WO2017007439A1 - A superhydrophobic nanocomposite coating method - Google Patents
A superhydrophobic nanocomposite coating method Download PDFInfo
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- WO2017007439A1 WO2017007439A1 PCT/TR2016/050208 TR2016050208W WO2017007439A1 WO 2017007439 A1 WO2017007439 A1 WO 2017007439A1 TR 2016050208 W TR2016050208 W TR 2016050208W WO 2017007439 A1 WO2017007439 A1 WO 2017007439A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin
- coating method
- nanocomposite coating
- solvent
- dispersing
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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
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Definitions
- the present invention relates to a nanocomposite coating method, which increases adsorption of the coating to the surface to which it is applied, and enables to obtain a superhydrophobic surface even if it is applied as a thin film thanks to its feature of bidirectional wetting.
- Superhydrophobic nanocomposite coatings are basically comprised of two components. While fibrous structures are used as additives, particles and nanoparticles can also be used in some applications. The particles are directly sprayed onto the surface or dip-coating is performed.
- An objective of the present invention is to provide a superhydrophobic nanocomposite coating method having the feature of bidirectional wetting.
- Another objective of the present invention is to provide a superhydrophobic nanocomposite coating method which increases adsorption of the coating onto the surface.
- a further objective of the present invention is to provide a superhydrophobic nanocomposite coating method which provides a transparent layer on the surface.
- Another objective of the present invention is to provide a superhydrophobic nanocomposite coating method which enables long useful lives for the surfaces subjected to the tough conditions.
- Figure 1 is the flow chart of the method of the present invention.
- Figure 2 is a schematic view of the method of the present invention when brush polymer is used as the matrix material.
- Figure 3 is a schematic view of the method of the present invention when block polymer is used as the matrix material.
- the superhydrophobic nanocomposite coating method (100) of the present invention comprises the steps of
- the coating method (100) of the present invention is developed for enhancing adsorption of the coating in obtaining superhydrophobic surfaces.
- the nanosized hydrophobic silica and/or clay particles are modified by surfactants having fluorine groups and thus surface energies of the particles are reduced (101).
- surfactants having - CF 2 and -CF 3 end and side groups are used.
- the surfactants used in these preferred embodiments of the invention are ethoxysilane (C 2 H 8 OSi), methoxysilane (CHeOSi) and chlorosilane (H 3 ClSi).
- the clay used in one embodiment of the invention is comprised of montmorillonite (MMT).
- a polymer matrix (102) which particles with modified surfaces are then dispersed in a polymer matrix (102).
- the matrix that is selected should comprise both a phase in which these hydrophobic particles can mix and a phase which will enhance surface adhesion capability of the coating. Therefore amphiphilic polymer matrixes with bidirectional wetting property are chosen.
- brush polymers having reactive functional group at the ends thereof or amphiphilic block polymers are used. Hydroxy- terminated polystrene (HO-PS) can be given as an example of a brush polymer and polystrene - polymethyl methacrylate block copolymer (PS-b-PMMA) as an example of block copolymer.
- HO-PS Hydroxy- terminated polystrene
- PS-b-PMMA polystrene - polymethyl methacrylate block copolymer
- a brush polymer is used as the matrix material; while the polymer main chains enable mixing with the hydrophobic particles, the reactive groups at the ends interact with the surface and form a covalent bond, and thus realize adsorption.
- a block polymer is used as the matrix material; while one of two incompatible polymer blocks bonded to each other from the ends thereof via a covalent bond enable mixing with the hydrophobic particles, the other polymer block enables interaction with the surface and thus adsorption.
- Both of the matrixes enable bidirectional wetting and allow both efficient dispersion of the particles and strong adsorption of the coating onto the surface at the same time.
- This resin which is obtained upon complete dispersion of the particles within the matrix is dispersed in a solvent medium (103). It is important that the selected solvent has a polarity that is suitable for the resin.
- the resins which are prepared with the said matrixes are preferably dissolved and dispersed within ketone groups and/or toluene groups (103).
- Surface application of the prepared solvent-resin mixture is preferably performed via spraying technique (104). This process can be applied on all kinds of metal, polymer, wood and ceramic surfaces regardless of the surface shape.
- the coated surface is lastly subjected to a heating process (105).
- the temperature applied for this process is optimized taking into consideration the curing temperature of the resin that is used and the evaporation temperature of the solvent.
- the heating process is preferably carried out at a temperature of 65-75°C.
- temperatures within the range of 180-205°C are suitable for the heating process. Volatility level of the solvent at that temperature is effective on the period of the heating process.
- the heating process (105) is carried out for a period of 5 minutes to 1 hour.
- the most important feature of the superhydrophobic nanocomposite coating obtained on the surface by means of the method (100) of the present invention is that it provides both homogenous dispersion and strong adsorption at the same time and thus it provides a long term resistance to the surface even in very thin applications where transparency is important.
- the surfaces coated with the method (100) of the present invention acquire features such as hydrophobicity, dirt repellency, non-frosting, paint nonadherence, adherence prevention. It provides long life when applied to vehicles, which are exposed to difficult conditions, such as vessels and airplanes where both aesthetics and resistance are important.
Abstract
The present invention relates to a nanocomposite coating method, which increases adsorption of the coating to the surface to which it is applied, and enables to obtain a superhydrophobic surface even if it is applied as a thin film thanks to its feature of bidirectional wetting, and which comprises the steps of reducing surface energy of nanosized hydrophobic particles by modifying them (101), dispersing the modified particles in the polymer matrix and preparing the resin (102), dispersing the resin in a solvent medium having a suitable polarity (103), applying the resin-solvent mixture on the surface (104), heating the surface taking into consideration the curing temperature of the resin and evaporation temperature of the solvent (105).
Description
A SUPERHYDROPHOBIC NANOCOMPOSITE COATING METHOD
Field of the Invention
The present invention relates to a nanocomposite coating method, which increases adsorption of the coating to the surface to which it is applied, and enables to obtain a superhydrophobic surface even if it is applied as a thin film thanks to its feature of bidirectional wetting.
Background of the Invention
Superhydrophobic nanocomposite coatings are basically comprised of two components. While fibrous structures are used as additives, particles and nanoparticles can also be used in some applications. The particles are directly sprayed onto the surface or dip-coating is performed.
In the superhydrophobic nanocomposite structures applied today; resins and polymers with low surface energy such as PS, PMMA, PU, PE are used as the matrix material by which particles and fibrous structures are dispersed, and alcohols and ketones are used as solvents. The fact that the surface energy of the resins used in the state of the art is low prevents strong adsorption of the coating structure onto the surface. This causes the coating to disbond from the surface after a period of time and leads to undesirable results both functionally and visually. For example, when a superhydrophobic nanocomposite coating is applied on an airplane surface with the methods of the state of the art, the said coating cannot resist the friction occurring during flight.
Summary of the Invention
An objective of the present invention is to provide a superhydrophobic nanocomposite coating method having the feature of bidirectional wetting.
Another objective of the present invention is to provide a superhydrophobic nanocomposite coating method which increases adsorption of the coating onto the surface.
A further objective of the present invention is to provide a superhydrophobic nanocomposite coating method which provides a transparent layer on the surface.
Another objective of the present invention is to provide a superhydrophobic nanocomposite coating method which enables long useful lives for the surfaces subjected to the tough conditions. Detailed Description of the Invention
"A superhydrophobic nanocomposite coating method" developed to fulfill the objective of the present invention is illustrated in the accompanying figures wherein,
Figure 1 is the flow chart of the method of the present invention.
Figure 2 is a schematic view of the method of the present invention when brush polymer is used as the matrix material.
Figure 3 is a schematic view of the method of the present invention when block polymer is used as the matrix material.
The superhydrophobic nanocomposite coating method (100) of the present invention comprises the steps of
- reducing surface energy of nanosized hydrophobic particles by modifying them (101),
- dispersing the modified particles in the polymer matrix and preparing the resin (102),
- dispersing the resin in a solvent medium having a suitable polarity (103),
- applying the resin-solvent mixture on the surface (104),
- heating the surface taking into consideration the curing temperature of the resin and evaporation temperature of the solvent (105).
The coating method (100) of the present invention is developed for enhancing adsorption of the coating in obtaining superhydrophobic surfaces. To this end, first of all, the nanosized hydrophobic silica and/or clay particles are modified by surfactants having fluorine groups and thus surface energies of the particles are reduced (101). In the preferred embodiment of the invention, surfactants having - CF2 and -CF3 end and side groups are used. The surfactants used in these preferred embodiments of the invention are ethoxysilane (C2H8OSi), methoxysilane (CHeOSi) and chlorosilane (H3ClSi). The clay used in one embodiment of the invention is comprised of montmorillonite (MMT).
These particles with modified surfaces are then dispersed in a polymer matrix (102). At this stage, the matrix that is selected should comprise both a phase in which these hydrophobic particles can mix and a phase which will enhance surface adhesion capability of the coating. Therefore amphiphilic polymer matrixes with bidirectional wetting property are chosen. For this purpose, in a preferred embodiment of the invention, brush polymers having reactive functional group at the ends thereof or amphiphilic block polymers are used. Hydroxy- terminated polystrene (HO-PS) can be given as an example of a brush polymer and polystrene - polymethyl methacrylate block copolymer (PS-b-PMMA) as an example of block copolymer.
In the case that a brush polymer is used as the matrix material; while the polymer main chains enable mixing with the hydrophobic particles, the reactive groups at
the ends interact with the surface and form a covalent bond, and thus realize adsorption.
In the case that a block polymer is used as the matrix material; while one of two incompatible polymer blocks bonded to each other from the ends thereof via a covalent bond enable mixing with the hydrophobic particles, the other polymer block enables interaction with the surface and thus adsorption.
Both of the matrixes enable bidirectional wetting and allow both efficient dispersion of the particles and strong adsorption of the coating onto the surface at the same time.
This resin which is obtained upon complete dispersion of the particles within the matrix is dispersed in a solvent medium (103). It is important that the selected solvent has a polarity that is suitable for the resin. In the case that a HO-PS brush polymer or a PS-b-PMMA block polymer is used as the matrix material, the resins which are prepared with the said matrixes are preferably dissolved and dispersed within ketone groups and/or toluene groups (103). Surface application of the prepared solvent-resin mixture is preferably performed via spraying technique (104). This process can be applied on all kinds of metal, polymer, wood and ceramic surfaces regardless of the surface shape.
The coated surface is lastly subjected to a heating process (105). The temperature applied for this process is optimized taking into consideration the curing temperature of the resin that is used and the evaporation temperature of the solvent. In one embodiment of the invention, if the resin is comprised of PS-b- PMMA and toluene, the heating process is preferably carried out at a temperature of 65-75°C. In another embodiment of the invention, if the resin is comprised of HO-PS and toluene, temperatures within the range of 180-205°C are suitable for the heating process. Volatility level of the solvent at that temperature is effective
on the period of the heating process. When toluene is used as the solvent, the heating process (105) is carried out for a period of 5 minutes to 1 hour.
The most important feature of the superhydrophobic nanocomposite coating obtained on the surface by means of the method (100) of the present invention is that it provides both homogenous dispersion and strong adsorption at the same time and thus it provides a long term resistance to the surface even in very thin applications where transparency is important. The surfaces coated with the method (100) of the present invention acquire features such as hydrophobicity, dirt repellency, non-frosting, paint nonadherence, adherence prevention. It provides long life when applied to vehicles, which are exposed to difficult conditions, such as vessels and airplanes where both aesthetics and resistance are important.
Claims
A superhydrophobic nanocomposite coating method (100) which enhances adsorption of the coating by enabling bidirectional wetting, comprising the steps of
- reducing surface energy of nanosized hydrophobic particles by modifying them (101),
- dispersing the modified particles in the polymer matrix and preparing the resin (102),
- dispersing the resin in a solvent medium having a suitable polarity (103),
- applying the resin-solvent mixture on the surface (104),
- heating the surface taking into consideration the curing temperature of the resin and evaporation temperature of the solvent (105); and characterized in that
- in the step of "reducing surface energy of nanosized hydrophobic particles by modifying them (101)", silica and/or clay particles are modified by surfactants having fluorine groups and
- in the step of "dispersing the modified particles in the polymer matrix and preparing the resin (102)", amphiphilic polymer matrixes having the feature of bidirectional wetting are used.
Superhydrophobic nanocomposite coating method (100) according to Claim 1, characterized by the step of reducing surface energy of nanosized hydrophobic particles by modifying them with surfactants having -CF2 and -CF3 end and side groups (101).
Superhydrophobic nanocomposite coating method (100) according to Claim 1, characterized by the step of reducing surface energy of nanosized montmorillonite (MMT) particles by modifying them (101).
4. Superhydrophobic nanocomposite coating method (100) according to Claim 1, characterized by the step of dispersing the modified particles in the brush polymer matrix having reactive functional group at the ends thereof and preparing the resin (102).
5. Superhydrophobic nanocomposite coating method (100) according to Claim 1, characterized by the step of dispersing the modified particles in the amphiphilic block copolymer matrix and preparing the resin (102).
6. Superhydrophobic nanocomposite coating method (100) according to Claim 4, characterized by the step of dispersing the modified particles in the hydroxy-terminated polystrene (HO-PS) matrix and preparing the resin (102).
7. Superhydrophobic nanocomposite coating method (100) according to Claim 5, characterized by the step of dispersing the modified particles in the polystrene - polymethyl methacrylate block copolymer (PS-b-PMMA) matrix and preparing the resin (102).
8. Superhydrophobic nanocomposite coating method (100) according to Claim 6 or 7, characterized by the step of dispersing the resin in a solvent medium having a suitable polarity (103) wherein ketone is used as the solvent.
9. Superhydrophobic nanocomposite coating method (100) according to Claim 6, characterized by the step of dispersing the resin in a solvent medium having a suitable polarity (103) wherein toluene is used as the solvent.
10. Superhydrophobic nanocomposite coating method (100) according to Claim 7, characterized by the step of dispersing the resin in a solvent
medium having a suitable polarity (103) wherein toluene is used as the solvent.
11. Superhydrophobic nanocomposite coating method (100) according to Claim 1, characterized by the step of applying the resin-solvent mixture on the surface (104) via spraying technique.
12. Superhydrophobic nanocomposite coating method (100) according to Claim 9, characterized by the step of heating the surface taking into consideration the curing temperature of the resin and evaporation temperature of the solvent (105) at temperatures of 180-205°C for a period of 5 minutes to 1 hour.
13. Superhydrophobic nanocomposite coating method (100) according to Claim 10, characterized by the step of heating the surface taking into consideration the curing temperature of the resin and evaporation temperature of the solvent (105) at temperatures of 65-75°C for a period of 5 minutes to 1 hour.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR201508263 | 2015-07-03 | ||
| TR2015/08263 | 2015-07-03 |
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| WO2017007439A1 true WO2017007439A1 (en) | 2017-01-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115772349A (en) * | 2022-11-14 | 2023-03-10 | 广州集泰化工股份有限公司 | Water-based acrylic coating and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115772349A (en) * | 2022-11-14 | 2023-03-10 | 广州集泰化工股份有限公司 | Water-based acrylic coating and preparation method and application thereof |
| CN115772349B (en) * | 2022-11-14 | 2024-03-26 | 广州集泰化工股份有限公司 | Water-based acrylic coating and preparation method and application thereof |
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