula (I)). A silanizing agent's leaving group(s) can determine the reactivity of the agent with the first or second particle(s), or other components of the coating, if applied after a coating has been applied. Where the first or second particles are a silicate or silica (e.g., fumed silica) the leaving group can be displaced to form Si-0-Si bonds. Leaving group effectiveness is ranked in the decreasing order as chloro > methoxy > hydro (H) > ethoxy (measured as trichloro > trimethoxy > trihydro >
triethoxy). This ranking of the leaving groups is consistent with their bond dissociation energy. The terminal functionality determines the level of hydrophobicity that results from application of the silane to the surface.
3.2.1 Some Sources of Second Particles Second particles such as those comprising fumed silica may be purchased from a variety of suppliers including, but not limited to, Cabot Corp., Billerica, MA (e.g., Nanogel TLD201, CAB-0-SIL TS-720 (silica, pretreated with polydimethylsiloxane), and M5 (untreated silica)) and Evonik Industries, Essen, Germany (e.g., ACEMATT silica such as untreated HK400, AEROXIDE silica, AEROXIDE TiO2 titanium dioxide, and AEROXIDE Alu alumina).
Some commercially available second particles are set forth in Table 6 along with their surface treatment by a silanizing agent or polydimethyl siloxane.
Table 6 Some commercially available second particles Nominal BET
Product Surface Level of Surface Area Particle Product Name Treatment Treatment of Base Size (nm) Source Product (m2/g) M-5 None None 200 --- Cab-O-Sil Aerosil0 None None 200 12 Evonik Aerosil0 None None 255 --- Evonik Aerosil0 None None 300 7 Evonik Aerosil0 None None 380 7 Evonik HP-60 None None 200 --- Cab-O-Sil PTG None None 200 --- Cab-O-Sil H-5 None None 300 --- Cab-O-Sil HS-5 None None 325 --- Cab-O-Sil EH-5 None None 385 --- Cab-O-Sil TS-610 Dimethyldichlorosila Intermediate 130 --- Cab-O-Sil ne TS-530 Hexamethyldisilazane High 320 --- Cab-O-Sil TS-382 Octyltrimethoxysilan High 200 --- Cab-O-Sil e TS-720 Polydimethylsiloxane High 200 --- Cab-O-Sil Aerosil0 Polydimethylsiloxane --- 100 14 Evonik Aerosil0 Hexamethyldisilazane --- 125-175 --- Evonik R504 (HMDS) and aminosilane Aerosil0 HMDS based on --- 220 --- Evonik R812S Aerosil0 300 BET Surface Area is Brunauer, Emmett and Teller surface area HexamOthyldisilazane Dimethyldichlorosilane I hi .--si si i CI "-I I
Polyclimethylsiloxane ,Octyitrimethoxysilane dAi--D( ¨0 µ
I
I iI C ssõ, r b¨
n As purchased, the particles may be untreated (e.g., M5 silica) and may not possess any HP/OP properties. Such untreated particles can be treated to covalently attach one or more groups or moieties to the particles that give them HP/OP properties, for example, by treatment with the silanizing agents discussed above.
3.2.2 Dispersants for Second Particles Second particles can be applied to a base coating of elastomeric binder after it has been applied to the surface of an object (or a part thereof) in the form of a second component having a composition comprising one or more independently selected second particles as described above (e.g., second particles having a size of about 1 nanometer (nm) to about 25 microns ([tm) wherein said particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles; wherein said second component optionally comprises one or more solvents (liquid dispersants).
If the elastomeric coating has not dried, or has been subjected to a solvent that dissolves at least the outermost portion of the binder (e.g., renders it sufficiently tacky), second particles may be applied directly to the elastomeric binder by contacting the second particles with the binder. Second particles may be contacted with the surface by any suitable means, including spraying them on the surface using a stream of gas (e.g., air, nitrogen, or an inert gas), exposing the binder coating to particles suspended in a gas, or contacting the base coat of elastomeric binder with a fluidized bed of second particles.
Second particles can also be applied to a base coating of elastomeric binder in a second coating component that, in addition to the second particles, contains a solvent (dispersant) that dissolves, expands or swells the outermost portion of the binder sufficiently (e.g., renders it tacky) to permit the second particles to become bound in at least the outermost portion of the binder base coat. Where second components of the coating composition comprise a solvent, the second particles are dispersed in the solvent for application. Second particles, and particularly smaller second particles (e.g., 1-50 nm or 1-100 nm), may form aggregates in solvents used as dispersants.
Suitable solvents include those with a surface energy lower than water including, but not limited to: alcohols, ketones, acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene, xylene, isopropyl acetate, 1,1,1,-trichloroethane, methyl isobutyl ketone (MIBK), tertbutyl acetate (t-butyl acetate), cyclohexane, methyl-cyclohexane, or mixtures comprising any two, three, four or more thereof. In an embodiment, the solvents are non-aqueous (e.g., they contain less than 10%, 5%, 4%, 3%, 2%, 1%, or 0.5 % of water by weight or they contain only insubstantial amounts of water). Solvents that are miscible with water are employed in the second coating component in another embodiment. In another embodiment, the solvent comprises a non-aqueous water miscible solvent. In one embodiment, the solvent employed in the second coating component is acetone or is comprised of acetone. In another embodiment the solvent employed in the second coating component is NMP (N-methylpyrrolidone) or is comprised of NMP. In other embodiments, the solvent employed in the second coating composition comprises a mixture of acetone or NMP with water, particularly a minor proportion of water (e.g., less than about 5%, less than about 4%, less than about 2%, less than about 1%, or less than about 0.5% water).
In one embodiment, the second component of the coating composition (i.e., the top coat) comprises:
i) one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles; and ii) optionally, one or more independently selected solvents, wherein when said one or more solvents are present, said second particles may be present in a weight percent range selected from (0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) based on the weight of the one or more solvents and second particles.
In another embodiment, the second component of the coating composition (i.e., the top coat) comprises:
(i) 0.1 to 3.5 parts by weight (e.g., 0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) of second particles that comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with the second particles;
(ii) a fluorinated polyolefin, (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV); and/or a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer; and (iii) a solvent for a the remainder of a total of 100 parts by weight.
In another embodiment, the fluorinated polyolefin (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV), if present, comprises from 0.1 to 1.0 parts by weight (e.g., 0.1-0.5, 0.5-1.0, or 0.3 -0.7 parts) of the composition.
In another embodiment, the Fluoroethylene-Alkyl Vinyl Ether (e.g., the constituent polymer found in Lumiflon TM), if present, comprises 0.06 to 0.6 parts by weight (e.g., 0.06-0Ø1, 0.1-0.2, 0.2 -0.4, or 0.4-0.6 parts ) of the composition. In such an embodiment the FEVE
may have an average molecular weight of about 1,000 to 3,000 (e.g., about 1,000 - 2,000, 2,000 -3,000, 1,500- 2,500, or about 1,000, about 1,500, about 2,000, about 2,500, or about 3,000 Dalton). Accordingly, one embodiment of the second component comprises per 100 parts by weight:
i) 0.1 to 3.5 parts by weight (e.g., 0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) of one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with said second particles;
ii) 0.1 to 1.0 parts by weight (e.g., 0.1-0.5, 0.5-1.0, or 0.3 -0.7 parts) of a fluorinated polyolefin, (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV); and/or 0.06 to 0.6 parts by weight (e.g., 0.06-0Ø1, 0.1-0.2, 0.2 -0.4, or 0.4-0.6 parts) of a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, having an average molecular weight of about 1,000 to 3,000 (e.g., about 1,000 - 2,000, 2,000 -3,000, 1,500-2,500, or about 1,000, 1,500, 2,000, 2,500, or 3,000 Da);
and (iii) one or more solvent for a the remainder of a total of 100 parts by weight.
Where the solvent employed in second coating compositions dissolves or renders at least the outermost layer of the elastomeric binder "tacky," second particles can be introduced into completely dried and cured base coats of elastomeric binder. That permits the repair of worn or abraded coatings that have lost HP/OP behavior over all or part of their surface.
4.0 Surface Preparation and Priming To improve the adherence and performance of the coatings described herein the surface to be coated, in whole or in part, should be clean, free of contaminants and capable of supporting the coatings (e.g., not friable).
Performance of the coatings in terms of their durability can be significantly improved by the application of a primer. Any primer compatible with both the surface of the object and the elastomeric coating can be employed.
A variety of primer compositions may be employed. In one embodiment the primers comprise one or more polymers that are elastic (i.e., have viscoelasticity), such as those that comprise the binder used in the first component of the coating compositions described herein (e.g., SBCs). In one embodiment, the primer comprises one or more polymers that are elastic (i.e., have viscoelasticity, e.g., SBCs) and a tackifier. In one embodiment, the primer is a Plasti Dip Tm metal primer f938 hp.
In one embodiment, when a tackifier is employed, it may be selected from resins (e.g.
rosins and their derivates; terpenes and modified terpenes; aliphatic, cycloaliphatic and aromatic resins (C5 aliphatic resins, C9 aromatic resins, and C5/C9 aliphatic/aromatic resins);
hydrogenated hydrocarbon resins (e.g., RegalrezTM 1094, Eastman Chemical Co., Kingsport TN), and mixtures thereof and/or terpene-phenol resins). In one embodiment the tackifier is an ester of hydrogenated rosin (e.g., FORALTM 105-E ester of hydrogenated rosin).
In other embodiments the primer is an elastomeric primer comprising triblock copolymers of styrene and ethylene/butylene and an ester of a hydrogenated thermoplastic rosin (e.g., FORALTM 105-E, Eastman Chemical). The polystyrene content of the triblock copolymers will typically be from about 8% to about 14%, from about 12% to about 20%, from about 18% to about 28%, from about 22% to about 32%, from about 26% to about 36%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about
16%, about 18%, about 19%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, or about 36%. Mixtures of any two or more, three or more, or four or more of such triblock copolymers may also be employed in the primer composition, and any one or more of such triblock copolymers may optionally comprise 1% to 3%, 1.4% to 2.0%, 1%
to 1.4%, 1.6% to 3%, or 2% to 3% bound maleic anhydride (maleated copolymers). Any of the foregoing triblock copolymers may be linear or branched (e.g., dendrimers or arborols).
In one embodiment wherein the elastomeric primer comprises triblock copolymers of styrene and ethylene/butylene and an ester of a hydrogenated thermoplastic rosin, the primer comprises two different maleated triblock copolymers of styrene and ethylene/butylene with a polystyrene: a first triblock copolymer of styrene and ethylene/butylene with a polystyrene having 0.4% to 1.6% (e.g., 0.5% to 1.5%, 0.6% to 1.4,% or 0.7% to 1.3%) substitution of maleic anhydride by weight of the first triblock copolymer (and optionally less than 0.3% free maleic anhydride); and a second triblock copolymer of styrene and ethylene/butylene with a polystyrene having 1.1% to 2.5% (e.g., 1.3 to 2.3 or 1.4 to 2.4%) substitution of maleic anhydride by weight of the second triblock copolymer. In such an embodiment the first and/or second triblock copolymers may be linear or branched copolymers(e.g., arborols or dendrimers) , and the second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1 (e.g., the first copolymer to second copolymer ratio is about 4:1 to about 5.5:1, about 5:1 to about 6:1, or about 5.5:1 to about 6.5:1). The ratio of the total triblock copolymer (first and second) to the ester of a hydrogenated thermoplastic rosin is typically 1:5 to 2.5:5 (triblock copolymers: ester(s) of hydrogenated thermoplastic rosin). Ratios for all three components include 7:1:25, 7.2:1.3:25, 7.6:1.6:25, and 8:1.8:25 (first triblock copolymer: second triblock copolymer:
ester of a hydrogenated thermoplastic rosin).
In any of the foregoing embodiments the primers may also comprise insubstantial amounts (e.g., less than about 2% by weight of the polymers present in the binder, such as less than 1.0%, 0.75%, 0.5%, 0.25%, or 0.1%) of colorants or particulates that are insoluble in the solvents that dissolve the elastomeric polymers and/or that would block the transmission of visible light in the dried cured coating (e.g., talc added for the flowability of particles of the polymers as produced).
In any of the foregoing embodiments the primers may also comprise first particles for texture development in the primer and/or the base coat (i.e., a base coat of elastomeric binder with or without first particles).
In another embodiment, when a tackifier is employed it may be a hydrocarbon resin. In one embodiment where hydrocarbon resins are employed, they may be selected from resins such as those prepared from petroleum based feedstocks (e.g., aliphatic (C5), aromatic (C9), DCPD
(dicyclopentadiene) resins, or mixtures of these).
Elastomeric primers not only promote bonding to substrate surfaces such as metals, but also provide for improved adhesion to the base coat. In addition, such primers compensate for differences in the coefficient of thermal expansion between the HP/OP coating and the substrate.
In other embodiments, primers comprise polyurethane polymers. Such polyurethane containing primers ("polyurethane primers") demonstrate excellent bonding to many substrates including metallic substrates. When employing a polyurethane primer, it is possible to incorporate first particles into the primer and/or the base coat (a base coat of elastomeric binder with or without first particles) for texture development. Thus, in addition to promoting adhesion, the primer can also serve to develop texture with increased surface area for improved adhesion of the base coat comprising an elastomeric binder, develop wear resistance, and develop hydrophobicity/oleophobicity. The HP/OP coatings applied over the elastomeric primers or two part polyurethane primers described herein display essentially equal resistance to the loss of hydrophobicity in Taber Abraser wear/abrasion resistance tests (as measured by Taber Abraser cycles) when abrasive (CS-10) and soft (CS-0) wheels are employed.
5.0 Coating Application Method:
The coatings described herein (including any underlying primer) can be applied to surfaces using any means known in the art including, but not limited to, brushing, painting, printing, stamping, rolling, dipping, spin-coating, spraying, or electrostatic spraying. In one embodiment, one or more of a primer, base coat and/or top coat are applied by spraying. In another embodiment, each of a primer (if present), base coat and top coat are applied by spraying.
In one embodiment the first and second coating compositions described herein are separately prepackaged in a delivery system/apparatus for spray applications, such as aerosol canisters (e.g., pre-pressurized aerosol cans). In such an embodiment, the first component and second component can be packaged in separate delivery systems/apparatus. A
propellant is added to the system/apparatus that serves to drive the components out of their canisters for delivery. Propellants will typically be a gas at 25 C and 1 atmosphere, but may be in a different phase (liquid) under pressure, such as in a pressurized aerosol delivery system. The propellant may be a gas (e.g., air or nitrogen) or a liquefiable gas having a vapor pressure sufficient to propel and aerosolize the first and/or second components as they exit their delivery system/apparatus). Some exemplary propellants include: liquefied petroleum gases, ethers (e.g., dimethyl ether (DME) and diethyl ether); C1-C4 saturated hydrocarbons (e.g., methane, ethane, propane, n-butane, and isobutene); hydrofluorocarbons (HFC) (e.g., 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3,-heptafluoropropane (HFC-227HFC), difluoromethane (HFC-32), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1-difluoroethane (HFC-152a)), and mixtures comprising any two, three or more of the foregoing.
In another embodiment, the propellant is a blend of n-butane and propane.
Generally, the surfaces will be rigid or semi-rigid, but the surfaces can also be flexible, for example in the instance of wires, tapes, rubberized materials, gaskets, and ribbons.
The coatings described herein can be applied to virtually any substrate to provide HP/OP
properties. The choice of coatings and coating processes that will be used may be affected by the compatibility of the substrate and its surface to the coating process and the component of the coating compositions. Among the considerations are the compatibility of the substrate and its surface with any solvents that may be employed in the application of the coatings and the ability of a desired coating to adhere to the substrate's surface.
Coatings may take any desired shape or form, limited only by the manner and patterns in which they can be applied. In some embodiments, the coating will completely cover a surface.
In other embodiments the coating will cover only a portion of a surface, such as one or more of a top, side or bottom of an object. In one embodiment, a coating is applied as a line or strip on a substantially flat or planar surface. In such an embodiment the line or strip may form a spill-resistant border.
The shape, dimensions and placement of HP/OP coatings on surfaces can be controlled by a variety of means including the use of masks, which can control not only the portions of a surface that will receive a coating, but also the portions of a surface that may receive prior treatments such as the application of a primer layer or cleaning by abrasion or solvents. For example, where sandblasting or a chemical treatment is used to prepare a portion of a surface for coating, a mask resistant to those treatments would be selected (e.g., a mask such as a rigid or flexible plastic, resin, or rubber/rubberized material). Masking may be attached to the surface through the use of adhesives, which may be applied to the mask agent, the surface, or both.
In another embodiment HP/OP coatings are applied to a ribbon, tape or sheet that may then be applied to a substrate by any suitable means including adhesive applied to the substrate, the ribbon or tape, or both. Ribbons, tapes and sheets bearing a superhydrophobic coating may be employed in a variety of applications, including forming spill proof barriers on surfaces.
Ribbons, tapes, and sheets are generally formed of a substantially flat (planar) flexible material where one side (the top) is made hydrophobic or superhydrophobic. This includes metal sheets, ribbons, and tapes such as aluminum tape or other tapes (e.g., metal adhesive tape, plastic adhesive tape, paper adhesive tape, fiberglass adhesive tape), wherein one side is coated with an HP/OP coating and adhesive is applied to the other side. Once such HP/OP
ribbons, tapes, and sheets are prepared, they can be applied to any type of surface including metal, ceramic, glass, plastic, or wood surfaces, for a variety of purposes.
In one embodiment, HP/OP coatings are applied to the surface of an object by a method comprising:
(a) applying a first component to all or part of the surface of an object;
followed by (b) applying a second component to all or the part of the surface of said object to which said first component was applied.
In another embodiment, HP/OP coatings are applied by a coating method comprising:
(a) applying a first component of a two-component coating composition to all or part of the surface of an object; followed by (b) applying a second component of the two-component coating composition to all or the part of the surface of said object to which said first component was applied.
In such an embodiment, the first component and second component may be applied using one or more methods selected independently from brushing, painting, printing, stamping, rolling, dipping, spin-coating, or spraying. Such a process is at least a two-step process, but may include additional steps, such as a second application of the second component making it a three or more step process.
In an embodiment, one or both of the first and second components are applied to a surface by spraying in a method comprising:
(a) spraying a first component of a two-component coating composition (e.g., an elastomeric binder and first particles) on all or part of the surface of an object; followed by (b) spraying a second component of said two-component coating composition (e.g., second particles and optionally a solvent) on all or part of the surface of an object to which said first component was applied. In one embodiment, the spraying may be conducted using first, second, or both components packaged in aerosol spray canisters.
In an embodiment of the above-described coating process, a base coat of elastomeric polymer binder and first particles (e.g., EXPANCEL particles) is applied as the first component.
Once the base coat loses sufficient solvent so that it: does not run when a second component is applied; is close to being dry to touch (e.g., is tacky); becomes dry to touch; or is dry, a second coating component (e.g., second particles and an optional dispersant such as acetone) is applied.
The solvent in the dispersant helps attach the functional second particles to the binder of the base coat. Other than allowing any solvent used as a dispersant to evaporate no additional curing cycle is needed.
The coating obtained is durable and delivers HP/OP behavior and can be applied to a variety of substrates including metals, ceramics, polymerics and fabrics and in a number of specific applications as set forth below.
6.0 Applications:
The elastomeric coating described herein may be employed in a variety of applications including, but not limited to, coatings for all or part of:
1) electronic equipment and their electronic components or subassemblies (e.g., circuit boards), including, but not limited to: cell phones, laptop computers, electronic tablets (e.g., iPads), cameras, video games, Global Positioning System (GPS) devices, radios, MP3 and electronic music players, watches, video equipment, security systems, satellite dishes and other portable electronics;
2) shoes (e.g., athletic shoes, casual shoes, dress shoes) and apparel for medical and recreational use;
3) toys such as toy vehicles (e.g., trucks, cars), bikes, scooters, playground equipment (e.g., swings, slides, teeter-totters), water toys, and toys for use in bathtubs;
4) cleaning products - toilet brushes, toilet plungers, mops, dust mops and cloths;
5) furniture and cooking preparation and serving surfaces including both indoor and outdoor furniture (e.g., lawn/patio furniture and park furniture such as tables, chairs and benches) or employed as spill resistant borders on surfaces that are substantially horizontal.
6) pet products (e.g., litter boxes, litter scoopers, drinking and food bowls, collars, litter particles, animal beds);
7) farm tools and home and garden tools including shovels, spades, and rakes;;
8) outdoor and exercise equipment (e.g., skis, snow boards), balls, in-line skates, roller skates);
9) appliances ¨ portions or entire refrigerator plates (e.g., spill proof borders), freezer liners, parts in washing machines, dishwashers, dehumidifiers, humidifiers, and dryers;
11) baby/toddler products (e.g., car seats, potty seats, bibs, silverware (made from plastics), cups, plates and diapers (or parts thereof);
12) food and beverage containers (e.g., bottles and containers for beverages, water, food);
13) sports equipment including balls (e.g., baseballs, tennis balls, footballs, soccer balls), gloves, backpacks, and tents;
14) bedding (sheets, mattresses, pillows, blankets);
15) food processing equipment and kitchen equipment including coatings and/or spill resistant borders for counters, backsplashes, the walls behind counters where food is prepared, and abattoirs (e.g., wall coatings and/or curtains used to section off a slaughter floor);
16) superhydrophobic body spray;
to 1.4%, 1.6% to 3%, or 2% to 3% bound maleic anhydride (maleated copolymers). Any of the foregoing triblock copolymers may be linear or branched (e.g., dendrimers or arborols).
In one embodiment wherein the elastomeric primer comprises triblock copolymers of styrene and ethylene/butylene and an ester of a hydrogenated thermoplastic rosin, the primer comprises two different maleated triblock copolymers of styrene and ethylene/butylene with a polystyrene: a first triblock copolymer of styrene and ethylene/butylene with a polystyrene having 0.4% to 1.6% (e.g., 0.5% to 1.5%, 0.6% to 1.4,% or 0.7% to 1.3%) substitution of maleic anhydride by weight of the first triblock copolymer (and optionally less than 0.3% free maleic anhydride); and a second triblock copolymer of styrene and ethylene/butylene with a polystyrene having 1.1% to 2.5% (e.g., 1.3 to 2.3 or 1.4 to 2.4%) substitution of maleic anhydride by weight of the second triblock copolymer. In such an embodiment the first and/or second triblock copolymers may be linear or branched copolymers(e.g., arborols or dendrimers) , and the second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1 (e.g., the first copolymer to second copolymer ratio is about 4:1 to about 5.5:1, about 5:1 to about 6:1, or about 5.5:1 to about 6.5:1). The ratio of the total triblock copolymer (first and second) to the ester of a hydrogenated thermoplastic rosin is typically 1:5 to 2.5:5 (triblock copolymers: ester(s) of hydrogenated thermoplastic rosin). Ratios for all three components include 7:1:25, 7.2:1.3:25, 7.6:1.6:25, and 8:1.8:25 (first triblock copolymer: second triblock copolymer:
ester of a hydrogenated thermoplastic rosin).
In any of the foregoing embodiments the primers may also comprise insubstantial amounts (e.g., less than about 2% by weight of the polymers present in the binder, such as less than 1.0%, 0.75%, 0.5%, 0.25%, or 0.1%) of colorants or particulates that are insoluble in the solvents that dissolve the elastomeric polymers and/or that would block the transmission of visible light in the dried cured coating (e.g., talc added for the flowability of particles of the polymers as produced).
In any of the foregoing embodiments the primers may also comprise first particles for texture development in the primer and/or the base coat (i.e., a base coat of elastomeric binder with or without first particles).
In another embodiment, when a tackifier is employed it may be a hydrocarbon resin. In one embodiment where hydrocarbon resins are employed, they may be selected from resins such as those prepared from petroleum based feedstocks (e.g., aliphatic (C5), aromatic (C9), DCPD
(dicyclopentadiene) resins, or mixtures of these).
Elastomeric primers not only promote bonding to substrate surfaces such as metals, but also provide for improved adhesion to the base coat. In addition, such primers compensate for differences in the coefficient of thermal expansion between the HP/OP coating and the substrate.
In other embodiments, primers comprise polyurethane polymers. Such polyurethane containing primers ("polyurethane primers") demonstrate excellent bonding to many substrates including metallic substrates. When employing a polyurethane primer, it is possible to incorporate first particles into the primer and/or the base coat (a base coat of elastomeric binder with or without first particles) for texture development. Thus, in addition to promoting adhesion, the primer can also serve to develop texture with increased surface area for improved adhesion of the base coat comprising an elastomeric binder, develop wear resistance, and develop hydrophobicity/oleophobicity. The HP/OP coatings applied over the elastomeric primers or two part polyurethane primers described herein display essentially equal resistance to the loss of hydrophobicity in Taber Abraser wear/abrasion resistance tests (as measured by Taber Abraser cycles) when abrasive (CS-10) and soft (CS-0) wheels are employed.
5.0 Coating Application Method:
The coatings described herein (including any underlying primer) can be applied to surfaces using any means known in the art including, but not limited to, brushing, painting, printing, stamping, rolling, dipping, spin-coating, spraying, or electrostatic spraying. In one embodiment, one or more of a primer, base coat and/or top coat are applied by spraying. In another embodiment, each of a primer (if present), base coat and top coat are applied by spraying.
In one embodiment the first and second coating compositions described herein are separately prepackaged in a delivery system/apparatus for spray applications, such as aerosol canisters (e.g., pre-pressurized aerosol cans). In such an embodiment, the first component and second component can be packaged in separate delivery systems/apparatus. A
propellant is added to the system/apparatus that serves to drive the components out of their canisters for delivery. Propellants will typically be a gas at 25 C and 1 atmosphere, but may be in a different phase (liquid) under pressure, such as in a pressurized aerosol delivery system. The propellant may be a gas (e.g., air or nitrogen) or a liquefiable gas having a vapor pressure sufficient to propel and aerosolize the first and/or second components as they exit their delivery system/apparatus). Some exemplary propellants include: liquefied petroleum gases, ethers (e.g., dimethyl ether (DME) and diethyl ether); C1-C4 saturated hydrocarbons (e.g., methane, ethane, propane, n-butane, and isobutene); hydrofluorocarbons (HFC) (e.g., 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3,-heptafluoropropane (HFC-227HFC), difluoromethane (HFC-32), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1-difluoroethane (HFC-152a)), and mixtures comprising any two, three or more of the foregoing.
In another embodiment, the propellant is a blend of n-butane and propane.
Generally, the surfaces will be rigid or semi-rigid, but the surfaces can also be flexible, for example in the instance of wires, tapes, rubberized materials, gaskets, and ribbons.
The coatings described herein can be applied to virtually any substrate to provide HP/OP
properties. The choice of coatings and coating processes that will be used may be affected by the compatibility of the substrate and its surface to the coating process and the component of the coating compositions. Among the considerations are the compatibility of the substrate and its surface with any solvents that may be employed in the application of the coatings and the ability of a desired coating to adhere to the substrate's surface.
Coatings may take any desired shape or form, limited only by the manner and patterns in which they can be applied. In some embodiments, the coating will completely cover a surface.
In other embodiments the coating will cover only a portion of a surface, such as one or more of a top, side or bottom of an object. In one embodiment, a coating is applied as a line or strip on a substantially flat or planar surface. In such an embodiment the line or strip may form a spill-resistant border.
The shape, dimensions and placement of HP/OP coatings on surfaces can be controlled by a variety of means including the use of masks, which can control not only the portions of a surface that will receive a coating, but also the portions of a surface that may receive prior treatments such as the application of a primer layer or cleaning by abrasion or solvents. For example, where sandblasting or a chemical treatment is used to prepare a portion of a surface for coating, a mask resistant to those treatments would be selected (e.g., a mask such as a rigid or flexible plastic, resin, or rubber/rubberized material). Masking may be attached to the surface through the use of adhesives, which may be applied to the mask agent, the surface, or both.
In another embodiment HP/OP coatings are applied to a ribbon, tape or sheet that may then be applied to a substrate by any suitable means including adhesive applied to the substrate, the ribbon or tape, or both. Ribbons, tapes and sheets bearing a superhydrophobic coating may be employed in a variety of applications, including forming spill proof barriers on surfaces.
Ribbons, tapes, and sheets are generally formed of a substantially flat (planar) flexible material where one side (the top) is made hydrophobic or superhydrophobic. This includes metal sheets, ribbons, and tapes such as aluminum tape or other tapes (e.g., metal adhesive tape, plastic adhesive tape, paper adhesive tape, fiberglass adhesive tape), wherein one side is coated with an HP/OP coating and adhesive is applied to the other side. Once such HP/OP
ribbons, tapes, and sheets are prepared, they can be applied to any type of surface including metal, ceramic, glass, plastic, or wood surfaces, for a variety of purposes.
In one embodiment, HP/OP coatings are applied to the surface of an object by a method comprising:
(a) applying a first component to all or part of the surface of an object;
followed by (b) applying a second component to all or the part of the surface of said object to which said first component was applied.
In another embodiment, HP/OP coatings are applied by a coating method comprising:
(a) applying a first component of a two-component coating composition to all or part of the surface of an object; followed by (b) applying a second component of the two-component coating composition to all or the part of the surface of said object to which said first component was applied.
In such an embodiment, the first component and second component may be applied using one or more methods selected independently from brushing, painting, printing, stamping, rolling, dipping, spin-coating, or spraying. Such a process is at least a two-step process, but may include additional steps, such as a second application of the second component making it a three or more step process.
In an embodiment, one or both of the first and second components are applied to a surface by spraying in a method comprising:
(a) spraying a first component of a two-component coating composition (e.g., an elastomeric binder and first particles) on all or part of the surface of an object; followed by (b) spraying a second component of said two-component coating composition (e.g., second particles and optionally a solvent) on all or part of the surface of an object to which said first component was applied. In one embodiment, the spraying may be conducted using first, second, or both components packaged in aerosol spray canisters.
In an embodiment of the above-described coating process, a base coat of elastomeric polymer binder and first particles (e.g., EXPANCEL particles) is applied as the first component.
Once the base coat loses sufficient solvent so that it: does not run when a second component is applied; is close to being dry to touch (e.g., is tacky); becomes dry to touch; or is dry, a second coating component (e.g., second particles and an optional dispersant such as acetone) is applied.
The solvent in the dispersant helps attach the functional second particles to the binder of the base coat. Other than allowing any solvent used as a dispersant to evaporate no additional curing cycle is needed.
The coating obtained is durable and delivers HP/OP behavior and can be applied to a variety of substrates including metals, ceramics, polymerics and fabrics and in a number of specific applications as set forth below.
6.0 Applications:
The elastomeric coating described herein may be employed in a variety of applications including, but not limited to, coatings for all or part of:
1) electronic equipment and their electronic components or subassemblies (e.g., circuit boards), including, but not limited to: cell phones, laptop computers, electronic tablets (e.g., iPads), cameras, video games, Global Positioning System (GPS) devices, radios, MP3 and electronic music players, watches, video equipment, security systems, satellite dishes and other portable electronics;
2) shoes (e.g., athletic shoes, casual shoes, dress shoes) and apparel for medical and recreational use;
3) toys such as toy vehicles (e.g., trucks, cars), bikes, scooters, playground equipment (e.g., swings, slides, teeter-totters), water toys, and toys for use in bathtubs;
4) cleaning products - toilet brushes, toilet plungers, mops, dust mops and cloths;
5) furniture and cooking preparation and serving surfaces including both indoor and outdoor furniture (e.g., lawn/patio furniture and park furniture such as tables, chairs and benches) or employed as spill resistant borders on surfaces that are substantially horizontal.
6) pet products (e.g., litter boxes, litter scoopers, drinking and food bowls, collars, litter particles, animal beds);
7) farm tools and home and garden tools including shovels, spades, and rakes;;
8) outdoor and exercise equipment (e.g., skis, snow boards), balls, in-line skates, roller skates);
9) appliances ¨ portions or entire refrigerator plates (e.g., spill proof borders), freezer liners, parts in washing machines, dishwashers, dehumidifiers, humidifiers, and dryers;
11) baby/toddler products (e.g., car seats, potty seats, bibs, silverware (made from plastics), cups, plates and diapers (or parts thereof);
12) food and beverage containers (e.g., bottles and containers for beverages, water, food);
13) sports equipment including balls (e.g., baseballs, tennis balls, footballs, soccer balls), gloves, backpacks, and tents;
14) bedding (sheets, mattresses, pillows, blankets);
15) food processing equipment and kitchen equipment including coatings and/or spill resistant borders for counters, backsplashes, the walls behind counters where food is prepared, and abattoirs (e.g., wall coatings and/or curtains used to section off a slaughter floor);
16) superhydrophobic body spray;
17) automotive parts (e.g., bumpers, internal plastic parts, engine parts, structural parts, fender well (wheel well) liners, and car seats, particularly for convertibles);
18) protective equipment (e.g., helmets, pads, and uniforms);
19) building products (e.g., rain spouts, doors, counters (polymer), flooring, ceilings, screens, and roofing);
20) laboratory equipment (e.g., trays, storage bins, tools, petri dishes, funnels, tubing and animal cages);
21) electrical equipment (e.g., electrical housings, electrical wiring, motors, switches, insulators, and circuit boards);
22) communications equipment (e.g., satellite dishes, antennas, and communications towers);
23) plastic and/or metal tubing and piping (e.g., PVC piping, copper piping, plastic and steel piping);
24) lavatory/bathroom equipment and fixtures (e.g., urinals, toilets, toilet seats, air and/or heat hand drying equipment, potty seat bowls, counters, sinks, and soap dispensers);
25) medical products including: beds and bed parts, bed pans, tubing, tubular products, catheters, stents, surgical tools and operating room equipment (such as robotic surgical tools), operating room equipment (e.g., tables, light fixtures), walls, floors, sinks, imaging equipment/machinery, laboratory testing equipment/machinery, and medical instruments (e.g., medical instruments used in surgical and nonsurgical applications);
26) wound care products, spray-on bandages, regular bandages, and body affecting products (e.g., skin and/or hair spray; and
27) aviation and boating equipment (e.g., airplane fuselage, wings and instrumentation), and boat bottoms, decks, and other places throughout a boat.
Use of the coating can be facilitated by providing the first and second components for preparing the coatings described herein in a form that permits facile application. In one embodiment the first and/or second components are prepackaged in solvent or propellant delivery systems such as aerosol canisters (e.g., aerosol cans).
7.0 COATING EVALUATION
Coatings prepared using the elastomeric binder first component and second coating composition described herein can be evaluated using one or more criteria including, but not limited to:
1. transparency and appearance, which are evaluated both quantitatively and qualitatively;
2. durability of the SH/OP behavior (wear resistance of the coating) to an applied force using:
2a. semi-quantitative glove rub test in which the thumb of a latex rubber gloved hand is stroked by hand over the surface of the coating that has been applied to a substantially planar surface until the coating no longer shows superhydrophobic behavior.
This test is a proxy for the ability of the surface to be handled and retain its HP/OP
properties. During the test, the area of the surface contacted with the rubber glove is approximately 25mm x 25mm and the force applied approximately 300 g (or about 0.5g/square mm). The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied (typically 20) to the tested surface to run (roll) off when the surface is inclined at 5 degrees from horizontal. Figure 4 shows an exemplary testing apparatus used to determine the end of SH/OP, 2b. loss of superhydrophobic behavior can also be judged after the surface is subject to the action of a cylindrical rubber finger moved across the surface. The finger is rubbed across the surface using a motorized American Association of Textile Chemists and Colorists (AATCC) CM-5 Crockmeter fitted with a 14/20 white rubber septum (outside diameter of 13 mm and inside diameter of 7 mm with a contact surface area of 94 mm2) to contact the coating with a force of 9N (Ace Glass, Inc., Vineland, NJ, Catalog No. 9096-244). The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied to the tested surface (typically 20 droplets) to run (roll) off when the surface is inclined at 5 degrees from horizontal, 2c. loss of superhydrophobic behavior when the samples are subject to Taber Abraser testing using CS-10 (abrasive) and/or CS-0 (non-abrasive) wheels at the indicated loads and speeds to determine the point at which the surfaces lose superhydrophobicity.
Unless indicated otherwise, a load of 1,000 g is employed. All Taber tests were conducted at a speed of 95 rpm unless stated otherwise. The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied to the tested surface (typically 20) to run (roll) off when the surface is inclined at 5 degrees from horizontal, 2d. time to the loss of superhydrophobicity under a shower of water. Water is applied from a showerhead placed 152.4 cm (60 inches) above a substantially planar test surface inclined at 5 degrees from the horizontal, the showerhead having 70 nozzles with a 1 mm diameter orifice arranged in 5 spokes of 5 nozzles and 15 spokes of 3 nozzles about a central point on the circular showerhead. The apparatus delivers a shower of 6 liters of water per minute using about 137900 to about 310275 Pa (about 20 to about 45psi) over an approximately circular area of about 150 cm in diameter at the level of the test surface.
The time to loss of superhydrophobic behavior is determined to be the period of time after which water droplets from the shower begin to "stick" to the surface (no longer freely run off the surface) of a sample placed in the shower;
3. coating thickness and/or surface roughness, expressed as the average roughness (Ra) unless stated otherwise. Surface roughness has been found to be an indicator that positively correlates with abrasion resistance (increasing abrasion resistance with increasing roughness);
4. the ability of coated surfaces to resist ice formation in dynamic testing and the adherence of ice to surfaces;
5. electrical properties including resistance and permittivity' 6. oleophobicity, using either the contact angle of light mineral oil with the coating or by assessing the interaction of droplets of various liquid hydrocarbons having different surface tensions employed in the ATCC 118-1997 Oil Repellancy test with the coating surface. For testing, a coating is applied to a 4x4 inch substantially planar plate. After the plate has dried and cured it is placed on a 5 1 degree slope relative to the horizontal and five droplets of a test hydrocarbon are applied beginning with KaydolTM (available from CBM Group of N.C.
inc., 1308 N. Ellis Ave., Dunn NC 28334). When droplets stick to the coating or wet the coating, the Score (Oil Repellency Grade Number) is assigned. Thus, KaydolTM
droplets rolling off earns a value of 1 or greater, 65:35 KaydolTM: n-hexadecane droplets rolling off earns a value of 2 or greater, and so on. All test are conducted at room temperature.
Score (Oil Repellency hydrocarbon Grade Number) 0 None (Fails KaydolTM) 1 KaydolTM (mineral oil) 2 65:35 KaydolTM: n-hexadecane 3 n-hexadecane 4 n-tetradecane 6 IF dodecane 6 n-decane 7 n-octane 8 n-heptane The oleophobicity of first or second particles (e.g., fumed silica treated with a silane, silazane, silanol, siloxane, fluorinated versions thereof, etc.) can be tested in the same manner.
In such tests the first and/or second particles are applied to a clean 4x4 inch aluminum plate by spraying a suspension containing 2% particles 98% acetone by weight to form a coating of particles that cover the aluminum plate. . After the plate has dried, the above-listed hydrocarbon liquids are tested on the particle coatings in the same manner as they would be on an elastomeric coating, and the particles scored in the same manner.
8.0 CERTAIN EMBODIMENTS
Embodiment 1, has is divided into two sub-embodiments, that are recited below as embodiments 1.1. and 1.2. In embodiment 1.1 the second component comprises second particles and one or more solvents, but does not require a fluoropolymer. In contrast, the second component of sub-embodiment 1.2 requires not only second particles, but also a fluorinated polyolefin and/or a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, and one or more solvents. In subsequent embodiments, any reference to embodiment 1 refers to either embodiment 1.1 and/or 1.2.
Embodiment 1.1 A combination of components for forming a coating comprising:
A) a first component which comprises:
i) an elastomeric binder comprising one or more styrenic block copolymers, wherein said elastomeric binder comprises from about 1% to about 30% of said one or more styrenic block copolymers by weight (e.g., about 1% to about 5%, about 5% to about 10%, about 10% to about 15%, about 15% to about 25%, or about 25% to about 30%
of said one or more styrenic block copolymers);
ii) optionally, one or more independently selected first particles having a size of about 30 microns to about 225 microns, wherein, when said first particles are present, the first component comprises from about 0.01% to about 5% of said first particles by weight (e.g., about 0.01% to about 5%, about 0.03% to about 1%, about 0.05% to about 0.15%, about 0.1% to about 2.5%, or about 0.2% to about 5% of said first particles by weight); and iii) one or more independently selected solvents; and B) a second component which comprises:
i) one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles; and ii) optionally, one or more independently selected solvents, wherein when said one or more solvents are present, said second particles may be present in a weight percent range selected from (0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) based on the weight of the one or more solvents and second particles.
Embodiment 1.2. A combination of components for forming a coating comprising:
A) a first component which comprises:
i) an elastomeric binder comprising one or more styrenic block copolymers, wherein said elastomeric binder comprises from about 1% to about 30% of said one or more styrenic block copolymers by weight (e.g., about 1% to about 5%, about 5% to about 10%, about 10% to about 15%, about 15% to about 25%, or about 25% to about 30% of said one or more styrenic block copolymers);
ii) optionally, one or more independently selected first particles having a size of about microns to about 225 microns, wherein, when said first particles are present, the 30 first component comprises from about 0.01% to about 5% of said first particles by weight (e.g., about 0.01% to about 5%, about 0.03% to about 1%, about 0.05% to about 0.15%, about 0.1% to about 2.5%, or about 0.2% to about 5% of said first particles by weight); and iii) one or more independently selected solvents; and B) a second component which comprises per 100 parts by weight:
i) 0.1 to 3.5 parts by weight (e.g., 0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) of one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with said second particles;
ii) 0.1 to 1.0 parts by weight (e.g., 0.1-0.5, 0.5-1.0, or 0.3 -0.7 parts) of a fluorinated polyolefin, (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV);
and/or 0.06 to 0.6 parts by weight (e.g., 0.06-0Ø1, 0.1-0.2, 0.2 -0.4, or 0.4-0.6 parts ) of a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, having an average molecular weight of about 1,000 to 3,000 (e.g., about 1,000 - 2,000, 2,000 -3,000, 1,500- 2,500, or about 1,000, 1,500, 2,000, 2,500, or 3,000 Da);
and iii) one or more independently selected solvents for a the remainder of a total of 100 parts by weight.
2. The combination of embodiment 1, wherein one or more of the styrenic block copolymers has a rubber phase crosslinked to the polystyrene phase.
3. The combination according to any of embodiments 1 to 2, wherein one or more of the styrenic block copolymers has a rubber phase comprising polybutadiene, polyisoprene, polyolefin or a mixture of any of those rubber phase components (e.g., linear triblock copolymers of styrene and ethylene/butylene with a polystyrene content of about 8% to about 36% by weight (e.g., about 8% to about 12%, about 12% to about 18%, about 18% to about 24%, about 24% to about 30%, about 30% to about 36%, about 10% to about 20%, or about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 17%, about 19%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, about 36%) or mixtures of any two or more, three or more, or four or more of such triblock copolymers, any one or more of which may optionally comprise 1% to 3% or 1.4% to 2.0 % maleic anhydride).
4. The combination according to any of embodiments 2 to 3, wherein said rubber component comprises 60%-98%, 60%-70%, 70%-80%, 60%-90%, 80%-90%, 83%-93%, 85%-95%, or 89%-98%, of the elastomer by weight (based on the dry weight of the elastomer present in the first component not including any contribution by the first particles or other materials present in that component).
5. The combination according to any of embodiments 1 to 4, wherein said first component further comprises one or more colorants, UV stabilizers, antioxidants, rheological agents, and/or fillers.
6. The combination according to any of embodiments 1 to 5, wherein said first component further comprises up to 30% by weight of one or more tackifiers (e.g., 1%-5%, 2%-8%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, or 25%-30%).
7. The combination of embodiment 6, wherein said one or more styrenic block copolymers and said one or more tackifiers together comprise up to about 30% by weight of said first component (e.g., up to about 10, 15, 20, 25, or 30%).
8. The combination according to any of embodiments 1 to 7, wherein said elastomeric binder comprises one, two, three, or more triblock copolymers.
9. The combination according to any of embodiments 1 to 8, wherein said elastomeric binder comprises one or more styrenic block copolymers of styrene and ethylene/butylene with a polystyrene content of about 8% to about 36% by weight (e.g., about 8% to about 14%, about 12% to about 20%, about 18% to about 28%, about 22% to about 32%, about 26% to about 36%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 16%, about 18%, about 19%, about 20%, about 22%, about 24%, about 26%, about
Use of the coating can be facilitated by providing the first and second components for preparing the coatings described herein in a form that permits facile application. In one embodiment the first and/or second components are prepackaged in solvent or propellant delivery systems such as aerosol canisters (e.g., aerosol cans).
7.0 COATING EVALUATION
Coatings prepared using the elastomeric binder first component and second coating composition described herein can be evaluated using one or more criteria including, but not limited to:
1. transparency and appearance, which are evaluated both quantitatively and qualitatively;
2. durability of the SH/OP behavior (wear resistance of the coating) to an applied force using:
2a. semi-quantitative glove rub test in which the thumb of a latex rubber gloved hand is stroked by hand over the surface of the coating that has been applied to a substantially planar surface until the coating no longer shows superhydrophobic behavior.
This test is a proxy for the ability of the surface to be handled and retain its HP/OP
properties. During the test, the area of the surface contacted with the rubber glove is approximately 25mm x 25mm and the force applied approximately 300 g (or about 0.5g/square mm). The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied (typically 20) to the tested surface to run (roll) off when the surface is inclined at 5 degrees from horizontal. Figure 4 shows an exemplary testing apparatus used to determine the end of SH/OP, 2b. loss of superhydrophobic behavior can also be judged after the surface is subject to the action of a cylindrical rubber finger moved across the surface. The finger is rubbed across the surface using a motorized American Association of Textile Chemists and Colorists (AATCC) CM-5 Crockmeter fitted with a 14/20 white rubber septum (outside diameter of 13 mm and inside diameter of 7 mm with a contact surface area of 94 mm2) to contact the coating with a force of 9N (Ace Glass, Inc., Vineland, NJ, Catalog No. 9096-244). The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied to the tested surface (typically 20 droplets) to run (roll) off when the surface is inclined at 5 degrees from horizontal, 2c. loss of superhydrophobic behavior when the samples are subject to Taber Abraser testing using CS-10 (abrasive) and/or CS-0 (non-abrasive) wheels at the indicated loads and speeds to determine the point at which the surfaces lose superhydrophobicity.
Unless indicated otherwise, a load of 1,000 g is employed. All Taber tests were conducted at a speed of 95 rpm unless stated otherwise. The end of superhydrophobic behavior is judged by the failure of more than half of the water droplets applied to the tested surface (typically 20) to run (roll) off when the surface is inclined at 5 degrees from horizontal, 2d. time to the loss of superhydrophobicity under a shower of water. Water is applied from a showerhead placed 152.4 cm (60 inches) above a substantially planar test surface inclined at 5 degrees from the horizontal, the showerhead having 70 nozzles with a 1 mm diameter orifice arranged in 5 spokes of 5 nozzles and 15 spokes of 3 nozzles about a central point on the circular showerhead. The apparatus delivers a shower of 6 liters of water per minute using about 137900 to about 310275 Pa (about 20 to about 45psi) over an approximately circular area of about 150 cm in diameter at the level of the test surface.
The time to loss of superhydrophobic behavior is determined to be the period of time after which water droplets from the shower begin to "stick" to the surface (no longer freely run off the surface) of a sample placed in the shower;
3. coating thickness and/or surface roughness, expressed as the average roughness (Ra) unless stated otherwise. Surface roughness has been found to be an indicator that positively correlates with abrasion resistance (increasing abrasion resistance with increasing roughness);
4. the ability of coated surfaces to resist ice formation in dynamic testing and the adherence of ice to surfaces;
5. electrical properties including resistance and permittivity' 6. oleophobicity, using either the contact angle of light mineral oil with the coating or by assessing the interaction of droplets of various liquid hydrocarbons having different surface tensions employed in the ATCC 118-1997 Oil Repellancy test with the coating surface. For testing, a coating is applied to a 4x4 inch substantially planar plate. After the plate has dried and cured it is placed on a 5 1 degree slope relative to the horizontal and five droplets of a test hydrocarbon are applied beginning with KaydolTM (available from CBM Group of N.C.
inc., 1308 N. Ellis Ave., Dunn NC 28334). When droplets stick to the coating or wet the coating, the Score (Oil Repellency Grade Number) is assigned. Thus, KaydolTM
droplets rolling off earns a value of 1 or greater, 65:35 KaydolTM: n-hexadecane droplets rolling off earns a value of 2 or greater, and so on. All test are conducted at room temperature.
Score (Oil Repellency hydrocarbon Grade Number) 0 None (Fails KaydolTM) 1 KaydolTM (mineral oil) 2 65:35 KaydolTM: n-hexadecane 3 n-hexadecane 4 n-tetradecane 6 IF dodecane 6 n-decane 7 n-octane 8 n-heptane The oleophobicity of first or second particles (e.g., fumed silica treated with a silane, silazane, silanol, siloxane, fluorinated versions thereof, etc.) can be tested in the same manner.
In such tests the first and/or second particles are applied to a clean 4x4 inch aluminum plate by spraying a suspension containing 2% particles 98% acetone by weight to form a coating of particles that cover the aluminum plate. . After the plate has dried, the above-listed hydrocarbon liquids are tested on the particle coatings in the same manner as they would be on an elastomeric coating, and the particles scored in the same manner.
8.0 CERTAIN EMBODIMENTS
Embodiment 1, has is divided into two sub-embodiments, that are recited below as embodiments 1.1. and 1.2. In embodiment 1.1 the second component comprises second particles and one or more solvents, but does not require a fluoropolymer. In contrast, the second component of sub-embodiment 1.2 requires not only second particles, but also a fluorinated polyolefin and/or a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, and one or more solvents. In subsequent embodiments, any reference to embodiment 1 refers to either embodiment 1.1 and/or 1.2.
Embodiment 1.1 A combination of components for forming a coating comprising:
A) a first component which comprises:
i) an elastomeric binder comprising one or more styrenic block copolymers, wherein said elastomeric binder comprises from about 1% to about 30% of said one or more styrenic block copolymers by weight (e.g., about 1% to about 5%, about 5% to about 10%, about 10% to about 15%, about 15% to about 25%, or about 25% to about 30%
of said one or more styrenic block copolymers);
ii) optionally, one or more independently selected first particles having a size of about 30 microns to about 225 microns, wherein, when said first particles are present, the first component comprises from about 0.01% to about 5% of said first particles by weight (e.g., about 0.01% to about 5%, about 0.03% to about 1%, about 0.05% to about 0.15%, about 0.1% to about 2.5%, or about 0.2% to about 5% of said first particles by weight); and iii) one or more independently selected solvents; and B) a second component which comprises:
i) one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles; and ii) optionally, one or more independently selected solvents, wherein when said one or more solvents are present, said second particles may be present in a weight percent range selected from (0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) based on the weight of the one or more solvents and second particles.
Embodiment 1.2. A combination of components for forming a coating comprising:
A) a first component which comprises:
i) an elastomeric binder comprising one or more styrenic block copolymers, wherein said elastomeric binder comprises from about 1% to about 30% of said one or more styrenic block copolymers by weight (e.g., about 1% to about 5%, about 5% to about 10%, about 10% to about 15%, about 15% to about 25%, or about 25% to about 30% of said one or more styrenic block copolymers);
ii) optionally, one or more independently selected first particles having a size of about microns to about 225 microns, wherein, when said first particles are present, the 30 first component comprises from about 0.01% to about 5% of said first particles by weight (e.g., about 0.01% to about 5%, about 0.03% to about 1%, about 0.05% to about 0.15%, about 0.1% to about 2.5%, or about 0.2% to about 5% of said first particles by weight); and iii) one or more independently selected solvents; and B) a second component which comprises per 100 parts by weight:
i) 0.1 to 3.5 parts by weight (e.g., 0.1-1, 1.0-2.0, 0.2-2.0, 0.5-1.5, 0.5-2.0, 0.75 -2.5, 1.5-2.0, 1.5-2.5, 2.0-3.0, 2.0-3.5, or 2.5-3.5) of one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with said second particles;
ii) 0.1 to 1.0 parts by weight (e.g., 0.1-0.5, 0.5-1.0, or 0.3 -0.7 parts) of a fluorinated polyolefin, (e.g., a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, such as DyneonTM THV);
and/or 0.06 to 0.6 parts by weight (e.g., 0.06-0Ø1, 0.1-0.2, 0.2 -0.4, or 0.4-0.6 parts ) of a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, having an average molecular weight of about 1,000 to 3,000 (e.g., about 1,000 - 2,000, 2,000 -3,000, 1,500- 2,500, or about 1,000, 1,500, 2,000, 2,500, or 3,000 Da);
and iii) one or more independently selected solvents for a the remainder of a total of 100 parts by weight.
2. The combination of embodiment 1, wherein one or more of the styrenic block copolymers has a rubber phase crosslinked to the polystyrene phase.
3. The combination according to any of embodiments 1 to 2, wherein one or more of the styrenic block copolymers has a rubber phase comprising polybutadiene, polyisoprene, polyolefin or a mixture of any of those rubber phase components (e.g., linear triblock copolymers of styrene and ethylene/butylene with a polystyrene content of about 8% to about 36% by weight (e.g., about 8% to about 12%, about 12% to about 18%, about 18% to about 24%, about 24% to about 30%, about 30% to about 36%, about 10% to about 20%, or about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 17%, about 19%, about 20%, about 22%, about 24%, about 26%, about 28%, about 30%, about 32%, about 34%, about 36%) or mixtures of any two or more, three or more, or four or more of such triblock copolymers, any one or more of which may optionally comprise 1% to 3% or 1.4% to 2.0 % maleic anhydride).
4. The combination according to any of embodiments 2 to 3, wherein said rubber component comprises 60%-98%, 60%-70%, 70%-80%, 60%-90%, 80%-90%, 83%-93%, 85%-95%, or 89%-98%, of the elastomer by weight (based on the dry weight of the elastomer present in the first component not including any contribution by the first particles or other materials present in that component).
5. The combination according to any of embodiments 1 to 4, wherein said first component further comprises one or more colorants, UV stabilizers, antioxidants, rheological agents, and/or fillers.
6. The combination according to any of embodiments 1 to 5, wherein said first component further comprises up to 30% by weight of one or more tackifiers (e.g., 1%-5%, 2%-8%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, or 25%-30%).
7. The combination of embodiment 6, wherein said one or more styrenic block copolymers and said one or more tackifiers together comprise up to about 30% by weight of said first component (e.g., up to about 10, 15, 20, 25, or 30%).
8. The combination according to any of embodiments 1 to 7, wherein said elastomeric binder comprises one, two, three, or more triblock copolymers.
9. The combination according to any of embodiments 1 to 8, wherein said elastomeric binder comprises one or more styrenic block copolymers of styrene and ethylene/butylene with a polystyrene content of about 8% to about 36% by weight (e.g., about 8% to about 14%, about 12% to about 20%, about 18% to about 28%, about 22% to about 32%, about 26% to about 36%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 16%, about 18%, about 19%, about 20%, about 22%, about 24%, about 26%, about
28%, about 30%, about 32%, about 34%, about 36%), or mixtures of any two or more, three or more, or four or more of such triblock copolymers.
10. The combination according to any of embodiments 1 to 9, wherein one or more of said styrenic block copolymers present in the elastomeric binder comprise maleic anhydride (e.g., maleated copolymers having 1% to 3%, 1.4% to 2.0%, 1% to 1.4%, 1.6% to 3%, or 2% to 3% maleic anhydride based on the weight of the copolymer).
11. The combination according to any of embodiments 1 to 10, wherein at least one, or at least two, of said one or more styrenic block copolymers is a linear copolymer or a branched copolymer (e.g., a dendrimer or arborol).
12. The combination according to any of embodiments 1 to 11, wherein the elastomeric binder comprises a first and a second maleated triblock copolymer of styrene and ethylene/butylene wherein:
said first maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content from about 8% to about 14%, with 0.4% to 1.6% (e.g., 0.5% to 1.5%, 0.6% to 1.4%, or 0.7% to 1.3%) substitution (content by weight) of maleic anhydride by weight of the first triblock copolymer (and optionally less than 0.3% maleic anhydride free); and said second maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content of about 22% to about 32%, with 1.1% to 2.5% (e.g., 1.3%
to 2.3%
or 1.4% to 2.4%) substitution of maleic anhydride by weight of the second triblock copolymer.
13. The combination of embodiment 12, wherein said first and/or second triblock copolymers are independently selected linear or branched (e.g., arborols or dendrimers) copolymers.
14. The combination according to any of embodiments 12 to 13, wherein said first and second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1 (e.g., the first copolymer to second copolymer ratio is: about 4:1 to about 5.5:1; about 5:1 to about 6:1; or about 5.5:1 to about 6.5:1).
15. The combination according to any of embodiments 1-14, wherein said first particles are selected from the group consisting of: glass, ceramic, rubber, plastic, thermoplastic, wood, cellulose, metal oxides, silicon dioxide, silicates, tectosilicates, germanium dioxide, plastic particles, carbide particles, nitride particles, boride particles (e.g., zirconium or titanium boride), spinel particles, diamond particles, fly ash particles, fibers and hollow glass spheres, hollow glass particles or hollow plastic particles (e.g., glass, polymer, plastic or thermoplastic particles, spheres, or microspheres), wherein said first particles optionally comprise a colorant (e.g., colored or pigmented glass particles, plastic particles, rubber particles, hollow glass or hollow plastic particles).
16. The combination according to any of embodiments 1 to 15, wherein said first particles comprise hollow glass or plastic particles (e.g., glass, polymer, plastic or thermoplastic particles or microspheres), and wherein said first particles optionally comprise a colorant.
17. The combination according to embodiment 16, wherein said hollow glass or hollow plastic particles have a size (average diameter) in a range selected from the group consisting of 5 to 50 microns, 6 to 45 microns, 5 to 20 microns, 20 to 35 microns, and 35 to 50 microns.
18. The combination according to any of embodiments 15 to 17, wherein said hollow plastic particles have a density selected from the group consisting of less than 60 kg/m3, less than 50 kg/m3, less than 40 kg/m3, less than 30 kg/m3, or less than 25 kg/m3, and wherein said hollow glass particles have a density selected from the group consisting of less than 125 kg/m3, less than 150 kg/m3, less than 200 kg/m3, less than 250 kg/m3, less than 300 kg/m3, less than 350 kg/m3, less than 400 kg/m3, less than 450 kg/m3, less than 500 kg/m3, less than 550 kg/m3, less than 600 kg/m3, or 600 kg/m3.
19. The combination according to any of embodiments 1 to 18, wherein the second particles have an average size in a range selected from the group consisting of from:
about 1 nm to about 100 nm; about 10 nm to about 200 nm; about 20 nm to about 400 nm; about 10 nm to 500 nm; about 40 nm to about 800 nm; about 100 nm to about 1 micron; about 200 nm to about 1.5 microns; about 500 nm to about 2 microns; about 500 nm to about 2.5 microns;
about 1 micron to about 10 microns; about 2 microns to about 20 microns; about 2.5 microns to about 25 microns; about 500 nm to about 25 microns; about 400 nm to about 20 microns;
and about 100 nm to about 15 microns.
20. The combination according to any of embodiments 1 to 19, wherein said second particles comprise a metal oxide, an oxide of a metalloid (e.g., silica), a silicate, or a glass.
21. The combination according to any of embodiments 1 to 20, wherein said second particles are comprised of silica and have an average size in a range selected from: about 1 nm to about 50 nm; about 1 nm to about 100 nm; about 1 nm to about 400 nm; about 1 nm to about 500 nm; about 2 nm to about 120 nm; about 5 nm to about 150 nm; about 5 nm to about 400 nm;
about 10 nm to about 300 nm; or about 20 nm to 400 nm.
22. The combination according to any of embodiments 1 to 21, wherein said second particles have an average size in the range of from 1 nm to 100 nm or from 2 nm to 200 nm.
23. The combination according to any of embodiments 1 to 22, wherein said second particles comprise one or more hydrophobic and/or oleophobic moieties.
24. The combination according to any of embodiments 1 to 23, wherein said second particles comprise one or more alkyl, fluoroalkyl, and/or perfluoroalkyl moieties that are covalently bound to the second particles directly, or bound indirectly through one or more atoms bound to the second particles.
25. The combination according to any of embodiments 1 to 24, wherein said one or more hydrophobic or oleophobic moieties result from contacting the second particles with one or more silanizing agents of formula (I):
R4,Si-X. (I) where n is an integer from 1 to 3;
each R is independently selected from (i) alkyl or cycloalkyl group optionally substituted with one or more fluorine atoms, (ii) Ci to 20 alkyl optionally substituted with one or more substituents independently selected from fluorine atoms and C60 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1t010 alkyl, C1t010 haloalkyl, C1t010 alkoxy, or C1t010 haloalkoxy substituents, (iii) C2 to 8 Or C6 to 20 alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1t010 alkyl, C1t010 haloalkyl, C1t010 alkoxy, or C1t010 haloalkoxy substituents, (iv) C60 14 aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents, (V) C4 to 20 alkenyl or C4 to 20 alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy, and (vi) ¨Z-((CF2)q(CF3))r, wherein Z is a C1t012 or a C2 to 8 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4;
each X is independently selected from -H, -Cl, -I, -Br, -OH, -0R2, -NHR3, or -N(R3)2 group;
each R2 is an independently selected C1 to 4 alkyl or haloalkyl group; and each R3 is an independently selected H, C1 to 4 alkyl, or haloalkyl group.
26. The combination according to embodiment 25, wherein each R is selected independently from:
(a) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms;
(b) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms;
(c) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms;
(d) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms when n is 2 or 3;
(e) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms when n is 2 or 3;
and (f) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms when n is 2 or 3.
27. The combination according to any of embodiments 25 to 26, wherein R is -Z-((CF2)q(CF3)),, wherein Z is a C1 to 12 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4.
28. The combination according to any of embodiments 25 to 27, wherein n is 1, 2, or 3.
10. The combination according to any of embodiments 1 to 9, wherein one or more of said styrenic block copolymers present in the elastomeric binder comprise maleic anhydride (e.g., maleated copolymers having 1% to 3%, 1.4% to 2.0%, 1% to 1.4%, 1.6% to 3%, or 2% to 3% maleic anhydride based on the weight of the copolymer).
11. The combination according to any of embodiments 1 to 10, wherein at least one, or at least two, of said one or more styrenic block copolymers is a linear copolymer or a branched copolymer (e.g., a dendrimer or arborol).
12. The combination according to any of embodiments 1 to 11, wherein the elastomeric binder comprises a first and a second maleated triblock copolymer of styrene and ethylene/butylene wherein:
said first maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content from about 8% to about 14%, with 0.4% to 1.6% (e.g., 0.5% to 1.5%, 0.6% to 1.4%, or 0.7% to 1.3%) substitution (content by weight) of maleic anhydride by weight of the first triblock copolymer (and optionally less than 0.3% maleic anhydride free); and said second maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content of about 22% to about 32%, with 1.1% to 2.5% (e.g., 1.3%
to 2.3%
or 1.4% to 2.4%) substitution of maleic anhydride by weight of the second triblock copolymer.
13. The combination of embodiment 12, wherein said first and/or second triblock copolymers are independently selected linear or branched (e.g., arborols or dendrimers) copolymers.
14. The combination according to any of embodiments 12 to 13, wherein said first and second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1 (e.g., the first copolymer to second copolymer ratio is: about 4:1 to about 5.5:1; about 5:1 to about 6:1; or about 5.5:1 to about 6.5:1).
15. The combination according to any of embodiments 1-14, wherein said first particles are selected from the group consisting of: glass, ceramic, rubber, plastic, thermoplastic, wood, cellulose, metal oxides, silicon dioxide, silicates, tectosilicates, germanium dioxide, plastic particles, carbide particles, nitride particles, boride particles (e.g., zirconium or titanium boride), spinel particles, diamond particles, fly ash particles, fibers and hollow glass spheres, hollow glass particles or hollow plastic particles (e.g., glass, polymer, plastic or thermoplastic particles, spheres, or microspheres), wherein said first particles optionally comprise a colorant (e.g., colored or pigmented glass particles, plastic particles, rubber particles, hollow glass or hollow plastic particles).
16. The combination according to any of embodiments 1 to 15, wherein said first particles comprise hollow glass or plastic particles (e.g., glass, polymer, plastic or thermoplastic particles or microspheres), and wherein said first particles optionally comprise a colorant.
17. The combination according to embodiment 16, wherein said hollow glass or hollow plastic particles have a size (average diameter) in a range selected from the group consisting of 5 to 50 microns, 6 to 45 microns, 5 to 20 microns, 20 to 35 microns, and 35 to 50 microns.
18. The combination according to any of embodiments 15 to 17, wherein said hollow plastic particles have a density selected from the group consisting of less than 60 kg/m3, less than 50 kg/m3, less than 40 kg/m3, less than 30 kg/m3, or less than 25 kg/m3, and wherein said hollow glass particles have a density selected from the group consisting of less than 125 kg/m3, less than 150 kg/m3, less than 200 kg/m3, less than 250 kg/m3, less than 300 kg/m3, less than 350 kg/m3, less than 400 kg/m3, less than 450 kg/m3, less than 500 kg/m3, less than 550 kg/m3, less than 600 kg/m3, or 600 kg/m3.
19. The combination according to any of embodiments 1 to 18, wherein the second particles have an average size in a range selected from the group consisting of from:
about 1 nm to about 100 nm; about 10 nm to about 200 nm; about 20 nm to about 400 nm; about 10 nm to 500 nm; about 40 nm to about 800 nm; about 100 nm to about 1 micron; about 200 nm to about 1.5 microns; about 500 nm to about 2 microns; about 500 nm to about 2.5 microns;
about 1 micron to about 10 microns; about 2 microns to about 20 microns; about 2.5 microns to about 25 microns; about 500 nm to about 25 microns; about 400 nm to about 20 microns;
and about 100 nm to about 15 microns.
20. The combination according to any of embodiments 1 to 19, wherein said second particles comprise a metal oxide, an oxide of a metalloid (e.g., silica), a silicate, or a glass.
21. The combination according to any of embodiments 1 to 20, wherein said second particles are comprised of silica and have an average size in a range selected from: about 1 nm to about 50 nm; about 1 nm to about 100 nm; about 1 nm to about 400 nm; about 1 nm to about 500 nm; about 2 nm to about 120 nm; about 5 nm to about 150 nm; about 5 nm to about 400 nm;
about 10 nm to about 300 nm; or about 20 nm to 400 nm.
22. The combination according to any of embodiments 1 to 21, wherein said second particles have an average size in the range of from 1 nm to 100 nm or from 2 nm to 200 nm.
23. The combination according to any of embodiments 1 to 22, wherein said second particles comprise one or more hydrophobic and/or oleophobic moieties.
24. The combination according to any of embodiments 1 to 23, wherein said second particles comprise one or more alkyl, fluoroalkyl, and/or perfluoroalkyl moieties that are covalently bound to the second particles directly, or bound indirectly through one or more atoms bound to the second particles.
25. The combination according to any of embodiments 1 to 24, wherein said one or more hydrophobic or oleophobic moieties result from contacting the second particles with one or more silanizing agents of formula (I):
R4,Si-X. (I) where n is an integer from 1 to 3;
each R is independently selected from (i) alkyl or cycloalkyl group optionally substituted with one or more fluorine atoms, (ii) Ci to 20 alkyl optionally substituted with one or more substituents independently selected from fluorine atoms and C60 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1t010 alkyl, C1t010 haloalkyl, C1t010 alkoxy, or C1t010 haloalkoxy substituents, (iii) C2 to 8 Or C6 to 20 alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1t010 alkyl, C1t010 haloalkyl, C1t010 alkoxy, or C1t010 haloalkoxy substituents, (iv) C60 14 aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents, (V) C4 to 20 alkenyl or C4 to 20 alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy, and (vi) ¨Z-((CF2)q(CF3))r, wherein Z is a C1t012 or a C2 to 8 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4;
each X is independently selected from -H, -Cl, -I, -Br, -OH, -0R2, -NHR3, or -N(R3)2 group;
each R2 is an independently selected C1 to 4 alkyl or haloalkyl group; and each R3 is an independently selected H, C1 to 4 alkyl, or haloalkyl group.
26. The combination according to embodiment 25, wherein each R is selected independently from:
(a) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms;
(b) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms;
(c) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms;
(d) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms when n is 2 or 3;
(e) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms when n is 2 or 3;
and (f) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms when n is 2 or 3.
27. The combination according to any of embodiments 25 to 26, wherein R is -Z-((CF2)q(CF3)),, wherein Z is a C1 to 12 divalent alkane radical or a C20 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4.
28. The combination according to any of embodiments 25 to 27, wherein n is 1, 2, or 3.
29. The combination according to any of embodiments 25 to 28, wherein all halogen atoms present in any one or more R groups are fluorine atoms.
30. The combination according to any of embodiments 25 to 29, wherein each X
is independently selected from -H, -Cl, -0R2, -NHR3, and -N(R3)2.
is independently selected from -H, -Cl, -0R2, -NHR3, and -N(R3)2.
31. The combination according to any of embodiments 25 to 30, wherein each X
is independently selected from -Cl, -0R2, -NHR3, and -N(R3)2.
is independently selected from -Cl, -0R2, -NHR3, and -N(R3)2.
32. The combination according to any of embodiments 25 to 31, wherein each X
is independently selected from -Cl, -NHR3, and -N(R3)2.
is independently selected from -Cl, -NHR3, and -N(R3)2.
33. The combination according to any of embodiments 1 to 32, wherein two, three, four, or more than four compounds of formula (I) are employed alone or in combination to modify at least one second particle; or wherein said second particles incorporated into said second component have an Oil Repellancy Grade Number greater than or equal to about 1, 2, 3, 4, 5, 6, 7, or 8 when measured as a coating applied to a metal plate in the absence of a binder.
34. The combination according to any of embodiments 1 to 33, wherein said second particles are treated with a silanizing agent selected from the group consisting of:
tridecafluoro-1,1,2,2-tetrahydrooctyl)silane ; (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane; n-octadecyltrimethoxysilane; n-octyltriethoxysilane; and nonafluorohexyldimethyl(dimethylamino)silane.
tridecafluoro-1,1,2,2-tetrahydrooctyl)silane ; (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane; n-octadecyltrimethoxysilane; n-octyltriethoxysilane; and nonafluorohexyldimethyl(dimethylamino)silane.
35. The combination according to any of embodiments 1 to 34, wherein said second particles are treated with a silanizing agent selected from the group consisting of dimethyldichlorosilane, hexamethyldisilazane, octyltrimethoxysilane, polydimethylsiloxane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane.
36. The combination according to any of embodiments 1 to 35, wherein said first component and/or said second component further comprise an independently selected solvent and/or propellant.
37. The combination of embodiment 36, wherein said solvent is an organic solvent or a mixture of two or more organic solvents, and wherein either said organic solvent or said mixture of two or more organic solvents comprises less than 10%, 5%, 2%, or 1% of water by weight.
38. The combination of embodiment 36 or 37, wherein said solvent or propellant comprises greater than 1%, greater than 2%, greater than 5%, up to 10%, up to 20%, or greater than 20% by weight of any one, two, three or more of each of air, nitrogen, an inert gas, an alkane, a ketone, an ether, a halogenated alkane, a halogenated alkene, an aromatic hydrocarbon, an alcohol, methane, ethane, propane, butane, pentane, hexane, heptane, ethylene, propene, acetone, methyl isobutyl ketone (MIKB), methyl ethyl ketone (MEK), dimethylether (DME), diethylether, methyl ethyl ether, methyl tert¨butyl ether, chloromethane, dichloromethane, carbontetrachloride, trichlorofluoromethane, clichlorodifluoromethane, methanol, ethanol, propanol, butanol, benzene, toluene, xylene, 1-chloro-4-(trifluoromethyl)-benzene, carbon disulfide, and isomers of any of the foregoing, based upon the total weight of solvent or propellant present in the composition.
39. The combination according to any of embodiments 1 to 38, wherein either the first component and/or second component further comprise a colorant or pigment.
40. The combination according to any of embodiments 1 to 39, wherein said elastomeric binder has an ultimate strength greater than about 20, 21, 22, 23, 24, 26, 28, 30, 32, or 34 Mega Pascals (MPa) (e.g., greater than about 2,500, 2,750, 2,800, 2,900, 3,000, 3,200, 3,500, 3,750, 4,000, 4,250, 4,500, 4,750, or 4,900 psi) according to ASTM D412.
41. A method of forming a hydrophobic coating on a portion of a surface comprising the following steps:
(a) applying a first component according to any of embodiments 1 to 40 to at least a portion of the surface, wherein the portion of the surface has optionally been treated with a primer (e.g, an elastomeric primer) on all or part of the surface to which said first component is to be applied; and (b) applying a second component according to any of embodiments 1 (i.e., 1.1 or 1.2) to 40 to all or a portion of the portion coated in step (a), wherein said coating has either hydrophobic or superhydrophobic properties, and optionally is also oleophobic or superoleophobic.
(a) applying a first component according to any of embodiments 1 to 40 to at least a portion of the surface, wherein the portion of the surface has optionally been treated with a primer (e.g, an elastomeric primer) on all or part of the surface to which said first component is to be applied; and (b) applying a second component according to any of embodiments 1 (i.e., 1.1 or 1.2) to 40 to all or a portion of the portion coated in step (a), wherein said coating has either hydrophobic or superhydrophobic properties, and optionally is also oleophobic or superoleophobic.
42. The method of embodiment 41, wherein said steps of applying said first component and applying said second component are conducted by methods selected independently from painting, printing, stamping, rolling, dipping, spin-coating, spraying, and electrostatic spraying.
43. A coating prepared by the method according to any of embodiments 41 to 42.
44. The coating of embodiment 43, wherein said coating is superhydrophobic and/or superoleophobic.
45. The coating according to any of embodiments 43 to 44, wherein said coating has an ultimate strength greater than about 20, 21, 22, 23, 24, or 26 mega Pascals (MPa) (e.g., greater than about 2,500, 2,750, 2,800, 2,900, 3,000, 3,200, 3,500, or 3,750 psi) according to ASTM
D412.
D412.
46. The coating according to any of embodiments 43 to 45, wherein said coating has a modulus at 100% elongation of greater than 10, 11, 12, or 13 mega Pascals (MPa) (e.g., greater than about 1,700, about 1,750, about 1,800, or about 1,850 psi) according to ASTM
D412.
D412.
47. The coating according to any of embodiments 43 to 46, having an elongation at break of greater than about 100%, 110%, 120%, 140%, 160%, 180%, 200%, 250%, 300%, 350%, 400%, or 420%.
48. The coating according to any of embodiments 43 to 47, having a relative electrical permittivity at 100 MHz from about 0.2 to about 4 at about 22 C (e.g., a relative electrical permittivity from about 0.2 to about 1, from about 1 to about 2, from about 2 to about 3, or from about 3 to about 4) as measured by ASTM D150 using a 0.11 mm thick film.
49. The coating according to any of embodiments 43 to 48, having a Total Luminous Transmittance of about 75% to about 85% and a haze of about 85% to about 90%
as measure by ASTM D1003-11 on a film about 25 microns thick.
as measure by ASTM D1003-11 on a film about 25 microns thick.
50. The coating according to any of embodiments 43-49, wherein said coating is superhydrophobic and retains its superhydrophobicity after being subjected to greater than 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 cycles on a Taber Abraser using CS-0 or CS-10 wheels and a 250 gram load at 95 rpm at room temperature, wherein the end of superhydrophobicity is determined to be the point when more than half of the water droplets applied to the portion of the surface subject to the action of the wheels do not roll off the surface when the surface is inclined at a 5 degree angle at room temperature.
51. The coating according to embodiment 50, wherein said coating retains its superhydrophobicity after being subjected to greater than 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100 cycles on a Taber Abraser using CS-0 or CS-10 wheels and a 1,000 gram load at 95 rpm at 20 C -25 C, wherein the end of superhydrophobicity is determined to be the point when more than half of the water droplets applied to the portion of the surface subject to the action of the wheels do not roll off the surface when the surface is inclined at a 5 degree angle at room temperature.
52. The coating according to any of embodiments 43 to 51, wherein said coating is superhydrophobic and when said coating is applied to a planar surface, it continues to display superhydrophobic behavior after being subjected to a continuous shower test of about six liters of water per minute at about 20 C-25 C for greater than 0.3, 0.5, 0.6, 1, 2, 3, or 3.5 hours, wherein the duration of superhydrophobic behavior is determined to be the time when more than half of the water droplets applied to a portion of the surface subject to said shower do not roll off the surface when it is inclined at a 5 degree angle at room temperature, wherein the shower test is conducted using a showerhead with 70 nozzles with a 1 mm diameter orifice arranged in 5 spokes of 5 nozzles and 15 spokes of 3 nozzles about a central point on a circular showerhead, and wherein the showerhead delivers approximately 6 liters of potable tap water per minute using about 137900 Pa (Pascals) to 310275 Pa (20-45 psi cycle over 5 minutes), and wherein the coating is placed about 1.5 meters below the showerhead.
53. The coating of embodiment 52, wherein, when said coating is subjected to said continuous shower test for a period of time sufficient to lose superhydrophobic behavior, the coating regains superhydrophobic behavior following drying at 20 C to 25 C and one atmosphere of pressure, said shower testing and drying collectively comprising a single test cycle.
54. The coating of embodiment 53, wherein said coating regains superhydrophobic behavior following more than 5, 10, 15, 20, 30, 40, 50, 75, 100, 150, or 200 of said test cycles.
55. A method according to embodiment 41 or 42, wherein applying according to step (b) is repeated to at least a portion of the coated surface if that portion of the coated surface loses said hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties, and wherein following the repetition of step (b), the coated portion regains hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties.
56. A method according to embodiment 41 or 42, wherein both steps (a) and (b) are repeated on at least a portion of the coated surface if that portion of the coated surface loses said hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties, and wherein following the repetition of steps (a) and (b), the coated portion regains hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties.
57. A coated surface, or a portion thereof, resulting from the process of embodiment 55 or 56.
58. A product comprising an aerosol spray container (e.g., a metal canister) containing a first component according to any of embodiments 1 to 40 and a propellant.
59. The product of embodiment 58, wherein the aerosol spray container comprises a valve assembly, a dip tube, and an actuator.
60. A product comprising an aerosol spray container (e.g., a metal canister) containing a second component according to any of embodiments 1 to 40 and a propellant.
61. The product of embodiment 60, wherein the aerosol spray container comprises a valve assembly, a dip tube, and an actuator.
62. A product comprising an aerosol spray container according to embodiment 58 or 59, and a second aerosol spray container according to embodiment 60 or 61.
9.0 EXAMPLES
Example 1 An HP/OP Elastomeric Coating One part by weight of elastomeric coating (24% by weight of solids) supplied as clear liquid from PLASTI DIP International, Inc. (Blaine, MN) is combined with two parts by weight of xylene and mixed. The mixture of elastomer and xylene is divided into six aliquots and the indicated amounts of EXPANCEL 461 DET d25 (0.01% to 0.5% by weight based on the total weight of the elastomer and xylene mixture) is added to separate aliquots. The aliquots are mixed to form first component compositions. The first component compositions are sprayed onto individual aluminum plates to form a base coat. The base coated aluminum plates are then top coated with a second component consisting of a 2% (w/w) dispersion in acetone of fumed silica particles modified to render them hydrophobic by reacting them with tridecafluoro tetrahydroctyl trichloro silane (fumed silica to silane ration is 2:1 by weight). Test data for plates is summarized in the table below and the data is plotted in Figure 5.
Coatings formed from PLASTI DIP elastomer have a tensile strength of 3,740 psi (ASTM D-638), salt spray resistance greater than 1,000 hours (ASTM B-117) and elongation at break of 430% (ASTM D-638) without added first or second particles.
Data on HP/OP Elastomeric Coatings from Example 1 Approximate Taber Abraser EXPANCEL Glove Shower Cycles to loss of SH behavior wt % Rubs (hr)*
CS-0 wheel CS-10 wheel ( ) 0.01% 100 22(13) 0.03% 325 72 (43) 1 0.06% 700 156 (93) 2 0.10% 750 167 (100) 3.5 0.30% 500 111 (67) 3.5 0.50% 400 89 (53) 3.5 Taber cycles estimated based upon a value of 4.5 glove rubs per Taber cycle using CS-0 wheels and 7.5 glove rubs per Taber cycle (sample rotation) using CS-10 wheels. The number in parentheses is for the CS-10 data estimate. Taber load was 250 g.
*Shower test was terminated at 3.5 hours.
Data in the table above and Figure 5 show that the abrasion resistance (glove rub performance and estimated Taber cycles) reaches a maximum when about 0.1% of EXPANCEL
particles are incorporated into the base coat. Shower time to loss of superhydrophobicity also increases with increasing amounts of EXPANCEL particles incorporated in the base coat.
Shower time to loss of superhydrophobic behavior saturates beyond 0.1%
addition.
Example 2 Six first component mixtures are prepared as in Example 1 using 0.1% of five different types of EXPANCEL particles (duplicate samples containing EXPANCEL 031 DU
400), and the first components are each applied to a different aluminum plate by spraying to form a base coat. The base coating on each plate is then top coated with a second component comprising a 2% (w/w) dispersion of fumed silica particles treated with tridecafluoro tetrahydroctyl trichlorosilane suspended in acetone. For samples containing EXPANCEL 031 DU
400) the aluminum plates were heated to 80 C for 2-3 minutes either before or after the application of the second component to expand the EXPANCEL particles. Test data for the plates are summarized in the table of performance data, below, and plotted in Figure 6.
Performance data by using 0.1% by weight of different EXPANCEL particles in elastomeric coating EXPANCEL Glove Taber Abraser Cycles to Shower type Rubs loss of SH behavior (hr) 461 DET d25 800 178 (106) 4 461 DE 40 d25 500 111 (67) 2.5 461 DET 40 d25 650 144 (87) 4 920 DE 80 d30 400 89 (53) 2.5 031 DU 40 75 17(10) 0.5 (heated before top coating) 031 DU 40 75 17(10) 0.5 (heated after top coating) Taber cycles estimated based upon a value of 4.5 glove rubs per Taber cycle using a 250g load, CS-0 wheels and 7.5 glove rubs per Taber cycle (sample rotation) using CS-10 wheels. The number in parentheses is for the CS-10 data estimate.
Data in the table above and Figure 6 show that incorporation of EXPANCEL 461 DET
d25 and EXPANCEL 461 DET 40 d25 produces a combination of resistance to the loss of HP/OP when being handled ("handleability" assessed by glove rubs and resistance to Taber abrasion testing), and shower time to loss of superhydrophobicity. Unexpanded EXPANCELs 031 DU 40 did not show good performance. The shower times track closely and positively correlate with glove rubs and Taber cycles (higher glove rubs correspond to higher shower time).
Example 3 Scaled Preparation of Fumed Silica Second Particles A series of aluminum plates primed with PLASTI DIP primer for metals according to the manufacturer's instructions are base coated as in Example 1, with 0.1%
d25 particles added to the first component, which is applied by spraying.
After the base coat has dried at room temperature, one set of plates is treated with a second component as in Example 1.
The second component comprises 20 g of 20 ¨ 80 nm fumed silica particles having a surface area of about 200 m2/g (Evonik Industries, Horsham PA), treated in an Osterizer kitchen blender for 10 minutes at room temperature with 10g of tridecafluoro tetrahydroctyl trichloro silane. A
second set of plates is also treated with a second component as in Example 1, using silica from the same supplier prepared in a larger batch using 5,000 g of the silica reacted with tridecafluoro tetrahydroctyl trichloro silane 2,500 g in a 10 kg reactor system at room temperature for 2-3 hours. In this example, after top coats are applied the plates are dried for 15 minutes at 170 F
(77 C). Two plates treated with fumed silica prepared in the blender and two plates treated with fumed silica prepared in the reactor are subjected to thickness and surface roughness measurements. The point at which the plates lose superhydrophobic behavior is also determined using Taber Abraser equipped with CS-0 wheels at a 1,000 g load and using glove rub testing.
Loss of superhydrophobic behavior is deemed to be the point at which more than half of the water droplets applied to the tested portion of a substantially planar surface inclined at 5 degrees from the horizontal do not roll off the plate.
Data on plates coated with fumed silica particles prepared in the blender is summarized in Table 7, and data on plates treated with fumed silica prepared in the reactor is shown in Table 8.
Table 7 Blender Grade NPT 74 Coating Ra Coating Ra Thickness (mils) Thickness (mils) Sample #1 Sample #1 Sample #2 Sample #2 0.73 2.61 1.1 3.267 0.67 2.66 1.01 3.337 0.49 0.82 0.76 1.08 Avg 0.6625 2.635 1.0025 3.302 Glove Rubs 600 Taber Abraser cycles to loss of SH 50 Table 8 Reactor Grade NPT 74 Coating Ra Coating Ra Thickness (mils) Thickness (mils) Sample #1 Sample #1 Sample #2 Sample #2 0.92 3.246 1.07 3.027 1.35 3.259 0.94 2.35 0.88 0.86 1.01 0.88 Avg 1.04 3.2525 0.9375 2.6885 Glove Rubs 900 Taber Abraser cycles to loss of SH 30 The data in Tables 7 and 8 indicate that superhydrophobic coatings prepared with fumed silicas produced in reactors on different scales display similar properties.
Example 4 Transparency and Haze Glass plates are coated with a near transparent coating based on elastomeric binder systems as in Example 1 with the exception that the plate marked P does not include first particles (EXPANCEL particless) in the base coat (first component). The plate marked SE-1 contains 0.1% of EXPANCEL particles in the first component. Samples are tested for Haze value and Total Luminous Transmittance (TLT) values using the method described in ASTM
D1003. The instrument is calibrated without a sample present using air as a standard.
Calibration values are TLT = 100 and Haze = 0. Clear, clean, uncoated glass plates have average readings of TLT = 90.6 and a haze reading of 0.18. Plates lacking first particles (P-coat) have about the same transparency as clear clean glass. The presence of EXPANCEL
particles in the base coat reduces the transparency by about 10%. The coating haze increases from about 0.18 for glass to about 61% for coatings without first particles and to about 90% for coatings including EXPANCEL particles in the base coating. See Table 9.
Table 9 P-Coat Sample Reading 1 Reading 2 Reading 3 Average Readings (no first particles) Transmittance 90.50 90.30 90.40 90.4 Haze 60.70 62.40 60.80 61.30 P-Coat Sample Reading 1 Reading 2 Reading 3 Average Readings (no first particles) SE-1 Sample (first particles included in the base coat) Transmittance 80.00 79.10 80.10 79.73 Haze 88.60 90.80 89.30 89.57 Example 5 Effect of Coating Thickness Six aluminum plates (10 cm x 10 cm) are primed with PLASTI DIP primer for metal (product f938 hp). Pairs of the primed plates are spray coated with first component as in Example 1(0.1% EXPANCELs) to achieve a base coat thicknesses of about 1, 1.5, or 2.6 ml respectively. One plate at each coating thickness is top coated with 2 ml of the second component as described in Example 1, and the second plate at each coating thickness is top coated with 4 ml of second component. Coating thicknesses, which include the primer thickness, and Taber Abraser data are summarized in Table 10A and data is plotted in Figure 7.
Table 10A Data summary for plates made with varying coating thicknesses Volume of Passes of Final Tabers (CS-10) Topcoat Base Thickness to end of super-Sample (mL) Coat (mil) hydrophobicity Notes some 1.1 2 1 0.55 35 tearing 2.1 2 3 1.5 35 no tearing 3.1 2 5 2.6 35 no tearing some 1.2 4 1 0.9 45 tearing 2.2 4 3 2.2 50 no tearing 3.2 4 5 2.9 50 no tearing Based on the data above, 2 ml of top coat (0.02 ml/cm2) produces no benefits in performance improvement at any thickness. However, when the top coat is increased to 4 ml (0.04 ml/cm2), it provides an adequate performance that increases with coating thickness. While not wishing to be bound by any theory, it appears that at the higher application rate the top coat penetrates to some depth into the base coat. When only 2 ml (0.02 ml/cm2) is applied the coating may be sufficient to just cover the base coat, but not enough to permit the second particles to penetrate at any significant level that will increase the durability of SH performance.
In addition, when the base coat is very thin, tearing becomes the failure mode.
Example 6 Effect of Priming with Polyurethane Primer Aluminum plates are primed with a two-part polyurethane coating (DESMOPHEN
670BA with DESMODUR N75 BA-XBMS, Bayer Material Science) prepared and applied per manufacturer's instructions. An elastomeric coating as described in Example 1(0.1% of EXPANCEL 461 DET d25) is employed in the first component. Coated plates are measured for coating thickness (including primer thickness) and their ability to resist the loss of superhydrophobic behavior using a Taber Abraser fitted with CS-10 (abrasive) wheels and CS-0 (soft rubber) wheels at a 1,000 g load is recorded. All end points for loss for superhydrophobic behavior are measured for water droplet roll off with the plates inclined at 5 degrees from the horizontal (5 degree tilt angle). Test data is summarized in Table 10B.
Table 10B Summary of data on Al plates primed with two-part polyurethane as primer Sample 1 2 3 Total Coating Total Coating Total Coating and Primer and Primer and Primer Thickness(mils) Thickness (mils) Thickness (mils) 3.25 3.13 4.7 3.13 3.06 4.9 3 3.1 4.16 3.32 3.45 4.24 4.15 4.01 4.47 Avg Thickness 3.37 3.35 4.494 CS-10 Wheel CS-0 Wheel Glove Rubs Tabers CS-10 40 Tabers CS-0 40 Glove Rubs >1000 Example 7 Nearly Transparent HP/OP Elastomeric Coating with Various First Particles Elastomeric coatings are prepared on aluminum test plates as described in Example 1, with the exception that the first component contains first particles as indicated in Table 11. The test plates are assessed for loss of superhydrophobic behavior using glove rubs as a rapid test for assessment of handleabilty and abrasion resistance/durability. Test data for all coated plates are summarized in Table 11.
Table 11 Summary of data for non near transparent elastomeric binder system based coatings Taber Abraser Particle Amount Glove Predicted Particle Particle Size weight Rubs cycles with Designation Type (micron) (%) (#s) CS-0 wheel*
Thermoplastic EXPANCEL Encapsulated with DET gas 10-40 0.01 100 22 Thermoplastic EXPANCEL Encapsulated with DET gas 10-40 0.1 750 167 Thermoplastic EXPANCEL Encapsulated with DET gas 10-40 0.5 400 89 Hollow Glass Spheres Hollow glass K25 spheres 25-90 0.5 800 178 Hollow Glass Spheres Hollow glass K46 spheres 15-70 0.5 >400 >89 *Projected based on GR/CS-0=4.5 Thermoplastic particles and hollow glass particles yield similar performance in increasing coating durability.
Example 8 Non-Transparent Elastomeric Coatings Prepared with Micronized Rubber First Particles PLASTI DIP (24% solids by weight) elastomeric coating (5 parts by weight of the liquid as provided by the supplier) is combined with seven parts by weight of xylene and mixed. To the resulting mixture of elastomer and xylene, micronized rubber particles (Lehigh Technology, Tucker, Georgia) about 4% or about 7.7% by weight are added to separate aliquots (based on the weight of the elastomer and xylene combined). The particles are mixed into each aliquot to form first component compositions. The first component compositions are applied to separate aluminum plates to form base coats, and the base coats are top coated with a second component as described in Example 1.
Test data showing resistance to the loss of superhydrophobicity based on glove rub testing and Taber testing for the coatings incorporating rubber particles is provided in Table 12.
That data shows the incorporation of elastomeric binder used in this example with micronized rubber particles produces highly durable surfaces that show increasing resistance to the loss of hydrophobicity with increasing amounts of rubber first particles incorporated into the binder up to at least 7.69%.
Table 12 Summary of data on non near transparent elastomeric binder based coatings Particle Particle Particle Amount Glove Taber Abraser Designation Type Size (i.tm) weight (%) Rubs (#s) cycles with CS-0*
Ground Micronized Rubber Rubber particles 70 4 1450 191 Ground Micronized Rubber Rubber particles 70 7.69 1800 237 *Projected based on GR/CS-0 wheel ratio of 7.6 for a 250 g load at 95 rpm.
Example 9 Non-Transparent Elastomeric Coating with Micronized Rubber Particles with and without Primer Elastomeric coatings are prepared as in Example 8 employing 7.69% of micronized rubber by weight in the first component. The coatings are applied to clean but unprimed aluminum plates or aluminum plates that have been treated with an elastomeric metal primer (PLASTI DIP metal primer) per the manufacturer's instructions. All plates are substantially planar. The top coating step is the same as in Example 8 and Example 1. The coated plates are assessed for resistance to the loss of SH behavior using a Taber Abraser fitted with CS-0 wheels or CS-10 wheels (as indicated) using 1,000 g loads at 95 rpm, resistance to the loss of SH
behavior using glove rubs, and coating thickness, which is measured including primer where present. The appearance of coating failures is also recorded for each plate and the data set forth in Table 13.
Table 13 Observations from Taber Abraser Testing of Plates With and Without Primer Coating Without Primer without primer Coating Thickness (mil) Comments Taber CS-0 6 cycles 1.5 Rips and Tears Taber CS-10 10 cycles 1.5 Rips and Tears Glove Rubs 1200 1.5 No Rips or Tears With primer Coating With Elastomeric Primer with elastomeric primer Coating Thickness (mil) Comments Taber CS-0 50 cycles 1.75 No Rips or Tears Taber CS-10 40 cycles 1.65 No Rips or Tears Glove Rubs 1600 1.75 No Rips or Tears The data indicates that samples with and without primer resist the loss of superhydro-phobicity with a very large number of glove rubs. Taber Abraser testing results in a loss of that property due to ripping and/or tearing of the coating in the absence of primer. Loss of super-hydrophobic behavior is assessed using the above-described droplet run off test with plates inclined at 5 degrees from the horizontal. Priming of the metal surfaces increases the number of Taber cycles the test samples can withstand without losing superhydrophobic behavior by about 4 to about 8 fold, regardless of whether non-abrasive rubber (CS-0) or abrasive (CS-10) wheels are employed.
Example 10 Thermal Stability of Elastomeric Coatings Elastomeric coatings incorporating EXPANCELs as in Example 1, or micronized rubber as in Example 8, are scraped from their plates and used for thermogravimetric analysis (TGA).
TGA data for the coatings is plotted in Figures 10 and 11, respectively.
Details of the test conditions are listed inside each of the graphs. Data from these charts show the following:
1. The coating containing EXPANCEL is stable up to 241 C (465 F) 2. The coating containing micronized rubber is stable up to 261 C (502 F) Based upon the data presented above the coatings may be used up to temperatures of 200 C or 400 F.
Example 11 HP/OP Coatings Employing Varying Proportions of a Styrenic Block Copolymer and Tackifier Three styrenic block copolymers (SBCs), FG 1901, FG 1924 and RP 6670, each obtained from KRATON , are dissolved in xylene at 20% by weight. RegalrezTM
tackifier, obtained from Eastman Chemical Company, is dissolved in xylene at 20% by weight.
Varying ratios of SBCs and tackifier solutions are mixed and UV stabilizers and antioxidants, 0.1% Irganox 1520L, 0.056% Tinuvin 328, and 0.056% Tinuvin 770DF (% by weight), are added.
Each of the mixtures of SBCs and tackifier formed is used as a first component and HP/OP coatings are prepared as in Example 1, using 0.1% EXPANCEL particles as first particles. The HP/OP coatings were tested for durability using a Taber Abraser equipped with CS-10 wheels and a 1,000 g load. The results are shown in Table 14.
Table 14 FG 1901/Regalrez 1094 FG 1924/Regalrez 1094 RP 6670/Regalrez Glove Taber Glove Taber Glove Taber Ratio Rubs cycles Ratio Rubs cycles Ratio Rubs cycles * 800 20 50/50 750 45 * 350 35 *
* 600 25 * 600 25 * Taber testing induced tearing.
Example 12 HP/OP Coatings Employing Maleated Styrene-Ethylene/Butylene-Styrene (SEBS) Block Copolymers Coatings were prepared using first components comprising maleated SBCs (e.g., maleated SEBS block copolymers) Table 15 Base Coat Total Component Exemplary Composition Component Parts by Weight Components (Total of 100 parts) (By weight where given) Maleated SBC 7 to 9 One or more maleated Styrene-Ethylene/Butylene-Styrene (SEBS) Block Copolymers (e.g., Kraton FG 1901, FG 1924 and/or RP 6670*
) Tackifier 3.5 to 7 Nonpolar hydrogenated hydrocarbon resin (e.g., produced by polymerization and hydrogenation of monomeric hydrocarbons) or esterified hydrogenated rosin.
e.g., Eastman RegalrezTM 1094 or ForalTM 105E
Antioxidant(s) 0.05 to 0.2 Antioxidant(s) (e.g., phenolic or hindered phenolic antioxidants e.g., Irganox 1520L
First Particles 0.05 to 20 Expancel 461 DET 40 d25 (0.05-0.2%) SoftSand 5-15%
Glass bubbles (e.g., Kl, S22, or A16/500) 1%-10%
UV stabilizer(s) 0.05 to 0.5 e.g., Tinuvin 328 and/or 770DF
Solvent Bring to 100 parts xylene (or mixed xylenes), acetone, n-hexane (or total including all mixed hexanes), 1-chloro-4-(trifluoromethyl)-other components benzene or mixtures thereof
9.0 EXAMPLES
Example 1 An HP/OP Elastomeric Coating One part by weight of elastomeric coating (24% by weight of solids) supplied as clear liquid from PLASTI DIP International, Inc. (Blaine, MN) is combined with two parts by weight of xylene and mixed. The mixture of elastomer and xylene is divided into six aliquots and the indicated amounts of EXPANCEL 461 DET d25 (0.01% to 0.5% by weight based on the total weight of the elastomer and xylene mixture) is added to separate aliquots. The aliquots are mixed to form first component compositions. The first component compositions are sprayed onto individual aluminum plates to form a base coat. The base coated aluminum plates are then top coated with a second component consisting of a 2% (w/w) dispersion in acetone of fumed silica particles modified to render them hydrophobic by reacting them with tridecafluoro tetrahydroctyl trichloro silane (fumed silica to silane ration is 2:1 by weight). Test data for plates is summarized in the table below and the data is plotted in Figure 5.
Coatings formed from PLASTI DIP elastomer have a tensile strength of 3,740 psi (ASTM D-638), salt spray resistance greater than 1,000 hours (ASTM B-117) and elongation at break of 430% (ASTM D-638) without added first or second particles.
Data on HP/OP Elastomeric Coatings from Example 1 Approximate Taber Abraser EXPANCEL Glove Shower Cycles to loss of SH behavior wt % Rubs (hr)*
CS-0 wheel CS-10 wheel ( ) 0.01% 100 22(13) 0.03% 325 72 (43) 1 0.06% 700 156 (93) 2 0.10% 750 167 (100) 3.5 0.30% 500 111 (67) 3.5 0.50% 400 89 (53) 3.5 Taber cycles estimated based upon a value of 4.5 glove rubs per Taber cycle using CS-0 wheels and 7.5 glove rubs per Taber cycle (sample rotation) using CS-10 wheels. The number in parentheses is for the CS-10 data estimate. Taber load was 250 g.
*Shower test was terminated at 3.5 hours.
Data in the table above and Figure 5 show that the abrasion resistance (glove rub performance and estimated Taber cycles) reaches a maximum when about 0.1% of EXPANCEL
particles are incorporated into the base coat. Shower time to loss of superhydrophobicity also increases with increasing amounts of EXPANCEL particles incorporated in the base coat.
Shower time to loss of superhydrophobic behavior saturates beyond 0.1%
addition.
Example 2 Six first component mixtures are prepared as in Example 1 using 0.1% of five different types of EXPANCEL particles (duplicate samples containing EXPANCEL 031 DU
400), and the first components are each applied to a different aluminum plate by spraying to form a base coat. The base coating on each plate is then top coated with a second component comprising a 2% (w/w) dispersion of fumed silica particles treated with tridecafluoro tetrahydroctyl trichlorosilane suspended in acetone. For samples containing EXPANCEL 031 DU
400) the aluminum plates were heated to 80 C for 2-3 minutes either before or after the application of the second component to expand the EXPANCEL particles. Test data for the plates are summarized in the table of performance data, below, and plotted in Figure 6.
Performance data by using 0.1% by weight of different EXPANCEL particles in elastomeric coating EXPANCEL Glove Taber Abraser Cycles to Shower type Rubs loss of SH behavior (hr) 461 DET d25 800 178 (106) 4 461 DE 40 d25 500 111 (67) 2.5 461 DET 40 d25 650 144 (87) 4 920 DE 80 d30 400 89 (53) 2.5 031 DU 40 75 17(10) 0.5 (heated before top coating) 031 DU 40 75 17(10) 0.5 (heated after top coating) Taber cycles estimated based upon a value of 4.5 glove rubs per Taber cycle using a 250g load, CS-0 wheels and 7.5 glove rubs per Taber cycle (sample rotation) using CS-10 wheels. The number in parentheses is for the CS-10 data estimate.
Data in the table above and Figure 6 show that incorporation of EXPANCEL 461 DET
d25 and EXPANCEL 461 DET 40 d25 produces a combination of resistance to the loss of HP/OP when being handled ("handleability" assessed by glove rubs and resistance to Taber abrasion testing), and shower time to loss of superhydrophobicity. Unexpanded EXPANCELs 031 DU 40 did not show good performance. The shower times track closely and positively correlate with glove rubs and Taber cycles (higher glove rubs correspond to higher shower time).
Example 3 Scaled Preparation of Fumed Silica Second Particles A series of aluminum plates primed with PLASTI DIP primer for metals according to the manufacturer's instructions are base coated as in Example 1, with 0.1%
d25 particles added to the first component, which is applied by spraying.
After the base coat has dried at room temperature, one set of plates is treated with a second component as in Example 1.
The second component comprises 20 g of 20 ¨ 80 nm fumed silica particles having a surface area of about 200 m2/g (Evonik Industries, Horsham PA), treated in an Osterizer kitchen blender for 10 minutes at room temperature with 10g of tridecafluoro tetrahydroctyl trichloro silane. A
second set of plates is also treated with a second component as in Example 1, using silica from the same supplier prepared in a larger batch using 5,000 g of the silica reacted with tridecafluoro tetrahydroctyl trichloro silane 2,500 g in a 10 kg reactor system at room temperature for 2-3 hours. In this example, after top coats are applied the plates are dried for 15 minutes at 170 F
(77 C). Two plates treated with fumed silica prepared in the blender and two plates treated with fumed silica prepared in the reactor are subjected to thickness and surface roughness measurements. The point at which the plates lose superhydrophobic behavior is also determined using Taber Abraser equipped with CS-0 wheels at a 1,000 g load and using glove rub testing.
Loss of superhydrophobic behavior is deemed to be the point at which more than half of the water droplets applied to the tested portion of a substantially planar surface inclined at 5 degrees from the horizontal do not roll off the plate.
Data on plates coated with fumed silica particles prepared in the blender is summarized in Table 7, and data on plates treated with fumed silica prepared in the reactor is shown in Table 8.
Table 7 Blender Grade NPT 74 Coating Ra Coating Ra Thickness (mils) Thickness (mils) Sample #1 Sample #1 Sample #2 Sample #2 0.73 2.61 1.1 3.267 0.67 2.66 1.01 3.337 0.49 0.82 0.76 1.08 Avg 0.6625 2.635 1.0025 3.302 Glove Rubs 600 Taber Abraser cycles to loss of SH 50 Table 8 Reactor Grade NPT 74 Coating Ra Coating Ra Thickness (mils) Thickness (mils) Sample #1 Sample #1 Sample #2 Sample #2 0.92 3.246 1.07 3.027 1.35 3.259 0.94 2.35 0.88 0.86 1.01 0.88 Avg 1.04 3.2525 0.9375 2.6885 Glove Rubs 900 Taber Abraser cycles to loss of SH 30 The data in Tables 7 and 8 indicate that superhydrophobic coatings prepared with fumed silicas produced in reactors on different scales display similar properties.
Example 4 Transparency and Haze Glass plates are coated with a near transparent coating based on elastomeric binder systems as in Example 1 with the exception that the plate marked P does not include first particles (EXPANCEL particless) in the base coat (first component). The plate marked SE-1 contains 0.1% of EXPANCEL particles in the first component. Samples are tested for Haze value and Total Luminous Transmittance (TLT) values using the method described in ASTM
D1003. The instrument is calibrated without a sample present using air as a standard.
Calibration values are TLT = 100 and Haze = 0. Clear, clean, uncoated glass plates have average readings of TLT = 90.6 and a haze reading of 0.18. Plates lacking first particles (P-coat) have about the same transparency as clear clean glass. The presence of EXPANCEL
particles in the base coat reduces the transparency by about 10%. The coating haze increases from about 0.18 for glass to about 61% for coatings without first particles and to about 90% for coatings including EXPANCEL particles in the base coating. See Table 9.
Table 9 P-Coat Sample Reading 1 Reading 2 Reading 3 Average Readings (no first particles) Transmittance 90.50 90.30 90.40 90.4 Haze 60.70 62.40 60.80 61.30 P-Coat Sample Reading 1 Reading 2 Reading 3 Average Readings (no first particles) SE-1 Sample (first particles included in the base coat) Transmittance 80.00 79.10 80.10 79.73 Haze 88.60 90.80 89.30 89.57 Example 5 Effect of Coating Thickness Six aluminum plates (10 cm x 10 cm) are primed with PLASTI DIP primer for metal (product f938 hp). Pairs of the primed plates are spray coated with first component as in Example 1(0.1% EXPANCELs) to achieve a base coat thicknesses of about 1, 1.5, or 2.6 ml respectively. One plate at each coating thickness is top coated with 2 ml of the second component as described in Example 1, and the second plate at each coating thickness is top coated with 4 ml of second component. Coating thicknesses, which include the primer thickness, and Taber Abraser data are summarized in Table 10A and data is plotted in Figure 7.
Table 10A Data summary for plates made with varying coating thicknesses Volume of Passes of Final Tabers (CS-10) Topcoat Base Thickness to end of super-Sample (mL) Coat (mil) hydrophobicity Notes some 1.1 2 1 0.55 35 tearing 2.1 2 3 1.5 35 no tearing 3.1 2 5 2.6 35 no tearing some 1.2 4 1 0.9 45 tearing 2.2 4 3 2.2 50 no tearing 3.2 4 5 2.9 50 no tearing Based on the data above, 2 ml of top coat (0.02 ml/cm2) produces no benefits in performance improvement at any thickness. However, when the top coat is increased to 4 ml (0.04 ml/cm2), it provides an adequate performance that increases with coating thickness. While not wishing to be bound by any theory, it appears that at the higher application rate the top coat penetrates to some depth into the base coat. When only 2 ml (0.02 ml/cm2) is applied the coating may be sufficient to just cover the base coat, but not enough to permit the second particles to penetrate at any significant level that will increase the durability of SH performance.
In addition, when the base coat is very thin, tearing becomes the failure mode.
Example 6 Effect of Priming with Polyurethane Primer Aluminum plates are primed with a two-part polyurethane coating (DESMOPHEN
670BA with DESMODUR N75 BA-XBMS, Bayer Material Science) prepared and applied per manufacturer's instructions. An elastomeric coating as described in Example 1(0.1% of EXPANCEL 461 DET d25) is employed in the first component. Coated plates are measured for coating thickness (including primer thickness) and their ability to resist the loss of superhydrophobic behavior using a Taber Abraser fitted with CS-10 (abrasive) wheels and CS-0 (soft rubber) wheels at a 1,000 g load is recorded. All end points for loss for superhydrophobic behavior are measured for water droplet roll off with the plates inclined at 5 degrees from the horizontal (5 degree tilt angle). Test data is summarized in Table 10B.
Table 10B Summary of data on Al plates primed with two-part polyurethane as primer Sample 1 2 3 Total Coating Total Coating Total Coating and Primer and Primer and Primer Thickness(mils) Thickness (mils) Thickness (mils) 3.25 3.13 4.7 3.13 3.06 4.9 3 3.1 4.16 3.32 3.45 4.24 4.15 4.01 4.47 Avg Thickness 3.37 3.35 4.494 CS-10 Wheel CS-0 Wheel Glove Rubs Tabers CS-10 40 Tabers CS-0 40 Glove Rubs >1000 Example 7 Nearly Transparent HP/OP Elastomeric Coating with Various First Particles Elastomeric coatings are prepared on aluminum test plates as described in Example 1, with the exception that the first component contains first particles as indicated in Table 11. The test plates are assessed for loss of superhydrophobic behavior using glove rubs as a rapid test for assessment of handleabilty and abrasion resistance/durability. Test data for all coated plates are summarized in Table 11.
Table 11 Summary of data for non near transparent elastomeric binder system based coatings Taber Abraser Particle Amount Glove Predicted Particle Particle Size weight Rubs cycles with Designation Type (micron) (%) (#s) CS-0 wheel*
Thermoplastic EXPANCEL Encapsulated with DET gas 10-40 0.01 100 22 Thermoplastic EXPANCEL Encapsulated with DET gas 10-40 0.1 750 167 Thermoplastic EXPANCEL Encapsulated with DET gas 10-40 0.5 400 89 Hollow Glass Spheres Hollow glass K25 spheres 25-90 0.5 800 178 Hollow Glass Spheres Hollow glass K46 spheres 15-70 0.5 >400 >89 *Projected based on GR/CS-0=4.5 Thermoplastic particles and hollow glass particles yield similar performance in increasing coating durability.
Example 8 Non-Transparent Elastomeric Coatings Prepared with Micronized Rubber First Particles PLASTI DIP (24% solids by weight) elastomeric coating (5 parts by weight of the liquid as provided by the supplier) is combined with seven parts by weight of xylene and mixed. To the resulting mixture of elastomer and xylene, micronized rubber particles (Lehigh Technology, Tucker, Georgia) about 4% or about 7.7% by weight are added to separate aliquots (based on the weight of the elastomer and xylene combined). The particles are mixed into each aliquot to form first component compositions. The first component compositions are applied to separate aluminum plates to form base coats, and the base coats are top coated with a second component as described in Example 1.
Test data showing resistance to the loss of superhydrophobicity based on glove rub testing and Taber testing for the coatings incorporating rubber particles is provided in Table 12.
That data shows the incorporation of elastomeric binder used in this example with micronized rubber particles produces highly durable surfaces that show increasing resistance to the loss of hydrophobicity with increasing amounts of rubber first particles incorporated into the binder up to at least 7.69%.
Table 12 Summary of data on non near transparent elastomeric binder based coatings Particle Particle Particle Amount Glove Taber Abraser Designation Type Size (i.tm) weight (%) Rubs (#s) cycles with CS-0*
Ground Micronized Rubber Rubber particles 70 4 1450 191 Ground Micronized Rubber Rubber particles 70 7.69 1800 237 *Projected based on GR/CS-0 wheel ratio of 7.6 for a 250 g load at 95 rpm.
Example 9 Non-Transparent Elastomeric Coating with Micronized Rubber Particles with and without Primer Elastomeric coatings are prepared as in Example 8 employing 7.69% of micronized rubber by weight in the first component. The coatings are applied to clean but unprimed aluminum plates or aluminum plates that have been treated with an elastomeric metal primer (PLASTI DIP metal primer) per the manufacturer's instructions. All plates are substantially planar. The top coating step is the same as in Example 8 and Example 1. The coated plates are assessed for resistance to the loss of SH behavior using a Taber Abraser fitted with CS-0 wheels or CS-10 wheels (as indicated) using 1,000 g loads at 95 rpm, resistance to the loss of SH
behavior using glove rubs, and coating thickness, which is measured including primer where present. The appearance of coating failures is also recorded for each plate and the data set forth in Table 13.
Table 13 Observations from Taber Abraser Testing of Plates With and Without Primer Coating Without Primer without primer Coating Thickness (mil) Comments Taber CS-0 6 cycles 1.5 Rips and Tears Taber CS-10 10 cycles 1.5 Rips and Tears Glove Rubs 1200 1.5 No Rips or Tears With primer Coating With Elastomeric Primer with elastomeric primer Coating Thickness (mil) Comments Taber CS-0 50 cycles 1.75 No Rips or Tears Taber CS-10 40 cycles 1.65 No Rips or Tears Glove Rubs 1600 1.75 No Rips or Tears The data indicates that samples with and without primer resist the loss of superhydro-phobicity with a very large number of glove rubs. Taber Abraser testing results in a loss of that property due to ripping and/or tearing of the coating in the absence of primer. Loss of super-hydrophobic behavior is assessed using the above-described droplet run off test with plates inclined at 5 degrees from the horizontal. Priming of the metal surfaces increases the number of Taber cycles the test samples can withstand without losing superhydrophobic behavior by about 4 to about 8 fold, regardless of whether non-abrasive rubber (CS-0) or abrasive (CS-10) wheels are employed.
Example 10 Thermal Stability of Elastomeric Coatings Elastomeric coatings incorporating EXPANCELs as in Example 1, or micronized rubber as in Example 8, are scraped from their plates and used for thermogravimetric analysis (TGA).
TGA data for the coatings is plotted in Figures 10 and 11, respectively.
Details of the test conditions are listed inside each of the graphs. Data from these charts show the following:
1. The coating containing EXPANCEL is stable up to 241 C (465 F) 2. The coating containing micronized rubber is stable up to 261 C (502 F) Based upon the data presented above the coatings may be used up to temperatures of 200 C or 400 F.
Example 11 HP/OP Coatings Employing Varying Proportions of a Styrenic Block Copolymer and Tackifier Three styrenic block copolymers (SBCs), FG 1901, FG 1924 and RP 6670, each obtained from KRATON , are dissolved in xylene at 20% by weight. RegalrezTM
tackifier, obtained from Eastman Chemical Company, is dissolved in xylene at 20% by weight.
Varying ratios of SBCs and tackifier solutions are mixed and UV stabilizers and antioxidants, 0.1% Irganox 1520L, 0.056% Tinuvin 328, and 0.056% Tinuvin 770DF (% by weight), are added.
Each of the mixtures of SBCs and tackifier formed is used as a first component and HP/OP coatings are prepared as in Example 1, using 0.1% EXPANCEL particles as first particles. The HP/OP coatings were tested for durability using a Taber Abraser equipped with CS-10 wheels and a 1,000 g load. The results are shown in Table 14.
Table 14 FG 1901/Regalrez 1094 FG 1924/Regalrez 1094 RP 6670/Regalrez Glove Taber Glove Taber Glove Taber Ratio Rubs cycles Ratio Rubs cycles Ratio Rubs cycles * 800 20 50/50 750 45 * 350 35 *
* 600 25 * 600 25 * Taber testing induced tearing.
Example 12 HP/OP Coatings Employing Maleated Styrene-Ethylene/Butylene-Styrene (SEBS) Block Copolymers Coatings were prepared using first components comprising maleated SBCs (e.g., maleated SEBS block copolymers) Table 15 Base Coat Total Component Exemplary Composition Component Parts by Weight Components (Total of 100 parts) (By weight where given) Maleated SBC 7 to 9 One or more maleated Styrene-Ethylene/Butylene-Styrene (SEBS) Block Copolymers (e.g., Kraton FG 1901, FG 1924 and/or RP 6670*
) Tackifier 3.5 to 7 Nonpolar hydrogenated hydrocarbon resin (e.g., produced by polymerization and hydrogenation of monomeric hydrocarbons) or esterified hydrogenated rosin.
e.g., Eastman RegalrezTM 1094 or ForalTM 105E
Antioxidant(s) 0.05 to 0.2 Antioxidant(s) (e.g., phenolic or hindered phenolic antioxidants e.g., Irganox 1520L
First Particles 0.05 to 20 Expancel 461 DET 40 d25 (0.05-0.2%) SoftSand 5-15%
Glass bubbles (e.g., Kl, S22, or A16/500) 1%-10%
UV stabilizer(s) 0.05 to 0.5 e.g., Tinuvin 328 and/or 770DF
Solvent Bring to 100 parts xylene (or mixed xylenes), acetone, n-hexane (or total including all mixed hexanes), 1-chloro-4-(trifluoromethyl)-other components benzene or mixtures thereof
63 Base Coat Total Component Exemplary Composition Component Parts by Weight Components (Total of 100 parts) (By weight where given) Top Coat Parts by weight Source Component Reactor Grade 0.05 to 6.0 (e.g., 2%) Ross Technology -- see Example 3 Solvent Bring to 100 parts by xylene (including mixed xylenes or technical weight total including grade), acetone, n-hexane (or mixed hexanes), 1-all other components chloro-4-(trifluoromethyl)-benzene or mixtures thereof = RP 6670 is a maleated form of KRATON series A polymers, which are hydrogenated block copolymers having styrene copolymerized with ethylene/butylene in the midblock (S-(EB/S)-S).
Styrenic block copolymers (SBCs FG 1901, FG 1924 and RP 6670, each obtained from KRATON ), tackifier (RegalrezTM 1094 or FORALTM 105E obtained from Eastman Chemical Company), UV
stabilizers (e.g., Tinuvin 328 and/or 770DF from BASF), antioxidants (e.g., frganox 1520L) and first particles are dissolved/suspended in solvent using solvent to adjust the total components by weight to 100 parts.
The HP/OP coatings were tested for durability using a Taber Abraser equipped with CS-wheels and a 1,000 g load. The results are shown in Table 14.
Styrenic block copolymers (SBCs FG 1901, FG 1924 and RP 6670, each obtained from KRATON ), tackifier (RegalrezTM 1094 or FORALTM 105E obtained from Eastman Chemical Company), UV
stabilizers (e.g., Tinuvin 328 and/or 770DF from BASF), antioxidants (e.g., frganox 1520L) and first particles are dissolved/suspended in solvent using solvent to adjust the total components by weight to 100 parts.
The HP/OP coatings were tested for durability using a Taber Abraser equipped with CS-wheels and a 1,000 g load. The results are shown in Table 14.
64
Claims (62)
1. A combination of components for forming a coating comprising:
A) a first component which comprises:
i) an elastomeric binder comprising one or more styrenic block copolymers, wherein said elastomeric binder comprises from about 1% to about 30% of said one or more styrenic block copolymers by weight;
ii) optionally, one or more independently selected first particles having a size of about 30 microns to about 225 microns, wherein, when said first particles are present, the first component comprises from about 0.01% to about 5%
of said first particles by weight; and iii) one or more solvents; and B) a second component which comprises either:
i) one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, and ii) optionally, one or more solvents;
or a second component which comprises per 100 parts by weight:
i) 0.1 to 3.5 parts by weight of one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with said second particles;
ii) 0.1 to 1.0 parts by weight of a fluorinated polyolefin;
and/or 0.06 to 0.6 parts by of a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, having an average molecular weight of about 1,000 to 3,000;
and iii) one or more solvent for a the remainder of a total of 100 parts by weight.
A) a first component which comprises:
i) an elastomeric binder comprising one or more styrenic block copolymers, wherein said elastomeric binder comprises from about 1% to about 30% of said one or more styrenic block copolymers by weight;
ii) optionally, one or more independently selected first particles having a size of about 30 microns to about 225 microns, wherein, when said first particles are present, the first component comprises from about 0.01% to about 5%
of said first particles by weight; and iii) one or more solvents; and B) a second component which comprises either:
i) one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, and ii) optionally, one or more solvents;
or a second component which comprises per 100 parts by weight:
i) 0.1 to 3.5 parts by weight of one or more independently selected second particles having a size of about 1 nanometer to about 25 microns, wherein said second particles comprise one or more independently selected alkyl, haloalkyl, or perfluoroalkyl moieties bound, either directly or indirectly, to said second particles, or one or more siloxanes or silazanes associated with said second particles;
ii) 0.1 to 1.0 parts by weight of a fluorinated polyolefin;
and/or 0.06 to 0.6 parts by of a Fluoroethylene-Alkyl Vinyl Ether (FEVE) copolymer, having an average molecular weight of about 1,000 to 3,000;
and iii) one or more solvent for a the remainder of a total of 100 parts by weight.
2. The combination of claim 1, wherein one or more of the styrenic block copolymers has a rubber phase crosslinked to the polystyrene phase.
3. The combination according claim 1, wherein one or more of the styrenic block copolymers has a rubber phase comprising polybutadiene, polyisoprene, polyolefin or a mixture of any of those rubber phase components (e.g., linear triblock copolymers of styrene and ethylene/butylene with a polystyrene content of about 8% to about 36% by weight or mixtures of any two or more, three or more, or four or more of such triblock copolymers, any one or more of which may optionally comprise 1% to 3% or 1.4% to 2.0 %
maleic anhydride).
maleic anhydride).
4. The combination according to claim 2, wherein said rubber component comprises 60%-98%, of the elastomer by weight, based on the dry weight of the elastomer present in the first component not including any contribution by the first particles or other materials present in the first component.
5. The combination according to claim 1, wherein said first component further comprises one or more colorants, UV stabilizers, antioxidants, rheological agents, and/or fillers.
6. The combination according to claim 1, wherein said first component further comprises up to 30% by weight of one or more tackifiers.
7. The combination of claim 6, wherein said one or more styrenic block copolymers and said one or more tackifiers together comprise up to about 30% by weight of said first component.
8. The combination according to claim 1, wherein said elastomeric binder comprises one, two, three, or more triblock copolymers.
9. The combination according to claim 1, wherein said elastomeric binder comprises one or more styrenic block copolymers of styrene and ethylene/butylene with a polystyrene content of about 8% to about 36% by weight, or mixtures of any two or more, three or more, or four or more of such triblock copolymers.
10. The combination according to claim 1, wherein one or more of said styrenic block copolymers present in the elastomeric binder comprise maleic anhydride.
11. The combination according to claim 1, wherein at least one, or at least two, of said one or more styrenic block copolymers is a linear copolymer or a branched copolymer.
12. The combination according to claim 1, wherein the elastomeric binder comprises a first and a second maleated triblock copolymer of styrene and ethylene/butylene wherein:
said first maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content from about 8% to about 14%, with 0.4% to 1.6% substitution of maleic anhydride by weight of the first triblock copolymer; and said second maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content of about 22% to about 32%, with 1.1% to 2.5% substitution of maleic anhydride by weight of the second triblock copolymer.
said first maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content from about 8% to about 14%, with 0.4% to 1.6% substitution of maleic anhydride by weight of the first triblock copolymer; and said second maleated triblock copolymer of styrene and ethylene/butylene has a polystyrene content of about 22% to about 32%, with 1.1% to 2.5% substitution of maleic anhydride by weight of the second triblock copolymer.
13. The combination of claim 12, wherein said first and/or second triblock copolymers are independently selected linear or branched
14. The combination according to, wherein said first and second triblock copolymers may be present in a weight ratio from about 4:1 to about 6.5:1.
15. The combination according to claim 1, wherein said first particles are selected from the group consisting of: glass, ceramic, rubber, plastic, thermoplastic, wood, cellulose, metal oxides, silicon dioxide, silicates, tectosilicates, germanium dioxide, plastic particles, carbide particles, nitride particles, boride particles (e.g., zirconium or titanium boride), spinel particles, diamond particles, fly ash particles, fibers and hollow glass spheres, hollow glass particles or hollow plastic particles (e.g., glass, polymer, plastic or thermoplastic particles, spheres, or microspheres), wherein said first particles optionally comprise a colorant (e.g., colored or pigmented glass particles, plastic particles, rubber particles, hollow glass or hollow plastic particles).
16. The combination according to claim 1, wherein said first particles comprise hollow glass or plastic particles, and wherein said first particles optionally comprise a colorant.
17. The combination according to claim 16, wherein said hollow glass or hollow plastic particles have a size (average diameter) in a range selected from the group consisting of 5 to 50 microns, 6 to 45 microns, 5 to 20 microns, 20 to 35 microns, and 35 to 50 microns.
18. The combination according to claim 15, wherein said hollow plastic particles have a density selected from the group consisting of less than 60 kg/m3, less than 50 kg/m3, less than 40 kg/m3, less than 30 kg/m3, or less than 25 kg/m3, and wherein said hollow glass particles have a density selected from the group consisting of less than 125 kg/m3, less than 150 kg/m3, less than 200 kg/m3, less than 250 kg/m3, less than 300 kg/m3, less than 350 kg/m3, less than 400 kg/m3, less than 450 kg/m3, less than 500 kg/m3, less than 550 kg/m3, less than 600 kg/m3, or 600 kg/m3.
19. The combination according to claim 1, wherein the second particles have an average size in a range selected from the group consisting of from: about 1 nm to about 100 nm;
about 10 nm to about 200 nm; about 20 nm to about 400 nm; about 10 nm to 500 nm; about 40 nm to about 800 nm; about 100 nm to about 1 micron; about 200 nm to about 1.5 microns; about 500 nm to about 2 microns; about 500 nm to about 2.5 microns; about 1 micron to about 10 microns; about 2 microns to about 20 microns; about 2.5 microns to about 25 microns; about 500 nm to about 25 microns; about 400 nm to about 20 microns; and about 100 nm to about 15 microns.
about 10 nm to about 200 nm; about 20 nm to about 400 nm; about 10 nm to 500 nm; about 40 nm to about 800 nm; about 100 nm to about 1 micron; about 200 nm to about 1.5 microns; about 500 nm to about 2 microns; about 500 nm to about 2.5 microns; about 1 micron to about 10 microns; about 2 microns to about 20 microns; about 2.5 microns to about 25 microns; about 500 nm to about 25 microns; about 400 nm to about 20 microns; and about 100 nm to about 15 microns.
20. The combination according to claim 1, wherein said second particles comprise a metal oxide, an oxide of a metalloid, a silicate, or a glass.
21. The combination according to claim 1, wherein said second particles are comprised of silica and have an average size of about 1 nm to about 500 nm.
22. The combination according to claim 1, wherein said second particles have an average size in the range of from 1 nm to 100 nm or from 2 nm to 200 nm.
23. The combination according to claim 1, wherein said second particles comprise one or more hydrophobic and/or oleophobic moieties.
24. The combination according to claim 1, wherein said second particles comprise one or more alkyl, fluoroalkyl, and/or perfluoroalkyl moieties that are covalently bound to the second particles directly, or bound indirectly through one or more atoms bound to the second particles.
25. The combination according to claim 1, wherein said one or more hydrophobic or oleophobic moieties result from contacting the second particles with one or more silanizing agents of formula (I):
R4Si-X n (I) where n is an integer from 1 to 3;
each R is independently selected from (i) alkyl or cycloalkyl group optionally substituted with one or more fluorine atoms, (ii) C1 to 20 alkyl optionally substituted with one or more substituents independently selected from fluorine atoms and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, C1 to 10 haloalkyl, C1 to 10 alkoxy, or C1 to 10 haloalkoxy substituents, (iii) C2 to 8 or C6 to 20 alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, C1 to 10 haloalkyl, C1 to 10 alkoxy, or C1 to 10 haloalkoxy substituents, (iv) C6 to 14 aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents, (V) C4 to 20 alkenyl or C4 to 20 alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy, and (vi) -Z-((CF2)q(CF3))r, wherein Z is a C1 to 12 or a C2 to 8 divalent alkane radical or a C2 to 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4;
each X is independently selected from -H, -Cl, -I, -Br, -OH, -OR2, -NHR3, or -N(R3)2 group;
each R2 is an independently selected C1 to 4 alkyl or haloalkyl group; and each R3 is an independently selected H, C1 to 4 alkyl, or haloalkyl group.
R4Si-X n (I) where n is an integer from 1 to 3;
each R is independently selected from (i) alkyl or cycloalkyl group optionally substituted with one or more fluorine atoms, (ii) C1 to 20 alkyl optionally substituted with one or more substituents independently selected from fluorine atoms and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, C1 to 10 haloalkyl, C1 to 10 alkoxy, or C1 to 10 haloalkoxy substituents, (iii) C2 to 8 or C6 to 20 alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C6 to 14 aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C1 to 10 alkyl, C1 to 10 haloalkyl, C1 to 10 alkoxy, or C1 to 10 haloalkoxy substituents, (iv) C6 to 14 aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents, (V) C4 to 20 alkenyl or C4 to 20 alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy, and (vi) -Z-((CF2)q(CF3))r, wherein Z is a C1 to 12 or a C2 to 8 divalent alkane radical or a C2 to 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4;
each X is independently selected from -H, -Cl, -I, -Br, -OH, -OR2, -NHR3, or -N(R3)2 group;
each R2 is an independently selected C1 to 4 alkyl or haloalkyl group; and each R3 is an independently selected H, C1 to 4 alkyl, or haloalkyl group.
26. The combination according to claim 25, wherein each R is selected independently from:
(a) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms;
(b) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms;
(c) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms;
(d) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms when n is 2 or 3;
(e) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms when n is 2 or 3;
and (f) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms when n is 2 or 3.
(a) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms;
(b) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms;
(c) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms;
(d) an alkyl or fluoroalkyl group having from 6 to 20 carbon atoms when n is 2 or 3;
(e) an alkyl or fluoroalkyl group having from 8 to 20 carbon atoms when n is 2 or 3;
and (f) an alkyl or fluoroalkyl group having from 10 to 20 carbon atoms when n is 2 or 3.
27. The combination according to claim 25, wherein R is -Z-((CF2)q(CF3))r, wherein Z is a C1 to 12 divalent alkane radical or a C2 to 12 divalent alkene or alkyne radical, q is an integer from 1 to 12, and r is an integer from 1 to 4.
28. The combination according to claim 25, wherein n is 1, 2, or 3.
29. The combination according to claim 25, wherein all halogen atoms present in any one or more R groups are fluorine atoms.
30. The combination according to claim 25, wherein each X is independently selected from -H, -Cl, -OR2, -NHR3, and -N(R3)2.
31. The combination according to claim 25, wherein each X is independently selected from -Cl, -OR2, -NHR3, and -N(R3)2.
32. The combination according to claim 25, wherein each X is independently selected from -Cl, -NHR3, and -N(R3)2.
33. The combination according to claim 1, wherein two, three, four, or more than four compounds of formula (I) are employed alone or in combination to modify at least one second particle.
34. The combination according to claim 1, wherein said second particles are treated with a silanizing agent selected from the group consisting of: tridecafluoro-1,1,2,2-tetrahydrooctyl)silane ; (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane; n-octadecyltrimethoxysilane; n-octyltriethoxysilane; and nonafluorohexyldimethyl(dimethylamino)silane.
35. The combination according to claim 1, wherein said second particles are treated with a silanizing agent selected from the group consisting of dimethyldichlorosilane, hexamethyldisilazane, octyltrimethoxysilane, polydimethylsiloxane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane.
36. The combination according to claim 1, wherein said first component and/or said second component further comprise an independently selected solvent and/or propellant.
37. The combination of claim 36, wherein said solvent is an organic solvent or a mixture of two or more organic solvents, and wherein either said organic solvent or said mixture of two or more organic solvents comprises less than 2%,of water by weight.
38. The combination of claim 36, wherein said solvent or propellant comprises any one, two, three or more of air, nitrogen, an inert gas, an alkane, a ketone, an ether, a halogenated alkane, a halogenated alkene, an aromatic hydrocarbon, an alcohol, methane, ethane, propane, butane, pentane, hexane, heptane, ethylene, propene, acetone, methyl isobutyl ketone (MIKB), methyl ethyl ketone (MEK), dimethylether (DME), diethylether, methyl ethyl ether, methyl tert¨butyl ether, chloromethane, dichloromethane, carbontetrachloride, trichlorofluoromethane, dichlorodifluoromethane, methanol, ethanol, propanol, butanol, benzene, toluene, xylene, 1-chloro-4-(trifluoromethyl)-benzene, carbon disulfide, and isomers of any of the foregoing, based upon the total weight of solvent or propellant present in the composition.
39. The combination according to claim 1, wherein either the first component and/or second component further comprise a colorant or pigment.
40. The combination according to any of claims 1 to 39, wherein said elastomeric binder has an ultimate strength greater than about 20 Mega Pascals (MPa) according to ASTM
D412.
D412.
41. A method of forming a hydrophobic coating on a portion of a surface comprising the following steps:
(a) applying a first component according to any of claims 1 to 40 to at least a portion of the surface, wherein the portion of the surface has optionally been treated with a primer on all or part of the surface to which said first component is to be applied ;
and (b) applying a second component according to any of claims 1 to 40 to all or a portion of the portion coated in step (a), wherein said coating has either hydrophobic or superhydrophobic properties, and optionally is also oleophobic or superoleophobic.
(a) applying a first component according to any of claims 1 to 40 to at least a portion of the surface, wherein the portion of the surface has optionally been treated with a primer on all or part of the surface to which said first component is to be applied ;
and (b) applying a second component according to any of claims 1 to 40 to all or a portion of the portion coated in step (a), wherein said coating has either hydrophobic or superhydrophobic properties, and optionally is also oleophobic or superoleophobic.
42. The method of claim 41, wherein said steps of applying said first component and applying said second component are conducted by methods selected independently from painting, printing, stamping, rolling, dipping, spin-coating, spraying, and electrostatic spraying.
43. A coating prepared by the method according to claim 41.
44. The coating of claim 43, wherein said coating is superhydrophobic and/or superoleophobic.
45. The coating according to claim 43, wherein said coating has an ultimate strength greater than about 20 mega Pascals (MPa) according to ASTM D412.
46. The coating according to any claim 43, wherein said coating has a modulus at 100%
elongation of greater than 10, mega Pascals (MPa)) according to ASTM D412.
elongation of greater than 10, mega Pascals (MPa)) according to ASTM D412.
47. The coating according to claim 43, having an elongation at break of greater than about 200%.
48. The coating according to claim 43, having a relative electrical permittivity at 100 MHz from about 0.2 to about 4 at about 22° C as measured by ASTM D150 using a 0.11 mm thick film.
49. The coating according to claim 43, having a Total Luminous Transmittance of about 75% to about 85% and a haze of about 85% to about 90% as measure by ASTM D1003-11 on a film about 25 microns thick.
50. The coating according to claim 43, wherein said coating is superhydrophobic and retains its superhydrophobicity after being subjected to greater than 20, cycles on a Taber Abraser using CS-0 or CS-10 wheels and a 250 gram load at room temperature, wherein the end of superhydrophobicity is determined to be the point when more than half of the water droplets applied to the portion of the surface subject to the action of the wheels do not roll off the surface when the surface is inclined at a 5 degree angle at room temperature.
51. The coating according to claim 50, wherein said coating retains its superhydrophobicity after being subjected to greater than 20 cycles on a Taber Abraser using CS-0 or CS-10 wheels and a 1,000 gram load at 20° C -25° C, wherein the end of superhydrophobicity is determined to be the point when more than half of the water droplets applied to the portion of the surface subject to the action of the wheels do not roll off the surface when the surface is inclined at a 5 degree angle at room temperature.
52. The coating according to claim 43, wherein said coating is superhydrophobic and when said coating is applied to a planar surface, it continues to display superhydrophobic behavior after being subjected to a continuous shower test of about six liters of water per minute at about 20° C-25° C for greater than 0.3 hours, wherein the duration of superhydrophobic behavior is determined to be the time when more than half of the water droplets applied to a portion of the surface subject to said shower do not roll off the surface when it is inclined at a 5 degree angle at room temperature, wherein the shower test is conducted using a showerhead with 70 nozzles with a Ii mm diameter orifice arranged in 5 spokes of 5 nozzles and 15 spokes of 3 nozzles about a central point on a circular showerhead, and wherein the showerhead delivers approximately 6 liters of potable tap water per minute using about 137900 Pa (Pascals) to 310275 PA, and wherein the coating is placed about 1.5 meters below the showerhead.
53. The coating of claim 52, wherein, when said coating is subjected to said continuous shower test for a period of time sufficient to lose superhydrophobic behavior, the coating regains superhydrophobic behavior following drying at 20° C to 25° C and one atmosphere of pressure, said shower testing and drying collectively comprising a single test cycle.
54. The coating of claim 53, wherein said coating regains superhydrophobic behavior following more 20 of said test cycles.
55. A method according to claim 41, wherein applying according to step (b) is repeated to at least a portion of the coated surface if that portion of the coated surface loses said hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties, and wherein following the repetition of step (b), the coated portion regains hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties.
56. A method according to claim 41, wherein both steps (a) and (b) are repeated on at least a portion of the coated surface if that portion of the coated surface loses said hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties, and wherein following the repetition of steps (a) and (b), the coated portion regains hydrophobic, superhydrophobic, oleophobic and/or superoleophobic properties.
57. A coated surface, or a portion thereof, resulting from the process of claim 55 .
58. A product comprising an aerosol spray container containing a first component according to any of claims 1 to 40 and a propellant.
59. The product of claim 58, wherein the aerosol spray container comprises a valve assembly, a dip tube, and an actuator.
60. A product comprising an aerosol spray container containing a second component according to any of claims 1 to 40 and a propellant.
61. The product of claim 60, wherein the aerosol spray container comprises a valve assembly, a dip tube, and an actuator.
62. A product comprising:
an aerosol spray container containing a first component according to any of claims 1 to 40 and a propellant; and an aerosol spray container containing a second component according to any of claims 1 to 40 and a propellant.
an aerosol spray container containing a first component according to any of claims 1 to 40 and a propellant; and an aerosol spray container containing a second component according to any of claims 1 to 40 and a propellant.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261663985P | 2012-06-25 | 2012-06-25 | |
US61/663,985 | 2012-06-25 | ||
US201261708760P | 2012-10-02 | 2012-10-02 | |
US61/708,760 | 2012-10-02 | ||
US201361768290P | 2013-02-22 | 2013-02-22 | |
US61/768,290 | 2013-02-22 | ||
PCT/US2013/031751 WO2014003852A2 (en) | 2012-06-25 | 2013-03-14 | Elastomeric coatings having hydrophobic and/or oleophobic properties |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2878189A1 true CA2878189A1 (en) | 2014-01-03 |
CA2878189C CA2878189C (en) | 2021-07-13 |
Family
ID=49783982
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2878189A Active CA2878189C (en) | 2012-06-25 | 2013-03-14 | Elastomeric coatings having hydrophobic and/or oleophobic properties |
Country Status (8)
Country | Link |
---|---|
US (2) | US9388325B2 (en) |
EP (1) | EP2864430A4 (en) |
CN (1) | CN104520392A (en) |
AU (1) | AU2013281220B2 (en) |
BR (1) | BR112014032676A2 (en) |
CA (1) | CA2878189C (en) |
MX (1) | MX2015000119A (en) |
WO (1) | WO2014003852A2 (en) |
Families Citing this family (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010042668A1 (en) | 2008-10-07 | 2010-04-15 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
EP2547832A4 (en) | 2010-03-15 | 2016-03-16 | Ross Technology Corp | Plunger and methods of producing hydrophobic surfaces |
PE20140834A1 (en) | 2011-02-21 | 2014-07-10 | Ross Technology Corp | SUPERHYDROPHIC AND OLEOPHOBIC COATING WITH BINDERS SYSTEM WITH LOW VOC CONTENT |
WO2013090939A1 (en) | 2011-12-15 | 2013-06-20 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
CA2878189C (en) | 2012-06-25 | 2021-07-13 | Ross Technology Corporation | Elastomeric coatings having hydrophobic and/or oleophobic properties |
CA2925495A1 (en) * | 2013-09-26 | 2015-04-02 | Ross Technology Corporation | Flexible superhydrophobic and/or oleophobic polyurethane coatings |
AR099038A1 (en) | 2014-01-08 | 2016-06-22 | General Cable Tech Corp | COVERED AIR CONDUCTOR |
BR112017002151A2 (en) * | 2014-08-05 | 2018-07-03 | Gen Cable Technologies Corp | fluorine coatings copolymers for air conductors |
MX2017004121A (en) * | 2014-09-29 | 2017-07-07 | Nano Tech Innovations Corp | Nano-engineered, halogen-free, super omniphobic coatings. |
CN104745045A (en) * | 2015-04-14 | 2015-07-01 | 广州希森美克新材料科技有限公司 | Super-hydrophobic and oleophobic composite coating and preparation method thereof |
US20160331091A1 (en) * | 2015-05-13 | 2016-11-17 | Corey J. Hall | Sleeve Wallet |
CN106280930A (en) * | 2015-06-11 | 2017-01-04 | 上海福岛化工科技发展有限公司 | Water alcohol acid aerosol finish paint and preparation method thereof |
CN104877564A (en) * | 2015-06-15 | 2015-09-02 | 安徽中恩化工有限公司 | Super-hydrophobic oil-proof self-cleaning aerosol and preparation method thereof |
WO2017007439A1 (en) * | 2015-07-03 | 2017-01-12 | Erciyes Universitesi | A superhydrophobic nanocomposite coating method |
US10221321B2 (en) | 2015-08-28 | 2019-03-05 | Battelle Memorial Institute | Paintable hydrophobic and lubricant-infused surface coatings and processes for making and using same |
US11168276B2 (en) | 2015-08-28 | 2021-11-09 | Battelle Memorial Institute | Reinforced composites with repellent and slippery properties |
CN105390180A (en) * | 2015-10-30 | 2016-03-09 | 太仓市天合新材料科技有限公司 | Novel insulating material |
CN105214602B (en) * | 2015-11-09 | 2018-02-06 | 郭鹏峰 | A kind of porous oil-absorbing material and its preparation and renovation process |
EP3374453B1 (en) | 2015-11-13 | 2020-01-08 | General Cable Technologies Corporation | Cables coated with fluorocopolymer coatings |
CN105486610B (en) * | 2015-11-22 | 2018-11-27 | 沈阳黎明航空发动机(集团)有限责任公司 | A kind of preparation and hydrophobicity performance evaluation method of hydrophobic coat |
CN105507061A (en) * | 2015-11-27 | 2016-04-20 | 湖北大学 | Superhydrophobic coating and preparation method thereof |
CN105440888B (en) * | 2015-12-17 | 2017-10-17 | 中国科学院兰州化学物理研究所 | A kind of preparation method of the super thin hot liquid coating of stabilization |
US20170182512A1 (en) | 2015-12-28 | 2017-06-29 | Swift IP, LLC | Method of applying and using viscous liquid rubber composition |
US9528005B1 (en) | 2015-12-28 | 2016-12-27 | Swift IP, LLC | Liquid rubber composition |
WO2017127500A1 (en) * | 2016-01-20 | 2017-07-27 | Battelle Memorial Institute | Stretchable hydrophobic materials and methods for making the same |
US10470513B2 (en) | 2016-03-01 | 2019-11-12 | Mips Ab | Helmet |
GB201603566D0 (en) * | 2016-03-01 | 2016-04-13 | Mips Ab | Helmet |
US10524598B2 (en) | 2016-05-03 | 2020-01-07 | Benny Green | Easily cleanable drinking assembly |
EP3452560A4 (en) * | 2016-05-04 | 2020-04-08 | General Cable Technologies Corporation | Compositions and coatings formed thereof with reduced ice adherence and accumulation |
AU2017325041A1 (en) * | 2016-09-11 | 2019-04-11 | Shenkar Engineering Design Art | Microspheres and method for producing them |
HUE064526T2 (en) | 2016-10-20 | 2024-03-28 | Gen Cable Technologies Corp | Durable coating compositions and coatings formed thereof |
WO2018106926A1 (en) * | 2016-12-08 | 2018-06-14 | Lintec Of America, Inc. | Improvements in artificial muscle actuators |
PT3601450T (en) * | 2017-03-31 | 2022-08-24 | Ppg Europe B V | Coating composition and use thereof |
US10328311B2 (en) | 2017-06-09 | 2019-06-25 | Acushnet Company | Golf ball incorporating at least one cast layer of thermoset polymer mixture having a centering time that is independent of cure time and is lower than the centering time of the thermoset polymer composition portion of the mixture |
US10427003B2 (en) | 2017-06-28 | 2019-10-01 | Acushnet Company | Golf ball having at least one layer consisting of a mixture of a thermoset or thermoplastic composition and a plurality of alkoxylated siloxane-surface treated particles and/or polyether-modified siloxane-surface treated particles |
WO2019023840A1 (en) * | 2017-07-31 | 2019-02-07 | Dow Global Technologies Llc | Ice-phobic coatings |
KR102428503B1 (en) | 2017-09-07 | 2022-08-04 | 다우 글로벌 테크놀로지스 엘엘씨 | Thermally conductive ice-phobic coating |
US10619022B2 (en) * | 2018-03-14 | 2020-04-14 | Bose Corporation | Surface treatments for wearable devices |
CN108587383B (en) * | 2018-05-07 | 2020-10-23 | 航天材料及工艺研究所 | Hydrophobic film for cork composite material surface and preparation method thereof |
CN109232946B (en) * | 2018-08-15 | 2022-03-25 | 杭州联通管业有限公司 | Anti-fouling plastic drain pipe and preparation method thereof |
US10767941B2 (en) | 2018-09-14 | 2020-09-08 | Ford Global Technologies, Llc | Method of forming a superhydrophobic layer on a motor vehicle heat exchanger housing and a heat exchanger incorporating such a housing |
WO2020056542A1 (en) * | 2018-09-17 | 2020-03-26 | Henkel Ag & Co. Kgaa | Two-part coating composition |
CN109406344A (en) * | 2018-09-18 | 2019-03-01 | 上海航天化工应用研究所 | A method of characterization azide polyethers elastomer surface and interface characteristic |
CN109486254A (en) * | 2018-10-04 | 2019-03-19 | 南京航空航天大学溧水仿生产业研究院有限公司 | Super-hydrophobic wear-resistant coating and preparation method thereof |
WO2020120006A1 (en) * | 2018-12-14 | 2020-06-18 | Merck Patent Gmbh | Surface coating compositions |
US11505704B2 (en) | 2019-05-03 | 2022-11-22 | Plz Corp. | Aerosol primer composition and method of use |
CN110452587B (en) * | 2019-08-27 | 2022-04-01 | 广西科技大学 | High-weather-resistance fluorocarbon coating and preparation method thereof |
CN111772802B (en) * | 2020-06-19 | 2023-09-19 | 南昌大学第二附属医院 | Manufacturing method of blood thinning type glove |
CN111718620B (en) * | 2020-07-10 | 2021-11-19 | 广州希森美克新材料科技股份有限公司 | Wear-resistant food-grade super-hydrophobic nano coating not stained with yoghourt |
CN111870707B (en) * | 2020-08-26 | 2023-06-02 | 成都纽瑞特医疗科技股份有限公司 | Zirconium [ 89 Zr]Carbon microsphere suspension, preparation method and application thereof |
WO2022054583A1 (en) * | 2020-09-11 | 2022-03-17 | 日本ゼオン株式会社 | Coating solution |
CN112606442B (en) * | 2020-11-25 | 2022-03-18 | 绍兴上虞明吉塑业有限公司 | Treatment process for preventing liquid from being easily stained on suction head |
CN112646485A (en) * | 2020-12-01 | 2021-04-13 | 中国矿业大学(北京) | Preparation method of hydrophobic wax-proof composite coating and hydrophobic wax-proof composite coating |
EP4019594A1 (en) | 2020-12-22 | 2022-06-29 | Christoph Dirks | Wall paint with reduced weight |
US20230151532A1 (en) * | 2021-11-18 | 2023-05-18 | Whirlpool Corporation | Functionalized surfaces for home appliances |
GB202207983D0 (en) * | 2022-05-30 | 2022-07-13 | Univ Of Northumbria At Newcastle | Methods of preparing functional surafces and surfaces prepared thereby |
CN116179043A (en) * | 2023-01-30 | 2023-05-30 | 南昌航空大学 | Super-hydrophobic drag-reducing coating, preparation method and application thereof |
CN116676002B (en) * | 2023-08-03 | 2023-10-10 | 天津天和盛新材料科技有限公司 | Self-repairing super-hydrophobic anti-reflection coating and coating |
Family Cites Families (715)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US870439A (en) | 1906-01-09 | 1907-11-05 | Charles F Kade | Adjustable bracket. |
US2191701A (en) | 1938-05-10 | 1940-02-27 | Montgomery Ward & Co Inc | Display apparatus |
US2976386A (en) | 1958-03-31 | 1961-03-21 | Lewis L Salton | Electric food warmers |
US3244541A (en) | 1961-02-03 | 1966-04-05 | 29 West Fifteenth Street Corp | Water-repellent compositions and methods of making same |
US3185426A (en) | 1961-05-03 | 1965-05-25 | Bjerke Alf Johan | Dismountable shelf supporting unit and bracket therefor |
US3980153A (en) | 1963-06-17 | 1976-09-14 | Peter Andrews | Motor vehicle oil drop pan apparatus device for indirectly saving lives and accidents on a highway |
US3212106A (en) | 1963-07-18 | 1965-10-19 | American Radiator & Standard | Coatings |
US3354022A (en) | 1964-03-31 | 1967-11-21 | Du Pont | Water-repellant surface |
US3579540A (en) | 1968-11-01 | 1971-05-18 | Howard G Ohlhausen | Method for protecting nonporous substrates and for rendering them water repellent |
GB1341605A (en) | 1970-06-24 | 1973-12-28 | Johnson & Johnson | Surgical drape or gown |
US3716502A (en) | 1970-11-27 | 1973-02-13 | Inmont Corp | Elastomeric thermoplastic polyester polyurethane compositions stabilized against hydrolysis |
US3975197A (en) | 1973-02-12 | 1976-08-17 | Minnesota Mining And Manufacturing Company | Coated aluminum substrates |
CA1002256A (en) * | 1973-02-22 | 1976-12-28 | Bristol-Myers Canada Limited | Clear, uniform aqueous aerosol systems |
US3967030A (en) | 1973-08-22 | 1976-06-29 | Union Carbide Corporation | Siloxanes |
US3976572A (en) | 1974-01-04 | 1976-08-24 | Michael Ebert | Aircraft fuel contaminant tester |
US3931428A (en) | 1974-01-04 | 1976-01-06 | Michael Ebert | Substrate coated with super-hydrophobic layers |
GB1465495A (en) * | 1974-05-15 | 1977-02-23 | Holloway Ltd E R | Cleaning compositions |
US3963349A (en) | 1974-08-27 | 1976-06-15 | American Hospital Supply Corporation | Method and apparatus for determining coagulation times |
US3950588A (en) | 1974-11-01 | 1976-04-13 | Minnesota Mining And Manufacturing Company | Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes) |
US4142724A (en) | 1976-04-30 | 1979-03-06 | Michael Ebert | Water maze game with super-hydrophobic surface |
US4199142A (en) | 1976-04-30 | 1980-04-22 | Michael Ebert | Toys and games using super-hydrophobic surfaces |
US4680173A (en) | 1977-04-28 | 1987-07-14 | Norman D. Burger | Aerosol dispensing system |
US4151327A (en) | 1978-02-24 | 1979-04-24 | Lawton William R | Complex amine/silane treated cellulosic materials |
GB2039792B (en) | 1978-03-06 | 1982-04-21 | Glacier Metal Co Ltd | Bonding plastics materials to steel |
DE7813233U1 (en) | 1978-04-29 | 1978-08-24 | Jenaer Glaswerk Schott & Gen., 6500 Mainz | GLASS OR GLASS-CERAMIC HEATING AND / OR COOKING SURFACE WITH GLUED FRAME AND FASTENING ELEMENTS |
US4301197A (en) | 1979-12-03 | 1981-11-17 | Ppg Industries, Inc. | Siloxane release surfaces on glass |
US4308353A (en) * | 1980-02-13 | 1981-12-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic styrene polymer and grafted block copolymer compositions |
JPS5952885B2 (en) * | 1980-11-12 | 1984-12-21 | 旭化成株式会社 | Novel manufacturing method for block copolymer resin |
US4311755A (en) | 1980-12-29 | 1982-01-19 | E. I. Du Pont De Nemours And Company | Non-stick coated steel article |
DE3104114C2 (en) | 1981-02-06 | 1984-06-14 | Schott Glaswerke, 6500 Mainz | Holder for a plate made of glass, glass ceramic or similar material, in particular for a cooking surface |
US4415405A (en) | 1981-08-19 | 1983-11-15 | Yale University | Method for engraving a grid pattern on microscope slides and slips |
US4397988A (en) * | 1982-04-22 | 1983-08-09 | Mobil Oil Corporation | Blends of p-methylstyrene polymer and diene-styrene or diene-(p-methylstyrene) block copolymers |
US4581149A (en) | 1982-07-29 | 1986-04-08 | Mobil Oil Corporation | Zwitterionic quaternary ammonium sulfonates and sulfates and lubricants and fuels containing same |
US4451619A (en) | 1982-09-30 | 1984-05-29 | Minnesota Mining And Manufacturing Company | Method of hydrophilizing or hydrophobizing polymers |
IT1161241B (en) | 1983-05-03 | 1987-03-18 | Tvs Spa | SWEET POTTERY WITH NON-STICK COATING AND METHOD TO OBTAIN IT |
US4474852A (en) | 1983-05-23 | 1984-10-02 | Thomas B. Crane | Hydrophobic colloidal oxide treated core material, method of production and composition comprised thereof |
US4536454A (en) | 1983-08-26 | 1985-08-20 | Pdi, Inc. | Flexible coating composition and method of applying same |
FR2565593B1 (en) | 1984-06-12 | 1986-12-12 | Rhone Poulenc Spec Chim | AQUEOUS EMULSION COMPOSITIONS FOR NON-STICK AND WATER REPELLENT TREATMENT OF CELLULOSIC MATERIALS |
JPS612784A (en) | 1984-06-14 | 1986-01-08 | Toyoda Gosei Co Ltd | Spray can packed with water-repellent surface treatment |
DE3583707D1 (en) | 1984-06-26 | 1991-09-12 | Asahi Glass Co Ltd | TRANSPARENT HEAVY DIRTING ITEM WITH LOW REFLECTION. |
JPS61161103A (en) | 1985-01-10 | 1986-07-21 | Terumo Corp | Hydrophilic porous membrane and its preparation |
EP0215903A1 (en) * | 1985-03-18 | 1987-04-01 | Product Resources International, Inc. | Exothermic stable foam compositions |
US4617057A (en) | 1985-06-04 | 1986-10-14 | Dow Corning Corporation | Oil and water repellent coating compositions |
US4614464A (en) | 1985-07-12 | 1986-09-30 | Christensen Harry N | Adjustable jig for hole formation |
US4646948A (en) | 1985-10-03 | 1987-03-03 | Container Mfg. Inc. | Measuring container with modified pour-spout and method and apparatus for filling the same |
US5212215A (en) * | 1985-10-29 | 1993-05-18 | Nihon Tokushu Toryo Co., Ltd. | Light anti-chipping coating |
US4716183A (en) * | 1985-11-22 | 1987-12-29 | Raychem Corp. | Styrene-diene block copolymer compositions |
JPS62246960A (en) | 1985-12-20 | 1987-10-28 | Nok Corp | Sealing material |
US4837260A (en) | 1986-05-23 | 1989-06-06 | Toagosei Chemical Industry Co., Ltd. | Cyanoacrylate compositions |
USD295950S (en) | 1986-09-04 | 1988-05-31 | Arbell Inc. | Pair of support brackets for a shelf or the like |
JPS63120773A (en) | 1986-11-10 | 1988-05-25 | Toray Silicone Co Ltd | Waterproof material composition composed of aqueous silicone emulsion |
DE3635260A1 (en) | 1986-10-16 | 1988-04-28 | Wacker Chemie Gmbh | METHOD FOR MAKING WATER REPELLENT OF SUCTIONABLE INORGANIC CONSTRUCTION MATERIALS |
US4753977A (en) | 1986-12-10 | 1988-06-28 | General Electric Company | Water repellent for masonry |
JPS63149601A (en) | 1986-12-15 | 1988-06-22 | Toyota Central Res & Dev Lab Inc | Anti-fogging optical member |
US4745139A (en) | 1987-02-09 | 1988-05-17 | Pdi, Inc. | Elastomeric coatings containing glass bubbles |
US4738426A (en) | 1987-03-23 | 1988-04-19 | Knape & Vogt Manufacturing Company | Resilient sleeve glass shelf bracket |
US4733843A (en) | 1987-03-23 | 1988-03-29 | Knape & Vogt Manufacturing Company | Flexible glass shelf bracket |
US4971912A (en) | 1987-07-14 | 1990-11-20 | Technicon Instruments Corporation | Apparatus and method for the separation of immiscible liquids |
JP2667830B2 (en) | 1987-09-07 | 1997-10-27 | 株式会社クラレ | Ethylene-vinyl alcohol copolymer composition |
US4826970A (en) | 1987-09-17 | 1989-05-02 | Hercules Incorporated | Carboxymethyl hydrophobically modified hydroxyethylcellulose |
US4803233A (en) | 1987-10-30 | 1989-02-07 | Dow Corning Corporation | Water-based silicone-organic polymer compositions and method therefor |
US5011963A (en) | 1988-02-09 | 1991-04-30 | Matsushita Electric Ind., Co., Ltd. | Terminal perfluoroalkylsilane compounds |
JPH01225656A (en) * | 1988-03-07 | 1989-09-08 | Japan Synthetic Rubber Co Ltd | Thermoplastic polymer composition |
DE68920894T2 (en) | 1988-03-08 | 1995-09-21 | Asahi Glass Co Ltd | Water and oil repellent composition. |
FR2632962A1 (en) | 1988-06-17 | 1989-12-22 | Pola Chem Ind Inc | WATERPROOFING AND OLEOFUGE COATING POWDERS, PROCESS FOR THE PRODUCTION THEREOF AND COSMETIC PRODUCTS CONTAINING THEM |
CA1336929C (en) | 1988-06-28 | 1995-09-05 | Kansai Paint Co., Ltd. | Water-repellent film-forming composition |
US4870907A (en) | 1988-08-09 | 1989-10-03 | Mckee Roy L | Towel rack convenience shelf |
JP2732260B2 (en) | 1988-09-09 | 1998-03-25 | 鐘淵化学工業株式会社 | Polyimide laminate with improved slipperiness |
JP2796976B2 (en) * | 1988-11-30 | 1998-09-10 | サンスター技研株式会社 | Moisture crosslinkable primer composition |
US5856378A (en) | 1988-12-02 | 1999-01-05 | Courtaulds Coatings (Holdings) Limited | Powder coating compositions |
IL89559A (en) * | 1989-03-09 | 1992-09-06 | Adhestick Ramle | Sprayable bird and animal pest repellent composition containing a tacky polyolefin and methods for the preparation and use thereof |
GB8906379D0 (en) | 1989-03-20 | 1989-05-04 | Am Int | Providing a surface with solvent-wettable and solvent-non wettable zones |
US4923260A (en) | 1989-08-29 | 1990-05-08 | White Consolidated Industries, Inc. | Refrigerator shelf construction |
GB8921041D0 (en) | 1989-09-16 | 1989-11-01 | Rtz Chemicals Ltd | Water-borne water repellents and their use |
JP2990608B2 (en) | 1989-12-13 | 1999-12-13 | 株式会社ブリヂストン | Surface treatment method |
JPH03193975A (en) | 1989-12-22 | 1991-08-23 | Minnesota Mining & Mfg Co <3M> | Water-repellant oil-repellant treating agent |
US5156611A (en) | 1990-02-05 | 1992-10-20 | Becton, Dickinson And Company | Blood microsampling site preparation method |
AU623752B2 (en) * | 1990-03-14 | 1992-05-21 | Dow Chemical Company, The | Bituminous binder compositions |
US5057050A (en) | 1990-03-20 | 1991-10-15 | Mattel, Inc. | Surface skimming toy |
US4983459A (en) | 1990-04-03 | 1991-01-08 | Ppg Industries, Inc. | Chemically reacted glass surface |
US6025025A (en) | 1990-04-03 | 2000-02-15 | Ppg Industries Ohio, Inc. | Water-repellent surface treatment |
US5328768A (en) | 1990-04-03 | 1994-07-12 | Ppg Industries, Inc. | Durable water repellant glass surface |
US5523161A (en) | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
US5707740A (en) | 1990-04-03 | 1998-01-13 | Ppg Industries, Inc. | Water repellent surface treatment with acid activation |
US5308705A (en) | 1990-04-03 | 1994-05-03 | Ppg Industries, Inc. | Water repellent surface treatment |
US5523162A (en) | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment for plastic and coated plastic substrates |
US5674967A (en) | 1990-04-03 | 1997-10-07 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
US5688864A (en) | 1990-04-03 | 1997-11-18 | Ppg Industries, Inc. | Autophobic water repellent surface treatment |
CA2022039A1 (en) | 1990-07-26 | 1992-01-27 | Julio O. Gun | Composition for producing a monomolecular film on the surfaces of various materials |
US5228905A (en) | 1990-08-14 | 1993-07-20 | Ppg Industries, Inc. | Water-borne treatment compositions for porous substrates |
US5300239A (en) | 1990-08-24 | 1994-04-05 | Dow Corning Toray Silicone Co., Ltd. | Water-repellent and oil-repellent treatment |
JP3072120B2 (en) | 1990-08-24 | 2000-07-31 | 東レ・ダウコーニング・シリコーン株式会社 | Water and oil repellent treatment agent |
JP2646150B2 (en) | 1990-08-27 | 1997-08-25 | 出光興産 株式会社 | Water repellent silica sol and method for producing the same |
JPH04124047A (en) | 1990-09-17 | 1992-04-24 | Nissan Motor Co Ltd | Method for water repellent treatment of glass surface |
EP0484746B1 (en) | 1990-10-25 | 1996-09-18 | Matsushita Electric Industrial Co., Ltd. | Chemically adsorbed monomolecular lamination film and method of manufacturing the same |
US5240774A (en) | 1990-10-25 | 1993-08-31 | Matsushita Electric Industrial Co., Ltd. | Fluorocarbon-based coating film and method of manufacturing the same |
US5238746A (en) | 1990-11-06 | 1993-08-24 | Matsushita Electric Industrial Co., Ltd. | Fluorocarbon-based polymer lamination coating film and method of manufacturing the same |
FR2669642B1 (en) | 1990-11-28 | 1993-05-07 | Lengrand Pascal | HYDROPHOBIC COMPOSITIONS FOR SURFACE COATING IN LIQUID OR PASTE CONDITIONS FOR USE AS A THICK OR SEMI-THICK COATING IN THE BUILDING AND DECORATION. |
JP2637869B2 (en) | 1990-12-10 | 1997-08-06 | 松下電器産業株式会社 | Adsorbed monomolecular film and method for producing the same |
DE69120788T2 (en) | 1990-12-25 | 1996-11-07 | Matsushita Electric Ind Co Ltd | Non-contaminating, absorbed film and process for its production |
JP3165672B2 (en) | 1991-01-23 | 2001-05-14 | 松下電器産業株式会社 | Article having water / oil repellent coating and method for producing the same |
DE69218811T2 (en) | 1991-01-23 | 1997-07-17 | Matsushita Electric Ind Co Ltd | Water and oil repellent adsorbed film and process for its manufacture |
CA2060294C (en) | 1991-02-06 | 2000-01-18 | Kazufumi Ogawa | Chemically absorbed film and method of manufacturing the same |
US5540493A (en) | 1991-03-07 | 1996-07-30 | Donnelly Technology Inc. | Encapsulated shelf with pre-encapsulated bracket |
US5441338A (en) | 1991-03-07 | 1995-08-15 | Donnelly Corporation | Snap-on shelf |
US5564809A (en) | 1991-03-07 | 1996-10-15 | Donnelly Technology, Inc. | Encapsulated shelf for refrigerated compartments |
US5362145A (en) | 1991-03-07 | 1994-11-08 | Donnelly Corporation | Molded refrigerator shelf |
DE69227451T2 (en) | 1991-04-15 | 1999-04-15 | Univ Groningen | METHOD FOR MODIFYING FLUOR-CONTAINING PLASTIC, MODIFIED PLASTIC AND BIOMATERIAL CONTAINING THIS PLASTIC |
US5424130A (en) | 1991-05-13 | 1995-06-13 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
EP0646151B1 (en) | 1991-06-14 | 1997-11-05 | W.L. Gore & Associates, Inc. | Surface modified porous expanded polytetrafluoroethylene and process for making |
US5312573A (en) * | 1991-08-01 | 1994-05-17 | Renewed Materials Industries, Inc. | Process for extruding mixtures of thermoplastic and thermoset materials |
US5192603A (en) * | 1991-09-13 | 1993-03-09 | Courtaulds Coatings Inc. | Protection of substrates against aquatic fouling |
US5202361A (en) | 1991-12-23 | 1993-04-13 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive |
JP2778322B2 (en) | 1992-01-14 | 1998-07-23 | 松下電器産業株式会社 | Thermosetting water-repellent coating and cooking device using it |
US5364299A (en) | 1992-01-29 | 1994-11-15 | Mattel, Inc. | Surface skimming toy |
AU673342B2 (en) | 1992-02-10 | 1996-11-07 | Minnesota Mining And Manufacturing Company | Radiation crosslinked elastomers |
EP0556451B1 (en) | 1992-02-19 | 1996-09-18 | Hughes Aircraft Company | Frozen premix, fillet-holding urethane adhesives/sealants |
DE4210010C2 (en) | 1992-03-27 | 1995-04-27 | Schott Glaswerke | Cooktop |
US5368892A (en) | 1992-04-10 | 1994-11-29 | Saint-Gobain Vitrage International | Non-wettable glass sheet |
JP2741823B2 (en) | 1992-05-27 | 1998-04-22 | 松下電器産業株式会社 | Surface treatment agent and method of using the same |
US5314940A (en) | 1992-06-22 | 1994-05-24 | Stone Donald D | High wet-friction elastomeric coatings including a thermoplastic rubber and petrolatum |
DE4224325C1 (en) * | 1992-07-23 | 1994-02-10 | Sanol Arznei Schwarz Gmbh | Active ingredient plasters for low-melting and / or volatile active ingredients and process for its manufacture |
US5228764A (en) | 1992-08-10 | 1993-07-20 | General Electric Company | Refrigerator shelf assembly |
US5366810A (en) | 1992-10-09 | 1994-11-22 | General Electric Company | Water-repellent wallboard |
US5747561A (en) | 1992-10-14 | 1998-05-05 | Smirnov; Aleksandr Vitalievich | Solid surface modifier |
US5316799A (en) | 1992-10-30 | 1994-05-31 | Advanced Chemical Technologies, Inc. | Method for applying paint with a water repellant composition |
EP0672080B1 (en) | 1992-12-04 | 1997-07-30 | Franz Haas Waffelmaschinen Industriegesellschaft M.B.H. | Process for producing biodegradable thin-walled starch-based mouldings |
IT1256721B (en) | 1992-12-16 | 1995-12-15 | Ausimont Spa | PROCESS FOR IMPROVING OIL AND HYDRO-REPELLENCE TO THE SURFACE OF POROUS CERAMIC MATERIALS |
US5435839A (en) | 1992-12-24 | 1995-07-25 | Matsushita Electric Industrial Co., Ltd. | Finishing agents and method of manufacturing the same |
EP0611077A3 (en) * | 1993-02-08 | 1994-12-28 | Rohm & Haas | Polyurethane elastomer blends. |
US5274159A (en) | 1993-02-18 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Destructable fluorinated alkoxysilane surfactants and repellent coatings derived therefrom |
US5352733A (en) | 1993-03-10 | 1994-10-04 | R. E. Hart Labs, Inc. | Water based, solvent free, two component aliphatic polyurethane coating |
US5348547A (en) | 1993-04-05 | 1994-09-20 | The Procter & Gamble Company | Absorbent members having improved fluid distribution via low density and basis weight acquisition zones |
US5338345A (en) | 1993-05-05 | 1994-08-16 | Eastman Kodak Company | Water-based water repellent coating compositions |
DE4318854C1 (en) | 1993-06-07 | 1994-06-23 | Schott Glaswerke | Glass-plate-mounting for use as cooking surface |
US5500216A (en) | 1993-06-18 | 1996-03-19 | Julian; Jorge V. | Topical hydrophobic composition and method |
JP2960304B2 (en) | 1993-06-30 | 1999-10-06 | 信越化学工業株式会社 | Water repellent for fiber |
DE4327475C2 (en) | 1993-08-16 | 1999-04-22 | Schott Glas | Process for forming a permanently elastic, easily detachable adhesive connection in the event of disassembly |
JPH0790691A (en) | 1993-09-24 | 1995-04-04 | Fujikura Ltd | Super water repellent coating film surface treated material and coating method thereof |
JPH07118577A (en) | 1993-10-22 | 1995-05-09 | Dow Corning Asia Kk | Water-repellent mildewproofing coating film-forming composition |
US5441809A (en) * | 1993-10-28 | 1995-08-15 | Brady U.S.A., Inc. | Dissipative cover tape surface mount device packaging |
DE69420668T2 (en) * | 1993-11-05 | 2000-03-23 | Sumitomo Chemical Co | Styrenic resin composition and injection molded and extruded articles |
DE69408268T2 (en) | 1993-11-09 | 1998-05-14 | Ricoh Kk | Image forming apparatus with a contact part in contact with an image carrier |
JP3367572B2 (en) | 1993-12-08 | 2003-01-14 | 日本板硝子株式会社 | Method of forming water-repellent coating |
US20030166840A1 (en) | 1994-01-24 | 2003-09-04 | Urry Dan W. | Photoresponsive polymers |
US5578361A (en) | 1994-01-26 | 1996-11-26 | Central Glass Company, Limited | Water-repellent composite grains, method for producing same, and water-repellent article using same |
US5489328A (en) | 1994-01-31 | 1996-02-06 | Shin-Etsu Chemical Co., Ltd. | Water repellent agent |
US6040382A (en) * | 1994-02-04 | 2000-03-21 | Phillips Petroleum Company | Polymer blend clarity |
CA2146791C (en) | 1994-04-29 | 2002-06-25 | Robert S. Herrmann | Sliding refrigerator shelf assembly |
US5466770A (en) | 1994-05-26 | 1995-11-14 | Minnesota Mining And Manufacturing Company | Fluorine-efficient oil- and water-repellent compositions |
FR2722493B1 (en) | 1994-07-13 | 1996-09-06 | Saint Gobain Vitrage | MULTI-LAYERED HYDROPHOBIC GLAZING |
EP0701020A2 (en) | 1994-07-27 | 1996-03-13 | Bayer Ag | Oil and water-repellent papers, process for making the same, and new fluorine-containing copolymers for making the same |
DE59504640D1 (en) | 1994-07-29 | 1999-02-04 | Wilhelm Prof Dr Barthlott | SELF-CLEANING SURFACES OF OBJECTS AND METHOD FOR THE PRODUCTION THEREOF |
DE69507551T2 (en) | 1994-08-12 | 1999-07-15 | Shinetsu Chemical Co | Water repellent composition |
US5736249A (en) | 1994-08-16 | 1998-04-07 | Decora, Incorporated | Non-stick polymer-coated articles of manufacture |
WO1996007621A1 (en) | 1994-09-08 | 1996-03-14 | Ford Motor Company | Volatile glass batch materials incorporated in frits |
US6120720A (en) | 1994-09-08 | 2000-09-19 | Gemtron Corporation | Method of manufacturing a plastic edged glass shelf |
EP0714870A1 (en) | 1994-11-29 | 1996-06-05 | Elf Atochem S.A. | Process and composition for the oleophobic and hydrophobic treatment of construction materials |
FR2727417B1 (en) | 1994-11-29 | 1997-01-03 | Atochem Elf Sa | CATIONIC FLUORINE COPOLYMERS FOR OLEOPHOBIC AND HYDROPHOBIC TREATMENT OF CONSTRUCTION MATERIALS |
JPH08239241A (en) | 1995-02-28 | 1996-09-17 | Toray Dow Corning Silicone Co Ltd | Water-repelling agent for glass and water-repelling glass |
US5725789A (en) | 1995-03-31 | 1998-03-10 | Minnesota Mining And Manufacturing Company | Aqueous oil and water repellent compositions |
CA2175849C (en) | 1995-06-01 | 2003-07-15 | George B. Goodwin | Autophobic water repellent surface treatment |
DE69601974T2 (en) | 1995-06-01 | 1999-10-21 | Ppg Industries Inc | Water-repellent surface treatment with integrated primer |
CA2175848C (en) | 1995-06-05 | 2000-01-11 | Ppg Industries Ohio, Inc. | Water repellent surface treatment with integrated primer |
US5618883A (en) * | 1995-06-07 | 1997-04-08 | Avery Dennison Corporation | Styrene ethylene-butylene and ethylene-propylene block copolymer hot melt pressure sensitive adhesives |
AT402369B (en) | 1995-07-03 | 1997-04-25 | Oemv Ag | METHOD AND DEVICE FOR SEPARATING A HYDROPHOBIC LIQUID FRACTION FROM AN AQUEOUS SUSPENSION |
JP3234748B2 (en) | 1995-07-14 | 2001-12-04 | キヤノン株式会社 | Method for selective water-repellent treatment of substrate, light-shielding member-formed substrate, and method for manufacturing color filter substrate using this light-shielding member-formed substrate |
US6835778B2 (en) * | 1995-08-29 | 2004-12-28 | Chevron Phillips Chemical Company Lp | Conjugated diene/monovinylarene block copolymers blends |
WO1997007993A1 (en) | 1995-08-31 | 1997-03-06 | First Medical, Inc. | Methods and articles for enhanced protein adsorption and fluid management on surfaces |
US5719226A (en) * | 1995-09-15 | 1998-02-17 | Shell Oil Company | Low viscosity hot melt disposables adhesive composition |
FR2739023B1 (en) | 1995-09-21 | 1997-10-31 | Oreal | AQUEOUS COMPOSITION FOR HOLDING AND/OR FIXING HAIR COMPRISING A FILM-GENERATING ACRYLIC OLIGOMER, SOLUBLE OR DISPERSIBLE IN AQUEOUS MEDIUMS AND USES |
DE69608660T2 (en) | 1995-10-02 | 2001-02-01 | Mitsubishi Materials Corp | HYDROPHOBIC METAL OXIDE POWDER AND THEIR USE |
DE19539789A1 (en) | 1995-10-26 | 1997-04-30 | Merck Patent Gmbh | Means and methods for producing water-repellent coatings on optical substrates |
US6221823B1 (en) | 1995-10-25 | 2001-04-24 | Reckitt Benckiser Inc. | Germicidal, acidic hard surface cleaning compositions |
JP3766707B2 (en) | 1995-10-25 | 2006-04-19 | ディップソール株式会社 | Water-soluble composition for water-repellent treatment of zinc and zinc alloy and water-repellent treatment method |
JPH09151357A (en) | 1995-11-28 | 1997-06-10 | Toray Dow Corning Silicone Co Ltd | Coating agent composition |
JPH09165553A (en) | 1995-12-15 | 1997-06-24 | Dow Corning Asia Ltd | Composition for forming water repelling membrane |
EP1015135B1 (en) | 1996-01-11 | 2005-06-08 | ROSS, Gregory Edye | Perimeter coating alignment method |
US5705079A (en) | 1996-01-19 | 1998-01-06 | Micron Display Technology, Inc. | Method for forming spacers in flat panel displays using photo-etching |
US5813741A (en) | 1996-01-23 | 1998-09-29 | White Consolidated Industries, Inc. | Adjustable shelf for a refrigerator |
US5658969A (en) * | 1996-01-29 | 1997-08-19 | Pierce & Stevens Corporation | Light weight plastisols and method of making same |
US6042948A (en) | 1996-02-01 | 2000-03-28 | Matsushita Electric Industrial Co., Ltd. | Water repellent coating film, method and apparatus for manufacturing the same, and water repellent coating material composition |
JPH09277487A (en) | 1996-02-16 | 1997-10-28 | Riso Kagaku Corp | Plate making method of thermosensible stencil base sheet, thermosensible stencil base sheet using it, and composition |
JP2982678B2 (en) | 1996-02-19 | 1999-11-29 | 東洋インキ製造株式会社 | Resin composition for water-repellent coating |
JPH09225299A (en) | 1996-02-28 | 1997-09-02 | Toyota Motor Corp | Activated carbon |
US6191122B1 (en) | 1996-03-29 | 2001-02-20 | DEGUSSA HüLS AKTIENGESELLSCHAFT | Partially hydrophobic precipitated silicas |
NZ332179A (en) | 1996-04-02 | 1999-11-29 | S | A method for imparting hydrophobicity to a surface of a substrate with low concentration organofunctional silanes |
CA2202834C (en) | 1996-04-17 | 2001-08-07 | Susumu Fujimori | Water repellent coating composition and coating films and coated articles using the same |
JP3253851B2 (en) | 1996-04-18 | 2002-02-04 | 株式会社日立製作所 | Super water repellent paint and super water repellent coating using the same |
EP0912294B1 (en) | 1996-05-03 | 2003-04-16 | Minnesota Mining And Manufacturing Company | Nonwoven abrasive articles |
WO1997044375A1 (en) | 1996-05-17 | 1997-11-27 | Minnesota Mining And Manufacturing Company | Fluorochemical polyurethanes, providing good laundry air-dry performance |
JP3498881B2 (en) | 1996-05-27 | 2004-02-23 | セントラル硝子株式会社 | Manufacturing method of water-repellent glass |
CN1171966C (en) | 1996-05-31 | 2004-10-20 | 东陶机器株式会社 | Antifouling member and coating composition |
CN1105756C (en) | 1996-06-19 | 2003-04-16 | 大金工业株式会社 | Coating composition, coating film, and process for prodn. of film |
US6090447A (en) | 1996-08-09 | 2000-07-18 | Asahi Glass Company, Ltd. | Process for forming a water-repellent thin film |
EP0825241B1 (en) | 1996-08-16 | 2003-03-26 | Nippon Telegraph And Telephone Corporation | Water repellent coating composition, method for preparing the same, and coating films and coated articles using the same |
DE69709800T2 (en) | 1996-08-19 | 2002-09-26 | Central Glass Co Ltd | Water-repellent glass pane and process for its manufacture |
US5697991A (en) | 1996-08-29 | 1997-12-16 | Crescent Marketing, Inc. | Glass treatment compound |
US6811716B1 (en) | 1996-10-24 | 2004-11-02 | Fibervisions A/S | Polyolefin fibers and method for the production thereof |
US6093559A (en) | 1996-10-24 | 2000-07-25 | Corning Incorporated | Producing low binding hydrophobic surfaces by treating with a low HLB number non-ionic surfactant |
EP0946250B1 (en) | 1996-11-12 | 2004-06-30 | Whatman Inc. | Hydrophilic polymeric phase inversion membrane |
US6119626A (en) | 1996-11-14 | 2000-09-19 | Canon Kabushiki Kaisha | Vacuum apparatus for forming a thin-film and method for forming thin-film |
DE19651478A1 (en) | 1996-12-11 | 1998-06-18 | Beiersdorf Ag | Sunscreen preparations containing surface-active mono- or oligoglyceryl compounds, water-soluble UV filter substances and optionally inorganic micropigments |
US6114446A (en) | 1996-12-25 | 2000-09-05 | Kansai Paint Co., Ltd. | Polymer composition capable of forming surface slidable on water |
US5890907A (en) | 1997-01-13 | 1999-04-06 | Clifford W. Estes Company, Inc. | Educational doll |
JPH10259038A (en) | 1997-01-24 | 1998-09-29 | Samsung Corning Co Ltd | Durable water-repelling glass and its production |
US5858551A (en) | 1997-01-31 | 1999-01-12 | Seydel Research, Inc. | Water dispersible/redispersible hydrophobic polyester resins and their application in coatings |
US7268179B2 (en) | 1997-02-03 | 2007-09-11 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
US5777043A (en) * | 1997-03-05 | 1998-07-07 | Shell Oil Company | Sealant formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers |
US5908708A (en) | 1997-03-05 | 1999-06-01 | Engelhard Corporation | Aqueous dispersion of a particulate solid having a hydrophobic outer surface and films produced thereby |
KR19980079940A (en) | 1997-03-05 | 1998-11-25 | 후지이 히로시 | Rainwater contamination-preventing coating film, coating composition, coating film forming method and coating material |
US6482524B1 (en) | 1997-03-11 | 2002-11-19 | Nippon Sheet Glass Co., Ltd. | Substrate having a treatment surface |
US20020155299A1 (en) | 1997-03-14 | 2002-10-24 | Harris Caroline S. | Photo-induced hydrophilic article and method of making same |
US5947574A (en) | 1997-06-04 | 1999-09-07 | Maytag Corporation | Refrigerator shelving assembly |
US5921411A (en) | 1997-06-09 | 1999-07-13 | Merl; Milton J. | Shelf assembly |
JP3334611B2 (en) | 1997-06-24 | 2002-10-15 | 日本板硝子株式会社 | Method for producing water-repellent article, water-repellent article and solution for forming water-repellent coating |
US6465556B1 (en) | 1997-07-01 | 2002-10-15 | Rhodia Inc. | Latex made with crosslinkable surface active agent |
FR2767270B1 (en) | 1997-08-14 | 2000-02-11 | Daniel Gamain | GAS PHASE TREATMENT PROCESS OF A SOLID MATERIAL TO MAKE IT HYDROPHOBIC, MATERIAL OBTAINED AND APPLICATIONS |
JPH1160653A (en) * | 1997-08-18 | 1999-03-02 | Denki Kagaku Kogyo Kk | Rubber-modified styrene polymer |
DE19737475A1 (en) | 1997-08-28 | 1999-03-04 | Bayer Ag | Coating compositions based on silanes containing epoxy groups |
ES2234145T3 (en) | 1997-09-12 | 2005-06-16 | Asahi Glass Company Ltd. | COMPOSITION OF SURFACE TREATMENT, SURFACE TREATMENT PROCEDURE, SUBSTRATE AND ARTICLE. |
US6045650A (en) | 1997-09-16 | 2000-04-04 | Sunsmart, Inc. | Hydrophilic materials and their method of preparation |
US5952053A (en) | 1997-09-26 | 1999-09-14 | Willamette Valley Company | Process for producing filled polyurethane elastomers |
DE69839662D1 (en) * | 1997-10-01 | 2008-08-14 | Denki Kagaku Kogyo Kk | Foil and foil for clamping packaging |
FR2769318B1 (en) | 1997-10-06 | 1999-12-10 | Saint Gobain Vitrage | HYDROPHOBIC COATING, ESPECIALLY FOR GLAZING |
US6105233A (en) | 1997-10-29 | 2000-08-22 | Neal; Albert D. | Shelf for a refrigerator and method of making |
US6017997A (en) | 1997-10-31 | 2000-01-25 | The B. F. Goodrich Company | Waterborne polyurethane having film properties comparable to rubber |
DE19748295A1 (en) | 1997-10-31 | 1999-05-06 | Max Planck Gesellschaft | Element with extremely water-repellent drying zones on the surface |
DE19748606A1 (en) | 1997-11-04 | 1999-05-06 | Ge Bayer Silicones Gmbh & Co | Superficially hydrophilized silicone elastomers, processes for their production and their use |
FR2770526B1 (en) | 1997-11-04 | 2000-01-14 | Atochem Elf Sa | STABLE AQUEOUS DISPERSIONS BASED ON WATER-SOLUBLE POLYMERS CONTAINING A CATIONIC DISPERSANT HAVING HYDROPHOBIC PATTERNS |
TW418116B (en) | 1997-11-04 | 2001-01-11 | Matsushita Electric Ind Co Ltd | Water-repellent coating and coating device |
DE19749380A1 (en) | 1997-11-07 | 1999-05-12 | Wacker Chemie Gmbh | Compositions containing aminosiloxanes |
JP3574734B2 (en) | 1997-11-27 | 2004-10-06 | 東京エレクトロン株式会社 | Method for manufacturing semiconductor device |
GB9726807D0 (en) | 1997-12-18 | 1998-02-18 | Mupor Ltd | Hydrophobic/Oleophobic surfaces and a method of manufacture |
WO1999034933A1 (en) | 1998-01-02 | 1999-07-15 | Ashland Inc. | Water repellent glass treatment for automotive applications |
DE69819292T2 (en) | 1998-01-13 | 2004-07-29 | Minnesota Mining & Manufacturing Company, St. Paul | Fluoropolymer and fluoropolymer compositions for imparting water and oil repellency to a substrate |
EP1047735B1 (en) | 1998-01-15 | 2003-04-02 | Cabot Corporation | Method of preparing hydrophobic silica |
US5948685A (en) | 1998-02-10 | 1999-09-07 | Angros; Lee | Analytic plate with containment border and method of use |
DE69926093T2 (en) | 1998-02-13 | 2006-05-11 | Central Glass Co., Ltd., Ube | Water-repellent solution and method for producing a water-repellent layer on a substrate by means of this solution |
WO1999047578A1 (en) | 1998-03-16 | 1999-09-23 | Reichhold, Inc. | Surface active polyesters |
KR100608543B1 (en) | 1998-03-17 | 2006-08-03 | 세이코 엡슨 가부시키가이샤 | Manufacturing method of display device and manufacturing method of thin firm light-emitting device |
DE19811790A1 (en) | 1998-03-18 | 1999-09-23 | Bayer Ag | Transparent paint binders containing nanoparticles with improved scratch resistance, a process for their preparation and their use |
US6352758B1 (en) | 1998-05-04 | 2002-03-05 | 3M Innovative Properties Company | Patterned article having alternating hydrophilic and hydrophobic surface regions |
US6264751B1 (en) | 1998-05-18 | 2001-07-24 | Hoya Corporation | Mechanism for performing water repellency processing on both sides simultaneously |
DE69927427T2 (en) | 1998-05-18 | 2006-03-16 | Shin-Etsu Chemical Co., Ltd. | Silane-surface treated silica particles, process for their preparation and their use |
JPH11340321A (en) | 1998-05-27 | 1999-12-10 | Sony Corp | Semiconductor device and its manufacture |
JP3842554B2 (en) | 1998-06-04 | 2006-11-08 | 日本板硝子株式会社 | Method for producing water-repellent film-coated article, water-repellent film-coated article, and liquid composition for water-repellent film coating |
US6589641B1 (en) | 1998-06-04 | 2003-07-08 | Seagate Technology Llc | Thin films of crosslinked fluoropolymer on a carbon substrate |
FR2781495B3 (en) | 1998-07-24 | 2000-09-01 | Saint Gobain Vitrage | HYDROPHOBIC TREATMENT COMPOSITION, PROCESS FOR FORMING A COATING FROM THIS COMPOSITION AND PRODUCTS PROVIDED WITH THIS COATING |
US6579620B2 (en) | 1998-07-31 | 2003-06-17 | Ntt Advanced Technology Corp. | Water-repellent coating and coating film |
JP2000053449A (en) | 1998-08-06 | 2000-02-22 | Murakami Corp | Non-fogging mirror and its production |
FR2782522B1 (en) | 1998-08-19 | 2003-10-03 | Atochem Elf Sa | WATERPROOFING COMPOSITION |
JP2000136377A (en) | 1998-08-24 | 2000-05-16 | Asahi Glass Co Ltd | Water-dispersible water and oil repellent composition |
FI109220B (en) | 1998-09-04 | 2002-06-14 | Kemira Chemicals Oy | A method for making water-repellent paper or paperboard and a bonding mixture |
US6649222B1 (en) | 1998-09-07 | 2003-11-18 | The Procter & Gamble Company | Modulated plasma glow discharge treatments for making superhydrophobic substrates |
EP0985741A1 (en) | 1998-09-07 | 2000-03-15 | The Procter & Gamble Company | Modulated plasma glow discharge treatments for making super hydrophobic substrates |
CA2345436A1 (en) * | 1998-10-09 | 2000-04-20 | H.B. Fuller Licensing & Financing, Inc. | Hot melt adhesive composition including surfactant |
EP1041092B1 (en) * | 1998-10-19 | 2005-11-02 | Denki Kagaku Kogyo Kabushiki Kaisha | Ethylene/aromatic vinyl copolymer and process for producing the same |
JP2001072734A (en) | 1998-10-23 | 2001-03-21 | Nitto Denko Corp | Aromatic polycarbodiimide and water-repellent sheet made therefrom |
US6136210A (en) | 1998-11-02 | 2000-10-24 | Xerox Corporation | Photoetching of acoustic lenses for acoustic ink printing |
US20020001676A1 (en) | 1998-11-03 | 2002-01-03 | Don Hayden | Capped silicone film and method of manufacture thereof |
US6245387B1 (en) | 1998-11-03 | 2001-06-12 | Diamon-Fusion International, Inc. | Capped silicone film and method of manufacture thereof |
IT1303808B1 (en) | 1998-12-01 | 2001-02-23 | Ausimont Spa | SURFACE TREATMENTS WITH BIFUNCTIONAL DIPERFLUOROPOLYETER DERIVATIVES. |
US6162877A (en) | 1998-12-04 | 2000-12-19 | Hercules Incorporated | Hydrophobically modified comb copolymers |
FR2787350B1 (en) | 1998-12-21 | 2002-01-04 | Saint Gobain Vitrage | GLASS WITH FUNCTIONAL MESOPOROUS COATING, ESPECIALLY HYDROPHOBIC |
IT1304497B1 (en) * | 1998-12-22 | 2001-03-19 | Enichem Spa | HIGH TRANSPARENCY POLYMERIC COMPOSITION. |
DE69942460D1 (en) * | 1998-12-22 | 2010-07-15 | Denki Kagaku Kogyo Kk | CROSS-COPOLYMERIZED OLEFINE / STYRENE / DIEN COPOLYMERS, THEIR MANUFACTURING METHOD AND USE |
SK285652B6 (en) | 1998-12-24 | 2007-05-03 | Qiagen Gmbh | Ultraphobic surface |
KR100579633B1 (en) * | 1999-01-21 | 2006-05-12 | 도요 보세키 가부시키가이샤 | Optical-use adhesive film and roll thereof |
DE19904423A1 (en) | 1999-02-04 | 2000-08-10 | Kloeber Johannes | Hydrophobically equipped, breathable underlayment |
US6214278B1 (en) * | 1999-02-17 | 2001-04-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Rubber-modified styrene copolymer |
US6291054B1 (en) | 1999-02-19 | 2001-09-18 | E. I. Du Pont De Nemours And Company | Abrasion resistant coatings |
US6224974B1 (en) | 1999-03-10 | 2001-05-01 | Consolidated Papers, Inc. | Water resistant, caustically removable coating, paper label and recyclable labeled glass bottle |
US6383642B1 (en) | 1999-04-09 | 2002-05-07 | Saint-Gobain Vitrage | Transparent substrate provided with hydrophobic/oleophobic coating formed by plasma CVD |
US6184408B1 (en) | 1999-04-28 | 2001-02-06 | Dow Corning Corporation | Method for preparation of hydrophobic precipitated silica |
US6280834B1 (en) | 1999-05-03 | 2001-08-28 | Guardian Industries Corporation | Hydrophobic coating including DLC and/or FAS on substrate |
AU4698300A (en) | 1999-05-03 | 2000-11-17 | Sustainable Technologies Corporation | Encapsulant compositions and methods for treating spills of hydrophobic and/or hydrophilic materials |
US6200626B1 (en) | 1999-05-20 | 2001-03-13 | Bausch & Lomb Incorporated | Surface-treatment of silicone medical devices comprising an intermediate carbon coating and graft polymerization |
EP1136539A4 (en) | 1999-08-02 | 2002-10-09 | Nippon Sheet Glass Co Ltd | Article coated with water-repellent film, liquid composition for coating with water-repellent film, and process for producing article coated with water-repellent film |
US6780497B1 (en) | 1999-08-05 | 2004-08-24 | Gore Enterprise Holdings, Inc. | Surface modified expanded polytetrafluoroethylene devices and methods of producing the same |
US6479612B1 (en) | 1999-08-10 | 2002-11-12 | E. I. Du Pont De Nemours And Company | Fluorochemical water and oil repellents |
AUPQ234599A0 (en) | 1999-08-20 | 1999-09-16 | Lamb, Robert Norman | Hydrophobic material |
US6437040B2 (en) | 1999-09-01 | 2002-08-20 | Rhodia Chimie | Water-soluble block copolymers comprising a hydrophilic block and a hydrophobic block |
US6660339B1 (en) | 1999-09-07 | 2003-12-09 | The Procter & Gamble Company | Process for hydrophobic treatment of water vapor permeable substrates |
WO2001019881A1 (en) * | 1999-09-13 | 2001-03-22 | Denki Kagaku Kogyo Kabushiki Kaisha | Cross-copolymerized olefin/aromatic vinyl/diene copolymer and process for producing the same |
WO2001019745A1 (en) | 1999-09-13 | 2001-03-22 | Nippon Sheet Glass Co., Ltd. | Method for partially treating a water-repellent glass sheet and the partially treated glass sheet |
US6803422B2 (en) * | 1999-09-13 | 2004-10-12 | Denki Kagaku Kogyo Kabushiki Kaisha | Cross-copolymerized olefin/aromatic vinyl compound/diene copolymer and process for its production |
US6451437B1 (en) | 1999-10-13 | 2002-09-17 | Chugoku Marine Paints, Ltd. | Curable composition, coating composition, paint, antifouling paint, cured product thereof and method of rendering base material antifouling |
US6564935B1 (en) | 1999-11-04 | 2003-05-20 | Nippon Sheet Glass Co., Ltd. | Coating solution, method and kit for preparing the same, and method for water-repellent treatment using the same |
US6423381B1 (en) * | 1999-11-12 | 2002-07-23 | Martin Colton | Protective, transparent UV curable coating method |
US6384130B1 (en) | 1999-12-03 | 2002-05-07 | Bayer Corporation | Liquid, hydrophobic, non-migrating, non-functional polyurethane plasticizers |
WO2001042372A1 (en) | 1999-12-08 | 2001-06-14 | Nippon Aerosil Co., Ltd. | Fine metal oxide powder having high dispersibility and toner composition comprising the same |
DE19959949A1 (en) | 1999-12-13 | 2001-06-21 | Bayer Ag | Hydrophobization with carboxyl-containing polysiloxanes |
DE60018805T2 (en) | 1999-12-24 | 2006-04-13 | Nippon Aerosil Co., Ltd. | SURFACE MODIFIED INORGANIC OXIDE POWDER, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF |
EP1113048A3 (en) | 1999-12-27 | 2002-01-30 | General Electric Company | Hydrophobicity imparting particulate |
DE10007859A1 (en) | 2000-02-21 | 2001-08-23 | Bayer Ag | Durable water- or oil-repellant surface, e.g. for car windows, includes a reservoir layer for the repellant below a porous surface layer |
US6432181B1 (en) | 2000-03-03 | 2002-08-13 | Resource Development, L.L.C. | Silicone compositions, methods of making and using VOC free, non-flammable creams, pastes and powders to render nonporous surfaces water, soil and stain repellent |
DE10016485A1 (en) | 2000-04-01 | 2001-10-11 | Dmc2 Degussa Metals Catalysts | Glass, ceramic and metal substrates with a self-cleaning surface, process for their production and their use |
US20020049276A1 (en) * | 2000-04-05 | 2002-04-25 | Zwick Paul D. | Thermoplastic elastomer gel compositions and method of making same |
AU2001251583A1 (en) | 2000-04-12 | 2001-10-30 | World Properties Inc. | Method for improving bonding of rigid, thermosetting compositions to hydrophilicsurfaces, and the articles formed thereby |
EP1409435A1 (en) | 2000-04-14 | 2004-04-21 | Nanogate Technologies GmbH | Ceramic material surface with hydrophobic or ultraphobic properties and method for the production thereof |
WO2001081487A1 (en) | 2000-04-21 | 2001-11-01 | Science & Technology Corporation @ Unm | Prototyping of patterned functional nanostructures |
DE10022246A1 (en) | 2000-05-08 | 2001-11-15 | Basf Ag | Coating agent for the production of difficult to wet surfaces |
JP2001316630A (en) | 2000-05-09 | 2001-11-16 | Nippon Paint Co Ltd | Coating material composition for topcoat |
US6660686B2 (en) | 2000-05-24 | 2003-12-09 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalyst and process for producing the same |
US6476095B2 (en) | 2000-06-02 | 2002-11-05 | Microphase Coatings, Inc. | Antifouling coating composition |
EP1164161A1 (en) | 2000-06-16 | 2001-12-19 | The Procter & Gamble Company | Thermoplastic hydrophilic polymeric compositions with high water solubility component |
US6403397B1 (en) | 2000-06-28 | 2002-06-11 | Agere Systems Guardian Corp. | Process for fabricating organic semiconductor device involving selective patterning |
JP3876961B2 (en) | 2000-06-29 | 2007-02-07 | 信越化学工業株式会社 | Surface treatment agent and water / oil repellent article |
JP2002020575A (en) * | 2000-07-10 | 2002-01-23 | Denki Kagaku Kogyo Kk | Rubber modified aromatic vinyl based copolymer composition |
US7004184B2 (en) | 2000-07-24 | 2006-02-28 | The Reagents Of The University Of Michigan | Compositions and methods for liquid metering in microchannels |
EP1180533A1 (en) | 2000-08-10 | 2002-02-20 | The Procter & Gamble Company | Thermoplastic hydrophilic, polymeric compostions with improved adhesive properties for moisture vapour permeable structures |
EP1193289A1 (en) | 2000-10-02 | 2002-04-03 | The Procter & Gamble Company | Improved thermoplastic hydrophilic polymeric compositions for moisture vapour permeable structures |
JP2004523598A (en) | 2000-08-10 | 2004-08-05 | ザ プロクター アンド ギャンブル カンパニー | Thermoplastic hydrophilic polymer composition with improved adhesive properties for moisture permeable structures |
US7785699B1 (en) | 2000-09-06 | 2010-08-31 | Ward Calvin B | Electrostatically charged porous water-impermeable absorbent laminate for protecting work surfaces from contamination |
AU2001294214A1 (en) | 2000-10-10 | 2002-04-22 | Asahi Glass Company, Limited | Composition for imparting water repellency and oil resistance |
US6451876B1 (en) | 2000-10-10 | 2002-09-17 | Henkel Corporation | Two component thermosettable compositions useful for producing structural reinforcing adhesives |
US6613860B1 (en) | 2000-10-12 | 2003-09-02 | 3M Innovative Properties Company | Compositions comprising fluorinated polyether silanes for rendering substrates oil and water repellent |
US6610363B2 (en) | 2000-10-18 | 2003-08-26 | Nanofilm, Ltd. | Composition with film forming alkylsilsesquioxane polymer and method for applying hydrophobic films to surfaces |
FR2815636B1 (en) * | 2000-10-20 | 2006-02-10 | Lhd Lab Hygiene Dietetique | NOVEL AMPHIPHILIC COPOLYMERS USEFULLY AS EMULSIFYING AGENTS |
DE10055135C2 (en) | 2000-11-07 | 2003-06-18 | Ecs Environment Care Sys Gmbh | Device for catching flying insects |
GB2368967A (en) | 2000-11-14 | 2002-05-15 | Secr Defence | System for the humidification of polymer electrolyte membrane fuel cells |
AU2002225780A1 (en) | 2000-11-15 | 2002-05-27 | Ssw Holding Company, Inc. | Coating with anti-microbial agent for refrigerator shelving |
CA2353207A1 (en) | 2000-11-20 | 2002-05-20 | C-Cure Corporation | Colored cement |
US6488347B1 (en) | 2000-11-21 | 2002-12-03 | Gemtron Corporation | Refrigerator shelf with one-piece internally ribbed/reinforced polymeric frame and reinforced suspension hooks |
US6423372B1 (en) | 2000-12-13 | 2002-07-23 | North Carolina State University | Tailoring the grafting density of organic modifiers at solid/liquid interfaces |
JP2002241695A (en) | 2000-12-15 | 2002-08-28 | Dow Corning Toray Silicone Co Ltd | Water-repellent silicone coating agent composition |
DE10063739B4 (en) | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrates with self-cleaning surface, process for their preparation and their use |
US6729704B2 (en) | 2000-12-22 | 2004-05-04 | General Electric Company | Removable glass encapsulated shelves |
FR2819518B1 (en) | 2001-01-12 | 2005-03-11 | Omya Ag | PROCESS FOR TREATING A MINERAL FILL BY A POLYDIALKYLSILOXANE AND A FATTY ACID, HYDROPHOBIC CHARGES THUS OBTAINED, AND THEIR APPLICATIONS IN "BREATHABLE" FILM POLYMERS |
JP4908681B2 (en) | 2001-02-09 | 2012-04-04 | 東レ・ダウコーニング株式会社 | Silicone resin composition for water repellent coating |
DE10106213A1 (en) | 2001-02-10 | 2002-08-22 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Self-cleaning paint coatings and methods and means of making the same |
WO2002068558A1 (en) | 2001-02-22 | 2002-09-06 | Shin-Etsu Chemical Co., Ltd. | Water-based water repellant for treatment of substrates |
CN1333018C (en) | 2001-03-15 | 2007-08-22 | 卡伯特公司 | Corrosion-resistant coating composition |
DE60228943D1 (en) | 2001-04-10 | 2008-10-30 | Harvard College | MICROLINS FOR PROJECTION SLITHOGRAPHY AND ITS PRODUCTION PROCESS |
US6884904B2 (en) | 2001-04-12 | 2005-04-26 | Air Products And Chemicals, Inc. | MDI-based polyurethane prepolymer with low monomeric MDI content |
DE10118346A1 (en) | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning, water-repellent textiles, used e.g. for tents, sports clothing and carpets, made by impregnating textile material with a suspension of hydrophobic particles and then removing the solvent |
DE10118352A1 (en) | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10118351A1 (en) | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
DE10120989A1 (en) | 2001-04-25 | 2002-11-07 | Inst Polymerforschung Dresden | Hydrophobic permanent coatings on substrates and processes for their production |
US20040102124A1 (en) | 2001-05-02 | 2004-05-27 | Migaku Suzuki | Highly permeable and water resistant barrier sheet, and absorber product using the barrier sheet |
DE60210321T8 (en) * | 2001-05-15 | 2007-02-15 | Denki Kagaku Kogyo K.K. | PROCESS FOR THE PRODUCTION OF OLEFIN / VINYLAROMAT COPOLYMER |
AU2002368540A1 (en) | 2001-05-16 | 2005-02-14 | North Carolina State University | Methods for forming tunable molecular gradients on substrates |
US6806299B2 (en) | 2001-05-18 | 2004-10-19 | The Regents Of The University Of California | Preparation of hydrophobic organic aeorgels |
US7211329B2 (en) | 2001-05-18 | 2007-05-01 | Schott Ag | Process for making a product with a long-lasting easily cleaned surface and product thereof |
US20030032681A1 (en) | 2001-05-18 | 2003-02-13 | The Regents Of The University Of Clifornia | Super-hydrophobic fluorine containing aerogels |
US20020192472A1 (en) | 2001-05-25 | 2002-12-19 | Bernd Metz | Easily cleanable coating |
US7005372B2 (en) | 2003-01-21 | 2006-02-28 | Novellus Systems, Inc. | Deposition of tungsten nitride |
WO2002096831A1 (en) | 2001-05-30 | 2002-12-05 | Moltech Invent S.A. | Hydrophilic protective layers bonded on hydrophobic substrates for use at elevated temperature |
JP2002356651A (en) | 2001-05-30 | 2002-12-13 | Dow Corning Toray Silicone Co Ltd | Silicone composition for water repellent coating |
US6851776B2 (en) | 2001-06-28 | 2005-02-08 | Gemtron Corporation | Refrigerator compartment housing vertically adjustable shelves, each formed from a piece of tempered glass to which is injection molded a frame in the form of front and rear border members |
DE10134477A1 (en) | 2001-07-16 | 2003-02-06 | Creavis Tech & Innovation Gmbh | Self-cleaning surfaces through hydrophobic structures and processes for their production |
US7568583B2 (en) | 2001-07-16 | 2009-08-04 | Maytag Corporation | Upright rear wall extension for refrigerator shelves |
US6689200B2 (en) | 2001-07-25 | 2004-02-10 | The Sherwin-Williams Company | Film-forming water-based water repellent coating compositions |
US7056868B2 (en) | 2001-07-30 | 2006-06-06 | Cabot Corporation | Hydrophobe associative polymers and compositions and methods employing them |
US7341789B2 (en) | 2001-08-10 | 2008-03-11 | 3M Innovative Properties Company | Stain resistant protective film and adhesive sheet having the same thereon |
US6786562B2 (en) | 2001-08-22 | 2004-09-07 | Engineered Glass Products Llc | Refrigeration shelf and method of making the same |
JP2003160361A (en) | 2001-09-14 | 2003-06-03 | Wilson:Kk | Two-pack type water repellent for glass surface |
US6956084B2 (en) | 2001-10-04 | 2005-10-18 | Bridgestone Corporation | Nano-particle preparation and applications |
JP2005518827A (en) | 2001-10-05 | 2005-06-30 | サーモディクス,インコーポレイテッド | Particle fixing coating and use thereof |
ATE386751T1 (en) * | 2001-10-23 | 2008-03-15 | Asahi Chemical Ind | HYDROGENATED COPOLYMER |
KR100447931B1 (en) | 2001-10-24 | 2004-09-08 | 한국화학연구원 | The super water-repellent organic/inorganic composite membrane |
FR2831547B1 (en) | 2001-10-26 | 2005-08-19 | Rhodia Chimie Sa | LIQUID SILICONE FORMULATION FOR THE PRODUCTION OF ANTI-ADHERENT AND HYDROFUGED ELASTOMERIC REINFORCED COATINGS ON A SOLID SUPPORT, FOR EXAMPLE PAPER |
FR2831551B1 (en) | 2001-10-31 | 2004-07-02 | Dehon Sa | WATERPROOFING COMPOSITION, WINDSCREEN WASHER WITH CONTAINER, PARTICULARLY FOR VEHICLE WINDSHIELD |
PL204021B1 (en) | 2001-11-02 | 2009-12-31 | Cnt Spo & Lstrok Ka Z Ogranicz | Superhydrophobous coating |
CN1538909A (en) | 2001-11-08 | 2004-10-20 | 日本板硝子株式会社 | Article coated with coating film, and functional article coated with coating film using the same |
IL146598A0 (en) | 2001-11-20 | 2002-07-25 | Silcoat Ltd | Method for the preparation of aggregates |
US20050165194A1 (en) | 2001-11-20 | 2005-07-28 | Rhodia Chimie | Crosslinking agent for a silicone composition which can be crosslinked at low temperature based on a hydrogenated silicone oil comprising Si-H units at the chain end and in the chain |
TW200300448A (en) | 2001-11-21 | 2003-06-01 | Novartis Ag | Conditioning solution for contact lenses |
AU2002358506A1 (en) | 2001-11-27 | 2003-06-10 | Basf Drucksysteme Gmbh | Laser engravable flexo printing elements for the production of flexo printing forms containing blends of hydrophilic polymers and hydrophobic elastomers |
US6890360B2 (en) | 2001-12-17 | 2005-05-10 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
KR20030052853A (en) | 2001-12-21 | 2003-06-27 | 주식회사 엘지이아이 | Shelf for refrigerator |
US6811844B2 (en) | 2001-12-21 | 2004-11-02 | E. I. Du Pont De Nemours And Company | Multilayer film |
FR2833963B1 (en) | 2001-12-21 | 2004-03-12 | Rhodia Chimie Sa | CROSSLINKER FOR A CROSSLINKABLE SILICONE COMPOSITION WITH LOW PLATINUM RATES, BASED ON HYDROGENATED SILICONE OIL COMPRISING Si-H PATTERNS AT THE END OF THE CHAIN AND IN THE CHAIN |
JP3698138B2 (en) | 2001-12-26 | 2005-09-21 | セイコーエプソン株式会社 | Water repellent treatment method, thin film forming method, organic EL device manufacturing method using the method, organic EL device, and electronic apparatus |
US20030125656A1 (en) | 2001-12-31 | 2003-07-03 | Vadim Davankov | Hemo-and biocompatible beaded polymeric material for purification of physiological fluids of organism, method of producing the material, as well as method of and device for purification of physiological fluids of organism with use of the material |
WO2003061537A1 (en) | 2002-01-17 | 2003-07-31 | Masachusetts Eye And Ear Infirmary | Minimally invasive retinal prosthesis |
CN1208388C (en) | 2002-01-17 | 2005-06-29 | 佳能株式会社 | Epoxy resin composition, surface treatment method, liquid jetting record head and liquid jetting recorder |
MXPA04007212A (en) | 2002-01-25 | 2004-10-29 | Ssw Holding Co Inc | Adhesively bonded, leak-proof shelf. |
US20030222043A1 (en) | 2002-01-25 | 2003-12-04 | Eric Rouch | Adhesively bonded, leak-proof shelf |
JP2003221406A (en) | 2002-01-31 | 2003-08-05 | Asahi Glass Co Ltd | Aqueous dispersion |
US6759454B2 (en) * | 2002-02-07 | 2004-07-06 | Kraton Polymers U.S. Llc | Polymer modified bitumen compositions |
JP2003272336A (en) | 2002-03-18 | 2003-09-26 | Asahi Glass Co Ltd | Mounting member made of glass for magnetic disk and method for manufacturing the same |
GB0206930D0 (en) | 2002-03-23 | 2002-05-08 | Univ Durham | Method and apparatus for the formation of hydrophobic surfaces |
WO2003082998A1 (en) | 2002-03-28 | 2003-10-09 | Nanogate Technologies Gmbh | Water-based coating fluid |
US6855375B2 (en) | 2002-03-28 | 2005-02-15 | Matsushita Electric Industrial Co., Ltd. | Method for producing water-repellent film |
DE10215962A1 (en) | 2002-04-11 | 2003-10-30 | Wacker Polymer Systems Gmbh | Organopolymers of silicone and their saponification products |
EP1857497B1 (en) | 2002-04-12 | 2008-08-13 | The Procter and Gamble Company | Liquid impermeable, moisture vapour permeable layers and films comprising thermoplastic hydrophilic polymeric compositions and having improved strength |
AT5980U1 (en) | 2002-04-15 | 2003-02-25 | Schaefer Philipp | FULL-SCORED WALKNAPPA LEATHER AND METHOD FOR PRODUCING THE SAME |
FR2838735B1 (en) | 2002-04-17 | 2005-04-15 | Saint Gobain | SELF-CLEANING COATING SUBSTRATE |
US20030203771A1 (en) | 2002-04-26 | 2003-10-30 | Ronald Rosenberg | Polyurethane elastomers from HDI prepolymers with reduced content of free HDI monomers |
US20030207629A1 (en) | 2002-05-01 | 2003-11-06 | Sobieski Robert T. | Highly durable, coated fabrics exhibiting hydrophobicity, oleophobicity and stain resistance and related methods |
US7166235B2 (en) | 2002-05-09 | 2007-01-23 | The Procter & Gamble Company | Compositions comprising anionic functionalized polyorganosiloxanes for hydrophobically modifying surfaces and enhancing delivery of active agents to surfaces treated therewith |
JPWO2003095499A1 (en) * | 2002-05-10 | 2005-09-15 | Psジャパン株式会社 | Styrenic polymer resin and composition thereof |
US6706408B2 (en) | 2002-05-16 | 2004-03-16 | Surmodics, Inc. | Silane coating composition |
FR2841063B1 (en) | 2002-06-18 | 2004-09-17 | Commissariat Energie Atomique | DEVICE FOR DISPLACING SMALL VOLUMES OF LIQUID ALONG A MICRO-CATENARY BY ELECTROSTATIC FORCES |
US6998051B2 (en) | 2002-07-03 | 2006-02-14 | Ferro Corporation | Particles from supercritical fluid extraction of emulsion |
WO2004009505A1 (en) | 2002-07-23 | 2004-01-29 | Shell Internationale Research Maatschappij B.V. | Hydrophobic surface treatment composition and method of making and using same |
AU2003281812A1 (en) | 2002-07-26 | 2004-02-23 | Arkema | Adhesive composition for a humid medium based on block copolymers comprising at least one hydrophilic block |
DE10236146A1 (en) | 2002-07-31 | 2004-02-19 | Basf Coatings Ag | Coating material, useful for scratch-resistant, transparent coatings, films, shaped parts, and multilayer effect coatings in automobile finishing, contains hydrophobic and hydrophilic nano particles based on silicon dioxide |
FR2843048B1 (en) | 2002-08-01 | 2004-09-24 | Commissariat Energie Atomique | DEVICE FOR INJECTING AND MIXING LIQUID MICRO-DROPS. |
EP1387169B1 (en) | 2002-08-02 | 2006-05-24 | Sony Deutschland GmbH | Method of attaching hydrophilic species to hydrophilic macromolecules and immobilizing the hydrophilic macromolecules on a hydrophobic surface |
DE10235446B3 (en) | 2002-08-02 | 2004-01-22 | WECO Bahnüberwege- und Auffangwannenbau GmbH | Collection system for a vehicle parking space and method for avoiding soil pollution in the area of the vehicle parking space |
DE10236728A1 (en) | 2002-08-09 | 2004-02-26 | Schott Glas | Easy to clean device |
US6871923B2 (en) | 2002-09-24 | 2005-03-29 | Maytag Corporation | Spill-proof refrigerator shelf |
US6966990B2 (en) | 2002-10-11 | 2005-11-22 | Ferro Corporation | Composite particles and method for preparing |
US7041088B2 (en) | 2002-10-11 | 2006-05-09 | Ethicon, Inc. | Medical devices having durable and lubricious polymeric coating |
JP4899143B2 (en) * | 2002-10-28 | 2012-03-21 | 東レ・デュポン株式会社 | Thermoplastic elastomer resin composition and molded article |
US20040087924A1 (en) | 2002-11-06 | 2004-05-06 | Kimberly-Clark Worldwide, Inc. | Semi-hydrophobic cover for an absorbent product |
JP4136614B2 (en) | 2002-11-14 | 2008-08-20 | 沖電気工業株式会社 | Method for producing super water-repellent film |
US6758887B2 (en) | 2002-11-29 | 2004-07-06 | United Technologies Corporation | Chromate free waterborne epoxy corrosion resistant primer |
US20060154048A1 (en) | 2002-12-10 | 2006-07-13 | Toyoyuki Teranishi | Article having functional coating film thereon, method for manufacture thereof, and applying material for forming functional coating film |
GB0229003D0 (en) | 2002-12-12 | 2003-01-15 | Int Coatings Ltd | Powder coating process |
GB0229004D0 (en) | 2002-12-12 | 2003-01-15 | Int Coatings Ltd | Powder coating apparatus and process |
DE10260067A1 (en) | 2002-12-19 | 2004-07-01 | Röhm GmbH & Co. KG | Coating composition for the production of reshapable scratch-resistant coatings with a dirt-repellent effect, scratch-resistant, formable dirt-repellent moldings and methods for the production thereof |
US6811884B2 (en) | 2002-12-24 | 2004-11-02 | Ppg Industries Ohio, Inc. | Water repellant surface treatment and treated articles |
US20040138083A1 (en) | 2003-01-10 | 2004-07-15 | Kimbrell Wiliam C. | Substrates having reversibly adaptable surface energy properties and method for making the same |
US7468333B2 (en) | 2003-01-10 | 2008-12-23 | Milliken & Company | Wash-durable, liquid repellent, and stain releasing polyester fabric substrates |
US6875818B2 (en) | 2003-01-16 | 2005-04-05 | Bridgestone Corporation | Polymer nano-strings |
US7083748B2 (en) | 2003-02-07 | 2006-08-01 | Ferro Corporation | Method and apparatus for continuous particle production using supercritical fluid |
US6931888B2 (en) | 2003-02-07 | 2005-08-23 | Ferro Corporation | Lyophilization method and apparatus for producing particles |
US7288311B2 (en) | 2003-02-10 | 2007-10-30 | Dai Nippon Printing Co., Ltd. | Barrier film |
DE10306891B4 (en) * | 2003-02-18 | 2016-07-14 | Ineos Styrolution Europe Gmbh | Transparent block copolymers of vinylaromatics and dienes |
US7150896B2 (en) | 2003-02-25 | 2006-12-19 | Dainippon Ink And Chemicals, Inc. | Method of producing a thermosensitive recording medium |
DE10308379A1 (en) | 2003-02-27 | 2004-09-09 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Dispersion of water in hydrophobic oxides for the production of hydrophobic nanostructured surfaces |
US7124450B2 (en) | 2003-03-05 | 2006-10-24 | Dennis Davidson | Flushable plunger cover |
FR2852312B1 (en) | 2003-03-10 | 2007-04-06 | Rhodia Chimie Sa | A METHOD FOR INCREASING THE HYDROFUGATION OF MINERAL BINDER COMPOSITIONS AND THE COMPOSITIONS WHICH MAY BE OBTAINED BY THIS METHOD AND THEIR USES |
JP2004308984A (en) | 2003-04-04 | 2004-11-04 | Matsushita Electric Ind Co Ltd | Cooker |
AU2003901735A0 (en) | 2003-04-11 | 2003-05-01 | Unisearch Limited | Durable superhydrophobic coating |
AU2003901734A0 (en) | 2003-04-11 | 2003-05-01 | Unisearch Limited | Transparent superhydrophobic coating |
US6923216B2 (en) | 2003-04-15 | 2005-08-02 | Entegris, Inc. | Microfluidic device with ultraphobic surfaces |
US6976585B2 (en) | 2003-04-15 | 2005-12-20 | Entegris, Inc. | Wafer carrier with ultraphobic surfaces |
US6938774B2 (en) | 2003-04-15 | 2005-09-06 | Entegris, Inc. | Tray carrier with ultraphobic surfaces |
US6852390B2 (en) | 2003-04-15 | 2005-02-08 | Entegris, Inc. | Ultraphobic surface for high pressure liquids |
US6845788B2 (en) | 2003-04-15 | 2005-01-25 | Entegris, Inc. | Fluid handling component with ultraphobic surfaces |
US7074294B2 (en) | 2003-04-17 | 2006-07-11 | Nanosys, Inc. | Structures, systems and methods for joining articles and materials and uses therefor |
US7056409B2 (en) | 2003-04-17 | 2006-06-06 | Nanosys, Inc. | Structures, systems and methods for joining articles and materials and uses therefor |
JP2005037881A (en) | 2003-04-21 | 2005-02-10 | Fuji Photo Film Co Ltd | Pattern forming method, image forming method, fine particle adsorption pattern forming method, conductive pattern forming method, pattern forming material, and planographic printing plate |
US6982242B2 (en) | 2003-04-23 | 2006-01-03 | Rohm And Haas Company | Aqueous detergent composition and method of use |
EP1475426B1 (en) | 2003-04-24 | 2006-10-11 | Goldschmidt GmbH | Process for the production of removable soil- and water-resistant surface coatings |
USD547640S1 (en) | 2003-04-28 | 2007-07-31 | Clairson, Inc. | Drawer bracket |
US7497533B2 (en) | 2003-04-28 | 2009-03-03 | Clairson, Inc. | Shelves, resilient drawer stops, and drawer brackets for supporting shelves and drawers |
EP1473355A1 (en) | 2003-04-29 | 2004-11-03 | The Procter & Gamble Company | A method for increasing the hydrophobicity of a lavatory bowl surface |
JP4293035B2 (en) | 2003-05-07 | 2009-07-08 | セイコーエプソン株式会社 | Liquid repellent film covering member, component of liquid ejection device, nozzle plate of liquid ejection head, liquid ejection head, and liquid ejection device |
ATE366283T1 (en) * | 2003-05-14 | 2007-07-15 | Dow Global Technologies Inc | BLOCK COPOLYMER COMPOSITION AND TRANSPARENT ELASTOMERIC ARTICLES MADE THEREFROM |
EP1479738A1 (en) | 2003-05-20 | 2004-11-24 | DSM IP Assets B.V. | Hydrophobic coatings comprising reactive nano-particles |
DE10325094B4 (en) | 2003-06-03 | 2006-02-16 | Rudolf Gmbh & Co. Kg Chemische Fabrik | Preparations for the oil and water repellent finishing of fabrics and their use |
WO2004110132A2 (en) | 2003-06-12 | 2004-12-23 | E.I. Dupont De Nemours And Company | Water vapor permeable hydrophilic membranes and devices made there-from and process for using the devices |
JP3865719B2 (en) | 2003-07-03 | 2007-01-10 | 昇太郎 望月 | Animal excrement disposal material |
EP1641975A1 (en) | 2003-07-08 | 2006-04-05 | Karl Scheidler | Methods and compositions for improving light-fade resistance and soil repellency of textiles and leathers |
US7344783B2 (en) | 2003-07-09 | 2008-03-18 | Shell Oil Company | Durable hydrophobic surface coatings using silicone resins |
US7034072B2 (en) | 2003-07-22 | 2006-04-25 | E. I. Dupont De Nemours And Company | Aqueous coating composition |
DE10336544A1 (en) | 2003-08-05 | 2005-02-24 | Degussa Ag | Two-component coating system for smooth surfaces with "easy-to-clean" properties |
US20060068118A1 (en) | 2003-08-13 | 2006-03-30 | Reeve John A | Silicon-containing treatments for solid substrates |
EP1660584B1 (en) | 2003-08-27 | 2014-05-21 | Dow Corning Corporation | Silicone oil-in-water (o/w) emulsions or compositions useful for water repellent applications |
AU2003269794A1 (en) | 2003-09-02 | 2005-03-16 | Sabanci Universitesi | Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them |
US7179758B2 (en) | 2003-09-03 | 2007-02-20 | International Business Machines Corporation | Recovery of hydrophobicity of low-k and ultra low-k organosilicate films used as inter metal dielectrics |
JP4518466B2 (en) | 2003-09-04 | 2010-08-04 | 石原薬品株式会社 | Super water-repellent film forming composition |
US7198855B2 (en) | 2003-09-12 | 2007-04-03 | Becton, Dickinson And Company | Methods of surface modification of a flexible substrate to enhance cell adhesion |
WO2005028562A1 (en) | 2003-09-17 | 2005-03-31 | Techno Polymer Co., Ltd. | Polymer composition for molded-article molding, molded article, hydrophilic molded article and process for producing the same, and layered article |
JP4635217B2 (en) | 2003-09-17 | 2011-02-23 | 学校法人慶應義塾 | Surface treatment agent and material, and surface treatment method |
TWI240648B (en) | 2003-09-30 | 2005-10-01 | Univ Nat Central | Method for making transparent zeolite film and structure of the zeolite film |
WO2005042437A2 (en) | 2003-09-30 | 2005-05-12 | Schott Ag | Antimicrobial glass and glass ceramic surfaces and their production |
US7265180B2 (en) * | 2003-10-01 | 2007-09-04 | Lanxess Corporation | Thermoplastic molding composition having high clarity |
US7175723B2 (en) | 2003-10-03 | 2007-02-13 | The Regents Of The University Of California | Structure having nano-fibers on annular curved surface, method of making same and method of using same to adhere to a surface |
ITBO20030593A1 (en) | 2003-10-13 | 2005-04-14 | Curvet Spa | PRODUCT AND METHOD FOR WATER REPELLENT TREATMENT OF SURFACES. |
US7425367B2 (en) | 2003-10-23 | 2008-09-16 | O'rear Iii Edgar A | Method for making an article water resistant and articles made therefrom |
JP4997765B2 (en) | 2003-12-04 | 2012-08-08 | 旭硝子株式会社 | Fluorine-containing compound, water-repellent composition and thin film |
US7767998B2 (en) | 2003-12-04 | 2010-08-03 | Alcatel-Lucent Usa Inc. | OFETs with active channels formed of densified layers |
US20050121782A1 (en) | 2003-12-05 | 2005-06-09 | Koichiro Nakamura | Selectively adherent substrate and method for producing the same |
US6942746B2 (en) | 2003-12-11 | 2005-09-13 | Optima, Inc. | Lens blocking system |
US8034173B2 (en) | 2003-12-18 | 2011-10-11 | Evonik Degussa Gmbh | Processing compositions and method of forming the same |
US7828889B2 (en) | 2003-12-18 | 2010-11-09 | The Clorox Company | Treatments and kits for creating transparent renewable surface protective coatings |
KR20050068860A (en) | 2003-12-30 | 2005-07-05 | 엘지.필립스 엘시디 주식회사 | Upper substrate for use in dual-plate organic electroluminescent device and method for fabricating the same |
US20080107864A1 (en) | 2004-01-15 | 2008-05-08 | Newsouth Innovations Pty Limited Rupert Myers Building | Method of Making a Surface Hydrophobic |
DE602005024924D1 (en) | 2004-02-11 | 2011-01-05 | Procter & Gamble | HYDROPHOBIC SURFACE-COATED VACUUM ARTICLES |
DE202004002438U1 (en) | 2004-02-16 | 2005-08-11 | Systec Pos-Technology Gmbh | Shopping cart or transport container |
DE102004008772A1 (en) | 2004-02-23 | 2005-09-08 | Institut für Neue Materialien Gemeinnützige GmbH | Abrasion resistant and alkali resistant low energy surface coatings or moldings |
FR2866643B1 (en) | 2004-02-24 | 2006-05-26 | Saint Gobain | SUBSTRATE, ESPECIALLY GLASS, WITH A HYDROPHOBIC SURFACE, WITH IMPROVED DURABILITY OF HYDROPHOBIC PROPERTIES |
US7213309B2 (en) | 2004-02-24 | 2007-05-08 | Yunzhang Wang | Treated textile substrate and method for making a textile substrate |
US7112369B2 (en) | 2004-03-02 | 2006-09-26 | Bridgestone Corporation | Nano-sized polymer-metal composites |
WO2005087867A1 (en) * | 2004-03-05 | 2005-09-22 | Gls Corporation | Block copolymer compositions for overmolding any nylon |
EP1738378A4 (en) | 2004-03-18 | 2010-05-05 | Nanosys Inc | Nanofiber surface based capacitors |
US7048889B2 (en) | 2004-03-23 | 2006-05-23 | Lucent Technologies Inc. | Dynamically controllable biological/chemical detectors having nanostructured surfaces |
JP4522739B2 (en) | 2004-03-31 | 2010-08-11 | 株式会社堀場製作所 | Concentration method of liquid sample, holding table for concentration, and trace element analysis method using the same |
US20070215004A1 (en) | 2004-04-12 | 2007-09-20 | Tarou Kuroda | Stain-Proofing Coating Composition |
US7342551B2 (en) | 2004-04-13 | 2008-03-11 | Electronic Controlled Systems | Antenna systems for reliable satellite television reception in moisture conditions |
FR2869604B1 (en) | 2004-04-28 | 2006-06-23 | Saint Gobain | ACTIVATION OF A GLASS SURFACE |
US7323033B2 (en) | 2004-04-30 | 2008-01-29 | Lucent Technologies Inc. | Nanostructured surfaces having variable permeability |
CN1957008A (en) | 2004-05-25 | 2007-05-02 | 西巴特殊化学品控股有限公司 | Perfluorinated esters, polyester, ethers and carbonates |
US7354624B2 (en) | 2004-05-28 | 2008-04-08 | Ppg Industries Ohio, Inc. | Multi-layer coatings and related methods |
US7354650B2 (en) | 2004-05-28 | 2008-04-08 | Ppg Industries Ohio, Inc. | Multi-layer coatings with an inorganic oxide network containing layer and methods for their application |
CN1960857A (en) | 2004-05-31 | 2007-05-09 | 三井化学株式会社 | Hydrophilic porous film and multi-layered film comprising the same |
US7879396B2 (en) | 2004-06-04 | 2011-02-01 | Applied Microstructures, Inc. | High aspect ratio performance coatings for biological microfluidics |
KR101069519B1 (en) | 2004-07-08 | 2011-09-30 | 삼성전자주식회사 | Alternating Organic Semiconductor Copolymers Containing Oligothiophene and n-Type Heteroaromatic Units in the Backbone Chain |
US20060013983A1 (en) | 2004-07-15 | 2006-01-19 | 3M Innovative Properties Company | Adhesive delivery of oil and water repellents |
US7150904B2 (en) | 2004-07-27 | 2006-12-19 | Ut-Battelle, Llc | Composite, ordered material having sharp surface features |
US7258731B2 (en) | 2004-07-27 | 2007-08-21 | Ut Battelle, Llc | Composite, nanostructured, super-hydrophobic material |
ITVA20040031A1 (en) | 2004-08-05 | 2004-11-05 | Lamberti Spa | HIGH DISSOLUTION SPEED HYDROXIALKYL GUAR DERIVATIVES |
US20060029808A1 (en) | 2004-08-06 | 2006-02-09 | Lei Zhai | Superhydrophobic coatings |
CN101044651A (en) | 2004-08-19 | 2007-09-26 | 通用汽车环球科技运作公司 | Surface modifications of fuel cell elements for improved water management |
US7344758B2 (en) | 2004-09-07 | 2008-03-18 | E.I. Du Pont De Nemours And Company | Hydrocarbon extenders for surface effect compositions |
WO2006028274A1 (en) | 2004-09-08 | 2006-03-16 | National University Corporation Nagoya University | Production of cell culture product and material for use in said production |
US7547424B2 (en) | 2004-09-21 | 2009-06-16 | Van Andel Research Institute | Method and apparatus for making partitioned slides |
EP1802721A4 (en) | 2004-10-05 | 2007-12-26 | Newsouth Innovations Pty Ltd | Hydrophobic and lyophobic coating |
MX2007004477A (en) | 2004-10-15 | 2008-11-04 | Donnelly Corp | Refrigerator shelf assembly. |
US7722951B2 (en) | 2004-10-15 | 2010-05-25 | Georgia Tech Research Corporation | Insulator coating and method for forming same |
JP2006131938A (en) | 2004-11-04 | 2006-05-25 | Stanley Electric Co Ltd | Method and device for producing super-water repellent film and product thereby |
US7204298B2 (en) | 2004-11-24 | 2007-04-17 | Lucent Technologies Inc. | Techniques for microchannel cooling |
FR2878707B1 (en) | 2004-12-03 | 2008-01-04 | Saint Gobain | SHELF, ESPECIALLY FOR REFRIGERATED FACILITIES, SUITABLE FOR SUPPORTING AT LEAST ONE ACCESSORY AND CORRESPONDING ACCESSORIES |
JP2006176559A (en) * | 2004-12-21 | 2006-07-06 | Ps Japan Corp | Vinylaromatic compound polymer composition excellent in solvent resistance and molding thereof |
US7906177B2 (en) | 2004-12-22 | 2011-03-15 | The Board Of Regents Of The University Of Oklahoma | Method for making an article hydrophobic and oleophobic as well as articles made therefrom and their use |
DE102004062742A1 (en) | 2004-12-27 | 2006-07-06 | Degussa Ag | Textile substrates with self-cleaning properties (lotus effect) |
GB2422608B (en) | 2004-12-30 | 2008-10-01 | Ind Tech Res Inst | Self-cleaning coating comprising hydrophobically-modified particles |
US20060145577A1 (en) | 2005-01-06 | 2006-07-06 | Gemtron Corporation | Shelf assembly for a refrigerator compartment |
US7695767B2 (en) | 2005-01-06 | 2010-04-13 | The Boeing Company | Self-cleaning superhydrophobic surface |
JP4855781B2 (en) | 2005-02-01 | 2012-01-18 | 日東電工株式会社 | Antireflection hard coat film, optical element and image display device |
DE102005004871A1 (en) | 2005-02-03 | 2006-08-10 | Degussa Ag | Highly viscous aqueous emulsions of functional alkoxysilanes, their condensed oligomers, organopolysiloxanes, their preparation and their use for the surface treatment of inorganic materials |
DE102005008927A1 (en) | 2005-02-24 | 2006-08-31 | Philipps-Universität Marburg | Hydrophobic polymer surface, useful as water-repellant coating in e.g. carpets and yarn, comprises a homo or a copolymer containing a side chain exhibiting fluoro-substituted aryl group |
AU2006222350B2 (en) | 2005-03-04 | 2010-08-12 | Steelcase Inc. | Shelf system |
WO2006097597A1 (en) | 2005-03-14 | 2006-09-21 | Rhodia Recherches Et Technologies | Composition comprising a thermoplastic polymer and a hydrophilizing agent |
US7767251B2 (en) | 2005-03-16 | 2010-08-03 | Shiping Wang | Repellent elastomeric article |
DE102005012329A1 (en) | 2005-03-17 | 2006-09-28 | Lanxess Deutschland Gmbh | Process for the hydrophobization of leather by means of alkylalkoxysilanes and hydrophobized leather |
US7908681B2 (en) | 2005-03-22 | 2011-03-22 | Smart Products And Inventions, Inc. | Plungers and devices for storing plumbing tools |
US8899704B2 (en) | 2005-03-25 | 2014-12-02 | Gemtron Corporation | Refrigerator shelf |
WO2006132694A2 (en) | 2005-04-01 | 2006-12-14 | Clemson University | Ultrahydrophobic substrates |
US20070075199A1 (en) | 2005-04-15 | 2007-04-05 | Stewart Brian J | Wire sideplates |
TW200704593A (en) | 2005-04-22 | 2007-02-01 | Dow Corning Toray Co Ltd | Solution or dispersion for substarate surface treatment comprising titanium oxide doped with metallic element, method for substrate surface treatment using the same, and surface-treated material obtained therefrom |
GB0508235D0 (en) | 2005-04-23 | 2005-06-01 | Eastman Kodak Co | A method of forming mirrors on a conducting substrate |
EP1874531A2 (en) | 2005-04-26 | 2008-01-09 | Nanosys, Inc. | Paintable nanofiber coatings |
US7527832B2 (en) | 2005-04-27 | 2009-05-05 | Ferro Corporation | Process for structuring self-cleaning glass surfaces |
US7524531B2 (en) | 2005-04-27 | 2009-04-28 | Ferro Corporation | Structured self-cleaning surfaces and method of forming same |
JP4310290B2 (en) | 2005-04-28 | 2009-08-05 | 株式会社ニデック | A flexible lens retainer for holding a spectacle lens and a spectacle lens peripheral edge processing apparatus having the same. |
DE102005021538A1 (en) | 2005-05-10 | 2006-11-16 | BSH Bosch und Siemens Hausgeräte GmbH | Carrier assembly and thus equipped refrigeration device |
ITVA20050035A1 (en) | 2005-05-17 | 2006-11-18 | Whirlpool Co | DOMESTIC REFRIGERATOR WITH SHELVES |
WO2006127583A1 (en) | 2005-05-25 | 2006-11-30 | H.B. Fuller Licensing & Financing, Inc. | Method of making water repellent laminates |
EP1726609A1 (en) | 2005-05-25 | 2006-11-29 | DSM IP Assets B.V. | Hydrophobic coating |
US20070005024A1 (en) | 2005-06-10 | 2007-01-04 | Jan Weber | Medical devices having superhydrophobic surfaces, superhydrophilic surfaces, or both |
US20060292345A1 (en) | 2005-06-14 | 2006-12-28 | Dave Bakul C | Micropatterned superhydrophobic silica based sol-gel surfaces |
EP1908804A4 (en) | 2005-06-29 | 2010-06-23 | Agc Si Tech Co Ltd | Process for producing water repellent particulate |
US7419615B2 (en) | 2005-06-30 | 2008-09-02 | The Boeing Company | Renewable superhydrophobic coating |
WO2007006777A1 (en) | 2005-07-11 | 2007-01-18 | Akzo Nobel Coatings International B.V. | Powder coating materials |
US7989619B2 (en) | 2005-07-14 | 2011-08-02 | Innovative Surface Technoloiges, Inc. | Nanotextured surfaces |
NZ565662A (en) | 2005-08-09 | 2010-10-29 | Univ Sunderland | Fingerprint analysis using mass spectrometry |
US7748806B2 (en) | 2005-08-29 | 2010-07-06 | Whirlpool Corporation | Encapsulated sliding shelf and over-molded frame |
US7452957B2 (en) | 2005-08-31 | 2008-11-18 | Kimberly-Clark Worldwide, Inc. | Hydrophilic silicone elastomers |
CN101253028B (en) | 2005-09-01 | 2010-06-16 | 詹森药业有限公司 | Use of alkoxylated amines to improve water repellency of wood |
US20090286023A1 (en) * | 2005-09-16 | 2009-11-19 | Pactiv Corporation | Polymer films with treated fillers and improved properties and products and methods using same |
WO2007053242A2 (en) | 2005-09-19 | 2007-05-10 | Wayne State University | Transparent hydrophobic article having self-cleaning and liquid repellant features and method of fabricating same |
JP2007111690A (en) | 2005-09-22 | 2007-05-10 | Akebono Brake Ind Co Ltd | Workpiece to be coated formed with multilayer coating film and method for forming multilayer coating film to workpiece to be coated |
USD612404S1 (en) | 2005-10-13 | 2010-03-23 | Clarion Technologies, Inc. | Refrigerator shelf |
WO2007052260A2 (en) | 2005-10-31 | 2007-05-10 | Shenkar College Of Engineering And Design | Use of poss nanostructured molecules for hydrophobic and self cleaning coatings |
US20070104922A1 (en) | 2005-11-08 | 2007-05-10 | Lei Zhai | Superhydrophilic coatings |
KR101399135B1 (en) | 2005-11-09 | 2014-05-26 | 미츠비시 가스 가가쿠 가부시키가이샤 | Moisture-resistant deoxidant |
FR2893266B1 (en) | 2005-11-14 | 2007-12-21 | Commissariat Energie Atomique | SUPERHYDROPHIL OR SUPERHYDROPHOBIC PRODUCT, PROCESS FOR PRODUCING THE SAME AND USE THEREOF |
US7265468B1 (en) | 2005-11-22 | 2007-09-04 | Mancl Dennis J | Water repellent motor sleeve |
JP2007144917A (en) | 2005-11-30 | 2007-06-14 | Asahi Glass Co Ltd | Super-water repellent film and super-water repellent automobile window using the same, super-water repellent sticking film and method for manufacturing the same, method for manufacturing super-water repellent transparent substrate, and method for super-water repellence treatment of automobile window |
USD607020S1 (en) | 2005-11-30 | 2009-12-29 | Bsh Bosch Und Siemens Hausgeraete Gmbh | Refrigerator shelf |
USD568344S1 (en) | 2005-11-30 | 2008-05-06 | Bsh Bosch Und Siemens Hausgeraete Gmbh | Refrigerator shelf |
EP1973587B1 (en) | 2005-12-12 | 2019-02-06 | AllAccem, Inc. | Methods and systems for preparing antimicrobial films and coatings |
US20070141114A1 (en) | 2005-12-15 | 2007-06-21 | Essilor International Compagnie Generale D'optique | Article coated with an ultra high hydrophobic film and process for obtaining same |
US20070141306A1 (en) | 2005-12-21 | 2007-06-21 | Toshihiro Kasai | Process for preparing a superhydrophobic coating |
KR101285471B1 (en) | 2005-12-22 | 2013-07-12 | 닛키 쇼쿠바이카세이 가부시키가이샤 | Coating liquid for forming low dielectric constant amorphous silica coating film and low dielectric constant amorphous silica coating film obtained from such coating liquid |
TWI322833B (en) | 2005-12-27 | 2010-04-01 | Ind Tech Res Inst | Water-repellent structure and method for making the same |
WO2007077673A1 (en) | 2005-12-28 | 2007-07-12 | Agc Si-Teck Co., Ltd. | Water-repellent inorganic powder and process for production thereof |
JP5145638B2 (en) | 2006-01-06 | 2013-02-20 | パナソニック株式会社 | Resin composition |
WO2007102960A2 (en) | 2006-01-30 | 2007-09-13 | Ashland Licensing And Intellectual Property Llc | Hydrophobic self-cleaning coating compositions |
US20080221009A1 (en) | 2006-01-30 | 2008-09-11 | Subbareddy Kanagasabapathy | Hydrophobic self-cleaning coating compositions |
US8258206B2 (en) | 2006-01-30 | 2012-09-04 | Ashland Licensing And Intellectual Property, Llc | Hydrophobic coating compositions for drag reduction |
US20080221263A1 (en) | 2006-08-31 | 2008-09-11 | Subbareddy Kanagasabapathy | Coating compositions for producing transparent super-hydrophobic surfaces |
US20090182085A1 (en) | 2006-01-30 | 2009-07-16 | Escobar Barrios Vladimir A | Polyurethane-based retention, covering, filling and reinforcement composition |
US20070184247A1 (en) | 2006-02-03 | 2007-08-09 | Simpson John T | Transparent, super-hydrophobic, disordered composite material |
US8598052B2 (en) | 2006-03-02 | 2013-12-03 | Daio Paper Corporation | Highly air-permeable and water-resistance sheet, a highly air-permeable and water-resistance sheet composite and an absorbent article, and a method for manufacturing a highly air-permeable and water-resistance sheet and a method for manufacturing a highly air-permeable and water-resistance sheet composite |
EP1992990A4 (en) | 2006-03-06 | 2011-03-30 | Asahi Glass Co Ltd | Treated substratum with hydrophilic region and water-repellent region and process for producing the same |
DE102006011153A1 (en) | 2006-03-10 | 2007-09-13 | Construction Research & Technology Gmbh | Fluoromodified additive for cementitious products, process for its preparation and its use |
FR2898898B1 (en) | 2006-03-22 | 2008-06-06 | Polyintell Sarl | MOLECULAR IMPRESSIONS FOR RECOGNITION IN AQUEOUS MEDIA, PROCESSES FOR THEIR PREPARATION AND USES THEREOF |
US7585916B2 (en) * | 2006-03-24 | 2009-09-08 | Kraton Polymers Us Llc | Block copolymer compositions |
US20070224898A1 (en) | 2006-03-27 | 2007-09-27 | Deangelis Alfred R | Electrically conductive water repellant fabric composite |
US20090011222A1 (en) | 2006-03-27 | 2009-01-08 | Georgia Tech Research Corporation | Superhydrophobic surface and method for forming same |
US20070231517A1 (en) | 2006-03-31 | 2007-10-04 | Golownia Robert F | Method of reducing the tendency for water insoluble films to form on the exposed surfaces of containers and articles which are used to contain water borne coatings and article |
WO2007123789A2 (en) | 2006-04-06 | 2007-11-01 | Symyx Technologies, Inc. | Water resistant film forming compositions incorporating hydrophilic activities |
US20070259156A1 (en) | 2006-05-03 | 2007-11-08 | Lucent Technologies, Inc. | Hydrophobic surfaces and fabrication process |
US20070274871A1 (en) | 2006-05-23 | 2007-11-29 | Genetix Limited | Well plate |
WO2007139773A2 (en) | 2006-05-25 | 2007-12-06 | Clarion Technologies, Inc. | Refrigerator shelf assembly |
WO2007139116A1 (en) * | 2006-05-29 | 2007-12-06 | Denki Kagaku Kogyo Kabushiki Kaisha | Process for production of cross copolymers, cross copolymers obtained by the process, and use thereof |
US20080044635A1 (en) | 2006-06-08 | 2008-02-21 | O'neill Michael | Barrier film for flexible articles |
US7731316B2 (en) | 2006-06-09 | 2010-06-08 | Maytag Corporation | Universal shelf module for a refrigerator |
US8354160B2 (en) | 2006-06-23 | 2013-01-15 | 3M Innovative Properties Company | Articles having durable hydrophobic surfaces |
JP4792338B2 (en) | 2006-07-04 | 2011-10-12 | 株式会社日立製作所 | Liquid transfer device |
EP2038452B1 (en) | 2006-07-05 | 2016-05-18 | Postech Academy-Industry- Foundation | Method for fabricating superhydrophobic surface |
WO2008004827A1 (en) | 2006-07-05 | 2008-01-10 | Postech Academy-Industry Foundation | Method for fabricating superhydrophobic surface and solid having superhydrophobic surface structure by the same method |
US20080193772A1 (en) | 2006-07-07 | 2008-08-14 | Bio-Rad Laboratories, Inc | Mass spectrometry probes having hydrophobic coatiings |
DE102006035786A1 (en) * | 2006-07-28 | 2008-03-13 | Tesa Ag | Adhesive film with high optical transparency for bonding as splinter protection on glass panes in consumer electronic components |
US8202614B2 (en) | 2006-08-09 | 2012-06-19 | Luna Innovations Incorporated | Additive particles having superhydrophobic characteristics and coatings and methods of making and using the same |
HUE028612T2 (en) | 2006-08-09 | 2017-01-30 | Innovation Chemical Tech Ltd | Nano structured phased hydrophobic layers on substrates |
US20080039576A1 (en) * | 2006-08-14 | 2008-02-14 | General Electric Company | Vulcanizate composition |
US20080070146A1 (en) | 2006-09-15 | 2008-03-20 | Cabot Corporation | Hydrophobic-treated metal oxide |
JP5466356B2 (en) | 2006-09-19 | 2014-04-09 | 学校法人慶應義塾 | High water-repellent composition |
IL178239A (en) | 2006-09-21 | 2012-02-29 | Eduard Bormashenko | Method of manufacturing superhydrophobic nanotextured polymer or metal surfaces |
KR100824712B1 (en) | 2006-09-21 | 2008-04-24 | 포항공과대학교 산학협력단 | Method for processing solid having fabricating superhydrophobic surface and superhydrophobic tube by the same method |
DE102006046368A1 (en) | 2006-09-29 | 2008-04-03 | Construction Research & Technology Gmbh | New functionalized polyurethane resins, based on fluoro-modified, stabilized oligo- or polyurethane binder, useful for permanent oil-, water- and dirt-repellent coating of surfaces |
US20080081858A1 (en) * | 2006-10-02 | 2008-04-03 | Genta Okazaki | High styrene SBS hot melt adhesive |
US7649289B2 (en) | 2006-10-11 | 2010-01-19 | Huang-Hsi Hsu | Water-repellent motor assembly for rotisserie and casing thereof |
EP1911801B1 (en) | 2006-10-13 | 2011-05-18 | Shin-Etsu Chemical Co., Ltd. | Coating emulsion composition, and water/oil-repellent paper and making method |
WO2008051221A2 (en) | 2006-10-23 | 2008-05-02 | Nano-Structured Consumer Products, Llc | Compositions and methods for imparting oil repellency and/or water repellency |
TWI311897B (en) | 2006-10-26 | 2009-07-01 | Delta Electronics Inc | Electronic apparatus with water blocking and draining structure and manufacturing method thereof |
CA2667579A1 (en) | 2006-10-27 | 2008-05-15 | The Regents Of The University Of California | Micro-and nanocomposite support structures for reverse osmosis thin film membranes |
JP2008135369A (en) | 2006-10-27 | 2008-06-12 | Canon Inc | Water repellent catalyst layer for polymer electrolyte fuel cell and manufacturing method for the same |
US7803499B2 (en) | 2006-10-31 | 2010-09-28 | Gm Global Technology Operations, Inc. | Super-hydrophobic composite bipolar plate |
EP1921051B1 (en) | 2006-11-07 | 2013-02-27 | Lafarge SA | Silica-based coating composition and its use for coating cement-bonded objects |
US7470818B2 (en) | 2006-11-13 | 2008-12-30 | E.I. Du Pont De Nemours & Company | Fluoroalkyl phosphate compositions |
US8047235B2 (en) | 2006-11-30 | 2011-11-01 | Alcatel Lucent | Fluid-permeable body having a superhydrophobic surface |
ES2372988T3 (en) * | 2006-12-14 | 2012-01-30 | Pactiv Corporation | EXPANDED AND EXTRUDED BIODEGRADABLE FOAMS AND REDUCED EMISSIONS MADE WITH BLOWING AGENTS BASED ON METHYR FORMAT. |
ITMI20062482A1 (en) | 2006-12-22 | 2007-03-23 | Ce S I Centro Studi Industriali Di Taddei Ing | WATER-REPELLENT, WATERPROOF HYBRID COATING FOR HUMIDITY FOR REINFORCED POLYMERIC COMPOSITE MATERIALS BY PECVD |
US20080166549A1 (en) | 2007-01-04 | 2008-07-10 | Nan Ya Plastics Corporation | Surface protection film for polarizer film |
ITMC20070008A1 (en) | 2007-01-17 | 2008-07-18 | Diasen Srl | WATERPROOFING REDUCING PROPAGATION OF FIRE. |
JP5866617B2 (en) | 2007-01-24 | 2016-02-17 | エトクス ケミカルズ リミテッド ライアビリティ カンパニー | Method for improving water transport properties of hydrophobic surfaces |
US20080193740A1 (en) | 2007-01-31 | 2008-08-14 | Nesbitt Jeffrey E | Composite building material and method for making composite building material |
DE102007005952A1 (en) | 2007-02-06 | 2008-08-07 | BSH Bosch und Siemens Hausgeräte GmbH | Refrigerating appliance with shelves suspended from a rail |
US8231191B2 (en) | 2007-02-16 | 2012-07-31 | Saint-Gobain Glass France | Shelf for supporting articles, particularly in refrigerated installations |
US20080206550A1 (en) | 2007-02-26 | 2008-08-28 | Michael Jeremiah Borlner | Hydrophobic surface |
US7943234B2 (en) | 2007-02-27 | 2011-05-17 | Innovative Surface Technology, Inc. | Nanotextured super or ultra hydrophobic coatings |
US7767758B2 (en) | 2007-02-28 | 2010-08-03 | Xerox Corporation | Silane functionalized fluoropolymers |
JP5045149B2 (en) | 2007-03-02 | 2012-10-10 | 日立電線株式会社 | Highly water-repellent / highly slidable coating member, method for producing the same, and highly water-repellent / slidable product using the same |
US20080220676A1 (en) | 2007-03-08 | 2008-09-11 | Robert Anthony Marin | Liquid water resistant and water vapor permeable garments |
US20080226694A1 (en) | 2007-03-13 | 2008-09-18 | Daniel Gelbart | Method for introducing superhydrophobic articles into the human body |
JP5297595B2 (en) | 2007-03-20 | 2013-09-25 | 凸版印刷株式会社 | Needle-like body and method for producing needle-like body |
US8236379B2 (en) | 2007-04-02 | 2012-08-07 | Applied Microstructures, Inc. | Articles with super-hydrophobic and-or super-hydrophilic surfaces and method of formation |
US20080248263A1 (en) | 2007-04-02 | 2008-10-09 | Applied Microstructures, Inc. | Method of creating super-hydrophobic and-or super-hydrophilic surfaces on substrates, and articles created thereby |
JP2008254279A (en) | 2007-04-03 | 2008-10-23 | Canon Inc | Liquid jet head |
US20080245273A1 (en) | 2007-04-05 | 2008-10-09 | Jouko Vyorkka | Hydrophobic coatings |
KR100854486B1 (en) | 2007-04-05 | 2008-08-26 | 한국기계연구원 | Manufacturing method for super water-repellent surface |
US20080250978A1 (en) | 2007-04-13 | 2008-10-16 | Baumgart Richard J | Hydrophobic self-cleaning coating composition |
KR20080094363A (en) | 2007-04-20 | 2008-10-23 | 엘지전자 주식회사 | Structure for modifying height of shelf and refrigerator having the same |
JP4579265B2 (en) | 2007-04-25 | 2010-11-10 | 信越化学工業株式会社 | Hydrophobic spherical silica fine particles having high fluidity, method for producing the same, toner external additive for developing electrostatic image using the same, and organic resin composition containing the same |
US8354480B2 (en) | 2007-04-26 | 2013-01-15 | Dow Corning Corporation | Aqueous silicone emulsion for imparting water repellency |
US20100213334A1 (en) | 2007-05-04 | 2010-08-26 | John Davenport | Shelf mounting system |
US7396395B1 (en) | 2007-05-08 | 2008-07-08 | Everest Textile Co., Ltd. | Composition of a water-repellent agent |
WO2008137973A1 (en) | 2007-05-08 | 2008-11-13 | Erik Jonas Jarvholm | Water repellant golf balls containing a hydrophobic or superhydrophobic outer layer or coating |
US20080286556A1 (en) | 2007-05-17 | 2008-11-20 | D Urso Brian R | Super-hydrophobic water repellant powder |
US8193406B2 (en) | 2007-05-17 | 2012-06-05 | Ut-Battelle, Llc | Super-hydrophobic bandages and method of making the same |
US8216674B2 (en) | 2007-07-13 | 2012-07-10 | Ut-Battelle, Llc | Superhydrophobic diatomaceous earth |
US20080295347A1 (en) | 2007-06-01 | 2008-12-04 | Eric Barkley Braham | Moisture resistant chalk line composition for use with chalk line devices |
US8980991B2 (en) | 2007-06-08 | 2015-03-17 | Xerox Corporation | Intermediate transfer members comprised of hydrophobic carbon nanotubes |
CA2634941A1 (en) | 2007-06-12 | 2008-12-12 | Starkey Laboratories, Inc. | Method and apparatus for hearing assistance device using superhydrophobic coatings |
SI2011766T1 (en) | 2007-06-15 | 2009-08-31 | Omya Development Ag | Surface-reacted calcium carbonate in combination with hydrophobic adsorbent for water treatment |
CN101772381A (en) | 2007-06-29 | 2010-07-07 | 瑞典树木科技公司 | Method to prepare superhydrophobic surfaces on solid bodies by rapid expansion solutions |
US7879768B2 (en) | 2007-07-04 | 2011-02-01 | Mud Enginneering | Drilling fluid composition comprising hydrophobically associating polymers and methods of use thereof |
DE502007002052D1 (en) | 2007-07-04 | 2009-12-31 | Evonik Degussa Gmbh | Shaped body with a superhydrophobic surface of high compressive and shear strength |
TWI349701B (en) | 2007-07-26 | 2011-10-01 | Ind Tech Res Inst | Superhydrophobic self-cleaning powders and fabrication method thereof |
DE102007035366A1 (en) | 2007-07-27 | 2009-01-29 | Bayer Materialscience Ag | Aqueous polymer secondary dispersions for the production of coatings |
WO2009018327A2 (en) | 2007-07-30 | 2009-02-05 | Soane Labs, Llc | Ultraphobic compositions and methods of use |
US8961589B2 (en) | 2007-08-01 | 2015-02-24 | Abbott Cardiovascular Systems Inc. | Bioabsorbable coating with tunable hydrophobicity |
US20090032088A1 (en) | 2007-08-03 | 2009-02-05 | Mario Rabinowitz | Sealants for Solar Energy Concentrators and Similar Equipment |
BRPI0814120A2 (en) * | 2007-08-03 | 2015-02-03 | Saint Gobain Abrasives Inc | ABRASIVE ARTICLE WITH ADHERENCE PROMOTING LAYER |
US20090042469A1 (en) | 2007-08-10 | 2009-02-12 | Ut-Battelle, Llc | Superhydrophilic and Superhydrophobic Powder Coated Fabric |
US7950756B2 (en) | 2007-08-28 | 2011-05-31 | Electrolux Home Products, Inc. | Drop-down shelf |
US20090064894A1 (en) | 2007-09-05 | 2009-03-12 | Ashland Licensing And Intellectual Property Llc | Water based hydrophobic self-cleaning coating compositions |
US20090084914A1 (en) | 2007-09-12 | 2009-04-02 | Clarion Technologies, Inc. | Refrigerator shelf assembly |
JP5056296B2 (en) | 2007-09-14 | 2012-10-24 | 富士通株式会社 | Method for switching accommodation sector of light projecting station apparatus and radio base station apparatus |
US8323732B2 (en) | 2007-09-18 | 2012-12-04 | Council Of Scientific & Industrial Research | Nanocomposite material useful for the preparation superhydrophobic coating and a process for the preparation thereof |
KR20090032707A (en) | 2007-09-28 | 2009-04-01 | 엠파워(주) | Method of fabricating superhydrophobic silica chain powders |
US20090084574A1 (en) * | 2007-09-28 | 2009-04-02 | Kim Gene Balfour | Poly(arylene ether) composition and its use in the fabrication of extruded articles and coated wire |
US20100003493A1 (en) | 2007-10-10 | 2010-01-07 | Ppg Industries Ohio, Inc. | Radiation curable coating compositions, related coatings and methods |
JP5058764B2 (en) * | 2007-10-23 | 2012-10-24 | 電気化学工業株式会社 | CROSS COPOLYMER MANUFACTURING METHOD, OBTAINED CROSS COPOLYMER, AND USE THEREOF |
US7829477B2 (en) | 2007-10-29 | 2010-11-09 | E.I. Dupont De Nemours And Company | Fluorinated water soluble copolymers |
EP2058430A1 (en) | 2007-11-08 | 2009-05-13 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Hydrophobic surface finish and method of application |
JP5164542B2 (en) | 2007-12-04 | 2013-03-21 | ニチハ株式会社 | How to paint building materials |
USD596931S1 (en) | 2007-12-04 | 2009-07-28 | Clairson, Inc. | Bracket |
US7892660B2 (en) | 2007-12-18 | 2011-02-22 | General Electric Company | Wetting resistant materials and articles made therewith |
BRPI0819414A2 (en) | 2007-12-18 | 2015-05-05 | Dow Global Technologies Inc | Composition, article, window frame, method for coating glass, method for attaching a window to a frame and kit |
US20090163637A1 (en) | 2007-12-21 | 2009-06-25 | Zhifeng Li | Filler system including densed fumed metal oxide |
MX2009000930A (en) | 2008-01-23 | 2009-09-23 | Ssw Holding Co Inc | Full extension refrigerator shelf and basket system. |
US7634877B2 (en) * | 2008-02-06 | 2009-12-22 | W. R. Grace & Co.—Conn. | Skid resistant surfaces |
MX2010013340A (en) | 2008-06-04 | 2011-04-26 | Ssw Holding Co Inc | Shelf with led assembly. |
US8637141B2 (en) | 2008-06-16 | 2014-01-28 | Massachusetts Institute Of Technology | Coatings |
MX345941B (en) | 2008-06-27 | 2017-02-27 | Ssw Holding Co Inc | Method for spill containment and shelves or the like therefore. |
US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US8663742B2 (en) | 2008-06-30 | 2014-03-04 | Stc.Unm | Durable polymer-aerogel based superhydrophobic coatings, a composite material |
KR20110042268A (en) | 2008-06-30 | 2011-04-26 | 에스티씨. 유엔엠 | A superhydrophobic aerogel that does not require per-fluoro compounds or contain any fluorine |
US20100004373A1 (en) | 2008-07-02 | 2010-01-07 | Jingxu Zhu | Compositions and processes for producing durable hydrophobic and/or olephobic surfaces |
BRPI0803841A2 (en) | 2008-07-07 | 2010-03-09 | Whirlpool Sa | system for moving a set of refrigeration equipment shelves and refrigeration equipment |
DE102008032568A1 (en) * | 2008-07-11 | 2010-01-14 | Tesa Se | Use of an adhesive film with a carrier film equipped on one side with an adhesive for covering microtiter plates |
FR2934481B1 (en) | 2008-07-30 | 2011-01-14 | Saint Gobain | SHELF, ESPECIALLY FOR REFRIGERATED FACILITIES. |
JP2012500865A (en) | 2008-08-21 | 2012-01-12 | イノーバ ダイナミクス インコーポレイテッド | Enhanced surfaces, coatings, and related methods |
FR2935242B1 (en) | 2008-09-03 | 2013-02-15 | Saint Gobain | SHELF, ESPECIALLY FOR REFRIGERATED FACILITIES |
WO2010042668A1 (en) | 2008-10-07 | 2010-04-15 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
USD596932S1 (en) | 2008-10-21 | 2009-07-28 | Crystal Spring Colony Farms Ltd. | Shelf bracket |
USD612405S1 (en) | 2008-11-06 | 2010-03-23 | Bsh Bosch Und Siemens Hausgeraete Gmbh | Glass refrigerator shelf |
USD613316S1 (en) | 2008-11-06 | 2010-04-06 | Bsh Bosch Und Siemens Hausgeraete Gmbh | Glass refrigerator shelf |
CA2743872A1 (en) * | 2008-11-14 | 2010-05-20 | Ross Technology Corporation | Long lasting, non-wetting, odor free, easily manageable animal litter and litter box usable therewith |
IT1392180B1 (en) * | 2008-12-11 | 2012-02-22 | Bouty Spa | A SELF-ADHESIVE MATRICAL SYSTEM INCLUDING A STYRENIC BLOCK COPOLYMER |
US8715906B2 (en) * | 2008-12-12 | 2014-05-06 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
KR101667825B1 (en) | 2008-12-25 | 2016-10-19 | 도아고세이가부시키가이샤 | Adhesive composition |
US8215732B2 (en) | 2009-01-15 | 2012-07-10 | Lg Electronics Inc. | Vertically adjustable refrigerator shelf with hidden drive unit |
US9250010B2 (en) | 2009-01-16 | 2016-02-02 | Whirlpool Corporation | Refrigerator shelf with glass receiving slot |
EP2223966B1 (en) | 2009-02-25 | 2017-08-16 | 3M Innovative Properties Company | Epoxy adhesive compositions with high mechanical strength over a wide temperature range |
US20100314575A1 (en) * | 2009-06-16 | 2010-12-16 | Di Gao | Anti-icing superhydrophobic coatings |
US20110027531A1 (en) * | 2009-07-03 | 2011-02-03 | Nitto Denko Corporation | Laminated film and pressure-sensitive adhesive tape |
US20110020637A1 (en) * | 2009-07-03 | 2011-01-27 | Nitto Denko Corporation | Laminated film and pressure-sensitive adhesive tape |
KR100990240B1 (en) * | 2009-07-10 | 2010-10-29 | 이승욱 | Elastic coating composition with heat conductive and spread function |
US20110033662A1 (en) * | 2009-07-23 | 2011-02-10 | Nitto Denko Corporation | Laminated film and pressure-sensitive adhesive tape |
US8513342B2 (en) | 2009-10-16 | 2013-08-20 | University of Pittsburgh—of the Commonwealth System of Higher Education | Durable superhydrophobic coatings |
BR112012011124A2 (en) * | 2009-11-12 | 2016-07-05 | Kraton Polymers Us Llc | block copolymer composition |
BR112012017173A2 (en) * | 2010-01-27 | 2016-04-19 | Kraton Polymers Us Llc | block copolymer composition |
EP2547832A4 (en) * | 2010-03-15 | 2016-03-16 | Ross Technology Corp | Plunger and methods of producing hydrophobic surfaces |
DE102010022265A1 (en) | 2010-05-31 | 2011-12-01 | Siemens Aktiengesellschaft | Hydrophobic coating and application |
GB2484751B8 (en) | 2010-10-23 | 2017-12-06 | Graham Jonathan | Touch-up paint |
EP2638107A1 (en) | 2010-11-10 | 2013-09-18 | 3M Innovative Properties Company | Hydrophobic fluorinated coatings |
US8779025B1 (en) | 2010-11-22 | 2014-07-15 | Donald David Stone | Method for increasing the wet coefficient of friction of a thermoplastic elastomer and composition therefor |
PE20140834A1 (en) * | 2011-02-21 | 2014-07-10 | Ross Technology Corp | SUPERHYDROPHIC AND OLEOPHOBIC COATING WITH BINDERS SYSTEM WITH LOW VOC CONTENT |
WO2013090939A1 (en) | 2011-12-15 | 2013-06-20 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
EP2812182A4 (en) * | 2012-02-08 | 2016-01-27 | Ross Technology Corp | Hydrophobic surfaces on injection molded or shaped articles |
CA2878189C (en) | 2012-06-25 | 2021-07-13 | Ross Technology Corporation | Elastomeric coatings having hydrophobic and/or oleophobic properties |
CA2925495A1 (en) | 2013-09-26 | 2015-04-02 | Ross Technology Corporation | Flexible superhydrophobic and/or oleophobic polyurethane coatings |
-
2013
- 2013-03-14 CA CA2878189A patent/CA2878189C/en active Active
- 2013-03-14 AU AU2013281220A patent/AU2013281220B2/en not_active Ceased
- 2013-03-14 WO PCT/US2013/031751 patent/WO2014003852A2/en active Application Filing
- 2013-03-14 BR BR112014032676A patent/BR112014032676A2/en not_active Application Discontinuation
- 2013-03-14 MX MX2015000119A patent/MX2015000119A/en unknown
- 2013-03-14 CN CN201380041551.6A patent/CN104520392A/en active Pending
- 2013-03-14 EP EP13809987.4A patent/EP2864430A4/en not_active Withdrawn
-
2014
- 2014-03-28 US US14/229,047 patent/US9388325B2/en active Active
- 2014-07-03 US US14/323,660 patent/US20150005424A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US9388325B2 (en) | 2016-07-12 |
EP2864430A2 (en) | 2015-04-29 |
AU2013281220B2 (en) | 2017-03-16 |
CA2878189C (en) | 2021-07-13 |
WO2014003852A9 (en) | 2014-04-17 |
CN104520392A (en) | 2015-04-15 |
AU2013281220A1 (en) | 2015-02-12 |
BR112014032676A2 (en) | 2017-06-27 |
US20150005424A1 (en) | 2015-01-01 |
WO2014003852A3 (en) | 2014-02-20 |
US20140205804A1 (en) | 2014-07-24 |
EP2864430A4 (en) | 2016-04-13 |
MX2015000119A (en) | 2015-04-14 |
WO2014003852A2 (en) | 2014-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2878189C (en) | Elastomeric coatings having hydrophobic and/or oleophobic properties | |
US10273368B2 (en) | Flexible superhydrophobic and/or oleophobic polyurethane coatings | |
AU2012220798B2 (en) | Superhydrophobic and oleophobic coatings with low VOC binder systems | |
AU2009302806B2 (en) | Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation | |
US20140296409A1 (en) | Composition and Coating for Hydrophobic Performance | |
Liu et al. | Robust, self-cleaning, anti-fouling, superamphiphobic soy protein isolate composite films using spray-coating technique with fluorinated HNTs/SiO2 | |
JP2009079120A (en) | Molded body and modifier comprising acrylic block copolymer | |
TW201036776A (en) | Process for the production of coated rubber particles, coated rubber particles, and solvent-free coating formulation | |
WO1998000241A1 (en) | Preparation and method for applying an anti-slip layer to a surface and product provided with an anti-slip layer | |
US6297312B1 (en) | One-pack waterborne adhesion coatings for thermoplastic olefins | |
JP2022524645A (en) | Hydrophobic coating coating composition and articles with a hydrophobic surface | |
Myint et al. | Paints based on waste expanded polystyrene | |
JP7334802B2 (en) | Surface treatment layer and article | |
AU2015227483B9 (en) | Highly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation | |
JP7198615B2 (en) | Curable resin composition and cured product thereof | |
WO2008077903A2 (en) | Stain repellent material | |
Seyedmehdi | Functional Coatings: Superhydrophopbic And Conductive Coatings | |
JP2020186332A (en) | Aqueous resin composition, surface treatment agent, and article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request |
Effective date: 20180307 |