CA2202673C - Water repellent surface treatment with acid activation - Google Patents

Water repellent surface treatment with acid activation Download PDF

Info

Publication number
CA2202673C
CA2202673C CA002202673A CA2202673A CA2202673C CA 2202673 C CA2202673 C CA 2202673C CA 002202673 A CA002202673 A CA 002202673A CA 2202673 A CA2202673 A CA 2202673A CA 2202673 C CA2202673 C CA 2202673C
Authority
CA
Canada
Prior art keywords
acid
substrate
water
group
coupons
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.)
Expired - Lifetime
Application number
CA002202673A
Other languages
French (fr)
Other versions
CA2202673A1 (en
Inventor
George B. Goodwin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vitro SAB de CV
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of CA2202673A1 publication Critical patent/CA2202673A1/en
Application granted granted Critical
Publication of CA2202673C publication Critical patent/CA2202673C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C19/00Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/104Pretreatment of other substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/328Polyolefins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/18Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/31Pre-treatment
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31Surface property or characteristic of web, sheet or block
    • Y10T428/315Surface modified glass [e.g., tempered, strengthened, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers

Abstract

The purpose of the present invention is to provide an article of manufacture including a substrate having a water repellent film thereon of improved durability and to provide a method for forming such a water repellent film on a substrate. The article of manufacture is constructed by activating the substrate with an acid solution and then applying a water repellent composition over the substrate which will form the water repellent film. The remarkable effect of the acid activation is to substantially increase the durability of the water repellency of the film. The acid solution preferably includes hydrochloric acid, sulfuric acid or an organic acid. Substrates may include but are not limited to glass, metal, plastic, enamels and ceramics. The water repellent composition preferably includes a perfluoroalkylalkyl silane.

Description

WATER REPELLENT SURFACE TREATMENT WITH ACID ACTIVATION
$ACKGROUND
Field of the Invention The present invention relates generally to the art of producing a water repellent film on various substrates, and s more particularly, to improving the durability of water repellent films by activating the substrate with an acid solution prior to applying the film.
Relevant Art io U.S. Patent No. 4,997,684 to Franz et al. discloses a method for providing a durable nonwetting surface on glass by contacting the glass with a perfluoroalkylalkyl silane and a fluorinated olefin compound and heating the glass to produce a durable non-wetting surface.
15 U.S. Patent No. 5,328,768 to Goodwin discloses a technique for producing a durable non-wetting surface on a glass substrate wherein the surface of the substrate is
- 2 -treated with a silica primer layer and a perfluoroalkylalkyl silane over the primer layer. The silica primer layer improves the durability of the water repellency of the surface. The glass substrate is cleaned with a water and s 50/50 by volume isopropanol/water solution prior to application of the primer.
U.S. Patent No. 5,523,162 to Franz et al. discloses a method for producing a durable non-wetting surface on a plastic substrate which includes treating the plastic io substrate with a silica primer~layer and a perfluoroalkylalkyl silane. The plastic substrate was cleaned with hexane then methanol prior to application of the primer.
While the foregoing U.S. patents disclose durable water repellent films, it can be appreciated by those skilled is in the art that making available additional technology to improve the durability of the water repellent surface is advantageous and desirable.
2o The present invention relates to a method of improving the durability of water repellent films. The water repellent film used in the practice of the invention is preferably a water repellent composition applied over the substrate, which forms the water repellent film. In the z5 practice of the invention, the durability of the water repellency of the film is improved by activating the substrate with an acid solution prior to applying the water repellent composition to the substrate.
The acid of the acid solution is preferably 3o hydrochloric acid, sulfuric acid or an organic acid such as tartaric acid. Other acids disclosed herein may also be used in the practice of the invention.
- 3 -Although not limiting to the invention, the substrate includes glass, metal, plastic, enamels and ceramics. The substrate may be coated or uncoated e.g. the substrate may be coated with one or more inorganic oxide s films.
DESCRIPTION~OF THE INVENTION
The instant invention relates to a method of improving the durability of a water repellent film; the water io repellent film is provided by the application of a water repellent composition over a substrate to form the water repellent film on the substrate. The durability of the water repellent film is improved by activating the substrate with an acid solution prior to applying the water repellent is composition. Unless otherwise stated or otherwise clear from the context of the discussion, it is to be understood that while the foregoing and following discussions describe the water repellent composition and acid solution as being applied to the substrate itself, it is primarily the surface of the 2o substrate which is affected by the present invention. Also, unless otherwise stated or otherwise clear from the context of the discussion, the term water repellent composition as used herein includes: water repellent compositions applied over the substrate directly as described in U.S. Patent No.
z5 4,983,459; water repellent compositions having an integral primer as described in U.S. Patent No. 5,523,161; water repellent compositions having a fluorinated olefin compound, as described in U.S. Patent No. 5,308,705; or water repellent compositions applied over a discrete primer layer applied to 3o the substrate as described in U_S. Patent No. 5,328,768.
- 4 -I. The Substrate:
The instant invention is not limited to any particular substrate surface and may include uncoated glass, metal, plastic, enamel or ceramic substrates. Further, the s method of the instant invention may be practiced on coating films or the outermost film of a stack of coating films, including inorganic oxide coating films on glass, metal, plastic, enamel and ceramic substrates. For example, inorganic oxide coatings for glass include but are not limited io to antimony-tin oxide, doped tin oxide, or transition metal oxides.
The method of the instant invention is also applicable to plastic substrates with a polysiloxane-based hard coating. These coatings of the polysiloxane sol-gel type i5 generally contain siloxanes and inorganic oxides which function as a suitable substrate for the deposition of a hydrophobic coating, the durability of which is enhanced by the use of a primer.
Metal substrates include galvanized steel, stainless zo steel and aluminum. Where the substrate may be thermally or chemically treated e.g. to increase its structural properties, the glass may be annealed or tempered by chemical or thermal means.
In the following discussion reference may be made to 2s substrate and substrate surface, where reference to substrate is made unless indicated otherwise, the reference to the substrate refers to the substrate surface which may be uncoated or coated with one or more films.
30 II. Optional Polishing Operation:
It has been determined that the durability of the water repellency of the water repellent film is extended by
- 5 -the method of the present invention regardless of whether the substrate surface is polished prior to acid activation.
Although not required, the step of polishing prior to acid activation is recommended.
The polishing step provides two benefits. The first is it roughens the substrate surface. The second is to partially remove contaminating residues from the substrate surface. Atomic Force Microscopy data has shown that the polishing of glass substrates has increased the mean roughness io of the glass surface from about 0.5 nanometers to about 4 nanometers (measured over a 100 square micron area). Fine surface scratches up to 10 nanometers deep in the glass substrate have not resulted in any measurable haze. This provides more glass surface area for subsequent reaction with is water repellent composition. Decontamination of the substrate surface can be shown by the contact angle of a drop of water on a freshly polished surface; the lower the contact angle the cleaner the substrate surface. As will be observed from the following data, polishing does not significantly 2o improve the durability of the water repellent film. However, the polishing is recommended to produce a more clean surface on the substrate prior to acid activation.
The polishing compounds that may be used in the practice of the present invention include but are not limited 2s to alumina, ceria, iron oxide, garnet, zirconia, silica, silicon carbide, chromic oxide, diamond, or other hard material with sufficiently small particle size as to not damage the substrate. Mixtures of these materials are suitable polishing compounds. Preferred polishing compounds 3o include alumina or ceria.
The polishing operation is performed by wiping the substrate with a pad containing a slurry of the polishing
- 6 -- compound. The preferred concentration of the polishing compound in water to form a polishing slurry is in the range of S to 30 weight percent. Lower and higher concentrations may be used but more or less slurry or more or less~contact s time with the substrate may be required to properly polish the substrate. The preferred polishing process includes wiping the substrate with the polishing slurry until the slurry no longer pulls away from any part of the substrate surface.
Where the slurry pulls away from a part of the substrate io surface, it typically does so because the slurry's cohesive forces are greater than the adhesive force of the slurry to the substrate. Adhesive forces of the slurry to the substrate increase as a result of the removal of surface impurities from the substrate. The polishing operation removes such i5 impurities causing the adhesive force of the slurry to the substrate to exceed the cohesive force of the slurry where upon the slurry no longer pulls away from any part of the substrate. The polishing operation may be performed by hand or by using powered equipment such as an orbital sander with a 2o non-abrasive pad which is wet with the polishing slurry.
III. The Water Repellent Composition:
The water repellent composition that may be used in the practice of the present invention preferably includes a 2s perfluoroalkylalkyl silane as disclosed in U.S.
Patent Nos. 4,983,459; 4,997,684; 5,308,705; 5,328,768;
5,523,161; and 5,523,162. Perfluoroalkylalkyl silanes that are preferred in the practice of the invention have the so general formula RmR'"SlXq_m-n, wherein R is a perfluoroalkylalkyl radical; m is 1, 2 or 3; n is 0, 1 or 2; and m+n is less than 4; R' is a vinyl or an alkyl radical, preferably methyl, _ 7 _ ethyl, vinyl or propyl; and X is preferably a radical such as halogen, acyloxy, and/or alkoxy. Preferred perfluoroalkyl moieties in the perfluoroalkylalkyl radicals range from CF3 to C3aF61, preferably C6F13 to C18F3~, and most preferably CeFl~ to s ClzFzs: the second alkyl moiety of the perfluoroalkylalkyl is preferably a substituted ethyl. R' is more preferably methyl or ethyl. Preferred radicals for X include hydrolyzable chloro, bromo, iodo, methoxy, ethoxy and acetoxy radicals.
Preferred perfluoroalkylalkyl silanes in accordance to with the present invention include perfluoroalkylethyl-trichlorosilane, perfluoroalkylethyltrimethoxysilane, perfluoroalkylethyltriacetoxysilane, perfluoroalkylethyl-dichloro(methyl)silane and perfluoroalkylethyldiethoxy-(methyl)silane.
IIIA.The Primer Layer or Integral Primer~
The water repellent film that may be used in the practice of the present invention may include a discrete primer layer interposed between the substrate and the water 2o repellent film, as disclosed in U.S. Patent Nos. 4,983,459;
5,308,705; 5,328,768; 5,523,161 and 5,523,162. Where a discrete primer layer is selected, the primer layer is first applied over the substrate prepared in accordance to the invention by application methods including pyrolytic deposition, magnetron sputtering or sol-gel condensation reactions. The water repellent composition is then applied over the primer layer. The primer layer, not limiting to the invention, may include a silica primer layer.
so Alternatively, the water repellent film that may be used in the practice of the present invention may include an integral primer which is included in the water repellent g _ composition, also as disclosed in one or more of U.S. Patent Nos. 4,983,459; 5,308,705; 5,523,161; and 5,523,162.
The integral primer, not limiting to the invention, may be a hydrolyzable silane or siloxane capable of hydrolytic s condensation to form silica gel which functions as the integral primer.
Suitable silanes capable of hydrolysis to silica gel have the general formula SiX4 wherein X is a hydrolyzable radical generally selected from the group of halogens, alkoxy io and acyloxy radicals. Preferred silanes are those wherein X
is preferably chloro, bromo, iodo, methoxy,.ethoxy and acetoxy. Preferred hydrolyzable silanes include tetrachlorosilane, tetramethoxysilane and tetraacetoxysilane.
Suitable siloxanes have the general formula is SIpOZX4},_2z, wherein X is selected from the group of halogen, alkoxy and acyloxy radicals, y is two or more, and z is one or more and 4y-2z is greater than zero. Preferred hydrolyzable siloxanes include hexachlorodisiloxane, octachlorotrisiloxane, and higher oligomer chlorosiloxanes.
2o Where the integral primer layer is selected, the water repellent composition is applied to the substrate prepared in accordance to the invention preferably as a solution in an aprotic solvent, preferably an alkane or mixture of alkanes, or a fluorinated solvent. Such solutions 2s may be applied to the substrate by any conventional technique such as dipping, flowing, wiping or spraying without the additional step of applying a separate primer layer_ IIIB. The Fluorinated Olefin Compound:
3o The water repellent composition that may be used in the practice of the present invention may also optionally include a fluorinated olefin compound also as disclosed in U.S. Patent Nos. 4,983,459; 4,997,684; 5,308,705; 5,328,768;
5,523,161; and 5,523,162 to provide lubricity to promote dirt repellency of the water repellent surface. A preferred olefin compound is selected from the group represented by the general s formula CmF2m,lCH=CH2, where m is from 1 to 30, preferably 1 to 16, more preferably 4 to 10.
Iy~ ~r~,e n"~ a n~t~ vation of the Present Invents on~
The acid solutions used in the practice of the io present invention are selected upon their ability to increase the durability of the water repellency of the substrate without damaging the substrate. Although not limiting to the invention, acid solutions that are preferably used in the practice of the invention include solutions of hydrochloric is acid, sulfuric acid and organic acids. Where organic acid solutions are selected, strong organic acid solutions are preferred, which includes acid solutions having a pH of less than about 5 and most preferably less than about 3. Other acids that may be used in the practice of the invention 20 include phosphoric acid, hydrobromic acid, nitric acid, acetic acid, trifluoroacetic acid, and/or citric acid.
Where the acid is hydrochloric acid, an acid solution of hydrochloric acid dissolved in deionized water where the acid concentration is in the range of 0_5-30 wt%
2s hydrochloric acid, in a balance of deionized water, may be used, 0.5-20 wt°s is acceptable, and 0.5-10 wt% is preferred.
Where the acid is sulfuric acid, an acid solution of sulfuric acid dissolved in deionized water where the acid concentration is in the range of 0.5-30 wt% sulf.uric acid dissolved in the 3o balance of deionized water may be used, 0.5-20 wt% is acceptable, and 0.5-10 wto is preferred. Where the acid is tartaric acid, an acid solution of tartaric acid dissolved in deionized water where the acid concentration is in the range of 1-40 wt% tartaric acid dissolved in the balance of deionized water may be used and 2-20 wt% is preferred. As can be appreciated, lower and higher acid concentrations'~are s acceptable, however using such concentrations may require correspondingly more or less activating time on the substrate to improve the durability of the water repellent film.
The acid activation of the substrate is accomplished by applying the acid solution to the substrate by any io conventional technique such as dipping, flowing, spraying and, preferably, wiping. While no set number of wipes are required, it has been found that wiping the substrate about six times provides acceptable results. Wiping is commonly done by applying moderate hand pressure to an absorbent acid-is resistant pad containing the acid solution, such as a cotton pad.
Where the acid solution is volatile and will evaporate from the substrate without leaving a residue, the acid is applied to the substrate, allowed to evaporate, 2o whereupon the water repellent composition is applied over the substrate. Volatile acid solutions are defined herein as those which are capable of volatilizing at ambient conditions within a short time period (i.e. within about 10 minutes or less) after application to the substrate. Examples of 2s volatile acid solutions that may be used in the practice of the present invention include hydrochloric, hydrobromic, acetic, nitric, and trifluoroacetic acid solutions.
Where the acid solution is non-volatile, or is volatile but leaves behind a residue upon evaporation, the 3o substrate should be rinsed after the acid activation step to remove the acid solution or its residue. After rinsing, the substrate is dried and the water repellent composition applied over the substrate. Non-volatile acid solutions are defined herein as those which are not capable of volatilizing at ambient conditions within a short time period (i.e. within about 10 minutes or less) after application to the substrate.
s Examples of non-volatile acids include sulfuric, tartaric, citric, and phosphoric acids. The rinsing solutions may include water or alcohol with water being preferred.
It is believed that during the acid activation step the acid solution increases the durability of the water io repellent surface by removing contaminating materials from the surface of the substrate and increasing the number of bonding sites on the surface of the substrate available for reaction with the water repellent composition.
is V. Durability Testing of The Water Repellent Film:
Durability of the water repellent film applied in accordance with the present invention is measured in terms of the ability of the film surface to maintain a contact angle over time under accelerated weathering conditions. The higher 2o the degree of contact angle that can be maintained by the sample tested over time or number of wiping cycles, the more durable the film and the greater the surface repels water.
The contact angles recited herein are measured by the sessile drop method using a modified captive bubble 2s indicator manufactured by Lord Manufacturing, Inc., equipped with Gaertner Scientific goniometer optics. The surface to be measured is placed in a horizontal position, facing upward, in front of a light source: A sessile drop of water is placed on top of the surface in front of the light source so that the so profile of the sessile drop can be viewed and the contact angle measured in degrees through the goniometer telescope equipped with circular protractor graduation.

Simulated weathering of the water repellent film is obtained via weathering chambers which include the Cleveland Condensing Cabinet (CCC) and QW Tester (products of The Q-Panel Company, Cleveland, OH). The CCC chamber was operated s at a vapor temperature of 140°F (60°C) in an indoor ambient environment which resulted in constant water condensation on the test surface. The QW Tester was operated with cycles of 8 hours UV (B313 lamps) at black panel temperature of 65-70°C
and 4 hours condensing humidity at 50°C atmosphere temperature.
io The abrasion resistance of the water repellent film was measured by the Taber Abrasion Test utilizing the Taber Abraser manufactured by Teledyne Taber of North Tonawanda, NY.
The Taber Abrasion Test consists of rotating a substrate to be tested in a horizontal orientation while a pair of abrading i5 wheels rotate on the surface. One revolution of the substrate equals one cycle. The weight per wheel can be varied to increase or decrease the rate of abrasion, and for the testing of the present invention, 500 gram of weight per wheel was applied. After abrasion, the water repellency was measured in 2o the abraded track with the sessile water drop method previously described.
The abrasion resistance of the water repellent film was measured by the Wet Sled Abrasion Test. In this test, two wiper blades are cycled across the surface of the water 25 repellent film while water or an abrasive slurry is applied in front of the wiper blades. A wiped area of about 1.5 inches (3.8 cm) by 7.5 inches (19.05 cm) is abraded by each wiper during this test with the result that two such areas are typically abraded on the substrate in side-by-side 30 orientation. The blades are typically cycled for 5000 cycles which result in 20,000 wiper strokes across each abraded area.

After abrasion the water repellency of the water repellent film is measured by the sessile water drop method.
The present invention will be further understood from the descriptions of specific examples which follow. In s the following examples, glass coupons were cut from a piece of glass cut from a float glass ribbon formed on a molten bath of tin. All polishing, activating and coating procedures described in the following examples were performed on the tin side of the coupons.
io Example 1 shows a comparison between the durability of a water repellent film formed on a set of glass coupons that were activated by an acid solution of hydrochloric acid is in accordance with the invention, hereinafter "acid activated"
and the durability of a water repellent film formed on a different set of glass coupons that were not activated by an acid solution of the invention. The two sets of glass coupons were each subdivided into four subsets. Each acid activated 2o subset was paired with a non-acid activated subset, and the four pairs of coupon subsets were then subjected to either the CCC, QW, Wet Sled Abrasion or Taber Abrasion testing methods.
More specifically, sixteen glass coupons of clear uncoated float glass measuring 2 x 6 x 0.182 inch (5.08 x 15.24 x 0.462 25 cm) were used for the CCC test, 3 x 4 x 0.182 inch (7.62 x 10.16 x 0.462 cm) for the QW test, 4 x 16 x 0.090 inch (10.16 x 40.64 x 0.3 cm) for the Wet Sled Abrasion test, and 4 x 4 x 0.090 inch (10.16 x 10.16 x 0.3 cm) for Taber Abrasion test were subjected to a heat treatment--which simulates the heat 3o cycles used in bending processes. This heat treatment consisted of subjecting the glass coupons for approximately 15 minutes to a temperature of 525 to 560°C in an electric furnace. After heat treatment the glass coupons were allowed to slowly cool in air to ambient conditions.
After cooling, the 16 glass coupons were polished by hand with a cerium oxide slurry to remove surface impurities.
s The cerium oxide slurry was formed by mixing a commercially available cerium oxide polishing powder with water to a concentration of roughly 20 wt% cerium oxide with balance water. Commercially available cerium oxide polishing powders include RhoditeT" 19A (3.2 micron average particle size) and to RhodoxT''' 76 (3.1 micron average particle size), both of which are listed as 50% cerium oxide, 90% rare earth oxide purity;
and are supplied by Universal Photonics, Inc. of Hicksville, NY. The cerium oxide slurry was applied to the glass coupons with a pad. Polishing was continued until the slurry no is longer pulled away from any portion of the glass coupon.
After polishing, the 16 glass coupons were cleaned with deionized water to remove any residue from the polishing pad or the polish, and dried with a paper towel.
The 16 coupons were divided into two groups, zo designated for discussion purposes as Group A including eight glass coupons and Group B including eight coupons.
The glass coupons of Group A were subjected to an acid activation with 1 Normal (approximately 3.7 wt%) hydrochloric acid solution. The acid solution was applied by 2s hand using an absorbent pad for 60 seconds. The glass coupons of Group B were not subjected to acid activation.
The glass coupons of Groups A a.nd B were then treated twice with a solution of 0.8 wt% silicon tetrachloride in Fluorinert~ FC-77 (hereinafter "FC-77"), a perfluorocarbon/
3o perfluoroether solvent product of 3M Corporation of St. Paul, MN. The silicon tetrachloride solution was applied to the glass coupons with an absorbent pad to form a silica primer layer on the glass coupons of Groups A and B.
The coupons of Groups A and B were then treated once with a solution of: 1) 2.5 wt% perfluoroalkylethyltrichloro-s silane (perfluoroalkyl moieties comprised primarily C6F13 to ClgF3.,); and 2) 2.5 wt% perfluoroalkylethylene (perfluoroalkyl moieties comprised primarily C6F13 to C18F3~) in FC-77 to deposit a perfluoroalkylalkyl silane water repellent composition on the glass coupons. The coupons of Groups A and B were heated io at 150°F (65.5°C) for about 10 hours to cure the coating and produce a water repellent film on the glass coupons. Excess silanes were removed from the glass surfaces by solvent washing. The solvent washing was conducted with PF-5060 (a perfluorohexane product of 3M Corporation). The ,coupons were i5 washed with the solvent by wiping with paper towel until visually clean.
The glass coupons of Group A were then further divided into four subsets or groups, identified for discussion purposes as Groups A1 (2 coupons), A2 (2 coupons), A3 (2 2o coupons) and A4 (2 coupons). The glass coupons of Group B
were similarly divided into Groups B1 (2 coupons), B2 (2 coupons), B3 (2 coupons) and B4 (2 coupons).
The Group A1 and B1 glass coupons were then weathered in the CCC weathering cabinet as described above.
2s One coupon from Group B1 broke during sample preparation and was remade prior to testing. This resulted in this coupon (and only this coupon) receiving 16 hours less CCC exposure time than is indicated in the table below for the remaining coupons.
3o The Group A2 and B2 glass coupons were weathered in the QUV-B313 weathering cabinet as described above.

The Group A3 and B3 glass coupons were subjected to the Wet Sled Abrasion Test. In the present example, the four coupons of Groups A3 and B3 resulted in the formation of eight separate abraded areas. One of the abraded areas on~each of s the four coupons of Group A3 and Group B3.was abraded for 200 cycles with a slurry of 0.5 wt% precipitated silica in water.
One coupon from Group A3 and one coupon from Group B3 were then selected and the remaining abrasion area of each of these coupons was abraded for 600 cycles with the same slurry. The io abrasion area of the remaining coupon of Group A3 and the remaining coupon of Group B3 not previously selected was then subjected to a 5000 cycle test using deionized water instead of the slurry.
The Group A4 and B4 glass coupons were subjected to i5 the Taber Abrasion Test.
For all of the glass coupons tested in Groups A1-A4 and B1-B4, the water repellent film's water repellency efficiency was determined by measuring the contact angle of a sessile drop of water placed upon the sample using the 2o modified captive bubble indicator manufactured by Lord Manufacturing, Inc., as described above. The coupons in Groups A1-A4 and B1-B4 were tested in duplicate. The sessile drop contact angles were measured for both glass coupons, and the results were averaged. The averaged results are shown in as the following tables:

T able 1 CC Table QUV-B313 Contact Angle () Conta ct Angle () Group B1 Group A1 Group B2 Group Hours w/o Acid With Acid Hours w/o Acid~With Acid Tabl e 3 Wet led Table 4 - Tabe r Abraser S

Contact ngle () Contact Angle () A

i5 Group B3 Group A3 Group Group A4 Cycles w/o Acid With Acid Cycles Jo Acid With Acid As can be seen from Table 1, under the CCC
weathering test, the acid activated Group A1 glass coupons maintained a contact angle of 101 degrees at 1494 hours, zs whereas the Group B1 glass coupons maintained only a 59 degree contact angle, showing a very substantial improvement in the durability and water repellency efficiency of the acid activated glass coupons over the non-acid activated glass coupons. The Group B1 coupons were not tested farther than 3o the 1996 hours CCC duration. Common test procedure calls for discontinuing the test after the contact angle either falls _ _ 18 _ below 60° or 3000 hours of test is reached. This procedure was generally followed for the data shown in all Tables 1-7.
As may be seen in Table 3, under the Wet Sled Abrasion Test, at 5000 cycles, the acid activated Group A3 s glass coupons maintained a contact angle of 97 degrees which far exceeded the 42 degree contact angle of the. Group B3 non-acid activated glass coupons, again showing a very substantial improvement in the durability and water repellency efficiency of the acid activated glass coupons over the non-acid lo activated glass coupons.
Similarly, as may be seen in Table 4, under the Taber Abrasion Test, the contact angle after 150 cycles of the acid activated Group A4 glass coupons was 83 degrees whereas the non-acid activated Group B4 glass coupons maintained only is a 75 degree contact angle.
Differences in the QUV-B313 data of Table 2 do not show the substantial improvement obtained by the other tests, but the differences in contact angles are considered to be within normal measurement variations and are not considered to 2o indicate less durability of the water repellent film within the context of that particular testing method.

Example 2 shows a comparison between the durability 2s of a water repellent film formed on a first set of glass coupons which were not acid activated; a second set of glass coupons acid activated with a hydrochloric acid solution; a third set of glass coupons acid activated with a sulfuric acid solution; and a fourth set of glass coupons acid activated 3o with a tartaric acid solution. The four sets of glass coupons were tested utilizing the CCC Weathering Chamber as described above.

Twelve glass coupons of 0.182 inch.(p.462 cm) thick:
clear uncoated float glass measuring 2 inches (5.D8 cm) in width and 6 inches (15.24 cm) in length were subjected to the same heat treatment as described in Example 1.
s The glass coupons were polished using an orbital sander with polyester felt pad with an aluminum oxide slurry to remove impurities. The aluminum oxide slurry was formed by mixing Microgrit~ WCA1T (Microgrit is a registered trademark of the Micro Abrasives Corps, Westfield, MA) with water in a io concentration of approximately 20 wt%. The polishing compound was applied to the glass coupons using the felt pad and an orbital sander until the slurry no longer pulled away from any portion of the glass coupon. After polishing, the glass coupons were cleaned with deionized water and paper towels as is in Example 1.
The 12 coupons were then divided into four groups, designated for purposes of discussion as Groups C, D; E and F, with three coupons in each group.
The coupons in Group C were not acid activated. The 2o glass coupons in Group D were acid activated with a 1 Normal (approximately 3.7 wt°s) hydrochloric acid solution. The glass coupons in Group E were acid activated with a 1 Normal (approximately 4.8 wt%) sulfuric acid solution. The glass coupons in Group F were acid activated with a 10 wto tartaric 2s acid solution. The acid solutions were applied to the glass coupons by wiping with a cotton pad for 1s-30 seconds. The glass coupons of Groups D, E and F were then washed with deionized water and paper towels.
The glass coupons of Groups C, D, E and F were then 3o each treated twice with a solution of 0.8 wt°s silicon tetrachloride in FC-77 on an absorbent pad to form a silica primer layer on the glass coupons.

The glass coupons of Groups C, D, E and F were then treated three times each with a solution of: 1) 2.5 wts perfluoroalkylethyltrichlorosilanes (perfluoroalkyl moieties comprised primarily C6F13 to ClgF3~) ; and 2) 2.5 wt%
perfluoroalkylethylene (perfluoroalkyl moieties comprised primarily C6F13 to C18F3~) in FC-77 to deposit a perfluoroalkylalkyl-silane water repellent composition on the glass coupons. The glass coupons of Groups C, D, E and F were then cured at 150°F (65.6°C) for 8 hours to cure the coating to and produce a water repellent film on the glass coupons.
Excess silanes were removed from the glass coupons by solvent washing. The solvent washing was conduct with PF-5060 and the coupons were washed with the solvent by wiping with a paper towel until visually clean.
i5 The glass coupons of Groups C, D, E and F were weathered in the CCC weathering cabinet as described above.
The water repellent film's water repellency efficiency was determined by measuring the contact angle of a sessile drop of water as described in Example 1. Each of the coupons in ao Groups C, D, E and F were prepared in triplicate, and the contact angles from each group were averaged. The averaged results are shown in the following table:

Table 5 - CCC

Contact Angle () Group C Group Group Group F
D E

Hours w/o Acid HC1 H_~~Q~ . Tartaric io 1278 56 72 63 67 As may be seen from Table 5, at 1278 hours, the contact angle for the acid activated glass coupons of the is Groups D, E and F remained much higher, at 72, 63 and 67 degrees, than the contact angle of the non-acid activated Group C coupons, which maintained only a 56 degree contact angle after weathering.
2o EXAMPLE 3 Example 3 shows a comparison of the durability of a water repellent film formed on a first set of glass coupons which were not acid activated with the durability of a water repellent film formed on a second set of glass coupons which 25 were acid activated with hydrochloric acid solution and a third set of glass coupons acid activated with a tartaric acid solution. The glass substrate was changed over the previous examples, to show that the superior results of the present invention are obtainable on various glass substrates.
3o Nine glass coupons measuring 0.119 inch (0.30 cm) thick of a chemically tempered glass sold by PPG Industries, Inc. of Pittsburgh, PA, HERCULITE~ II glass measuring 2 inches (5.08 cm) in width by 6 inches (15.24 cm) in length were selected. Unlike Examples 1 and 2 above, no heat treatment was applied to the glass coupons of Example 3 prior to polishing.
s The glass coupons were polished using an orbital sander with polyester felt pad and an aluminum oxide slurry, cleaned with deionized water and paper towel as described in Example 2.
The glass coupons were divided into three groups, to designated for purposes of discussion as Groups G, H and I, each group containing 3 coupons. The glass coupons of Group G
were not acid activated. The glass coupons of Group H were acid activated with a 1 Normal hydrochloric acid solution as described in the foregoing examples. The glass coupons of is Group I were acid activated with a 10 wt% tartaric acid solution as described in the foregoing examples. The acid solutions of Groups H and I were wiped on the coupons for 15-30 seconds. The Group H and I glass coupons were then washed with deionized water as described in the foregoing examples.
2o The glass coupons of Groups G, H and I were then treated twice each with a solution of 0.8 wt% silicon tetrachloride in FC-77 as described in the foregoing examples to form a silica primer layer on the glass coupons.
The glass coupons of Groups G, H and I were then as treated three times each with a solution of: 1) 2.5 wts perfluoroalkylethyltrichlorosilanes (perfluoroalkyl moieties comprised primarily C6F13 to C18F3~) ; and 2) 2.5 wto perfluoroalkylethylene (perfluoroalkyl moieties comprised primarily C6F13 to CleF3~) in FC-77 as described in the foregoing 3o examples to deposit a water repellent composition on the glass substrates. The coupons of Groups G, H and I were cured at 150°F (65.5°C) for 8 hours to cure the coating and produce water repellent film on the glass coupons, and excess silanes were removed from the glass surfaces by solvent washing with PF-5060 as described in the foregoing examples.
The coupons of Groups G, H and I were weathered in s the CCC weathering cabinet as described in the foregoing examples.
The water repellent film's water repellency efficiency of the glass coupons of Groups G, H and I was determined by measuring the contact angle of a sessile drop of io water as described in the foregoing examples. While the glass coupons of Groups G, H and I were prepared in triplicate, an HCl-treated coupon of Group H broke prior to weathering. Thus the reported values for the HC1 treated glass coupons are averages of duplicate, not triplicate samples. The reported i5 values for Groups G and I are averages of triplicate values.
The averaged results are shown in the following table:
Table 6 - CCC
Contact Angle (°) Group G Group H Group I
2o Hours w/o Acid HCl Tartaric As can be seen from Table 6, at 2310 hours of weathering, the Group G, non acid activated coupons maintained only a 54 degree contact angle, whereas the acid activated s coupons of Groups H and I maintained contact angles of 89 and 77 degrees respectively, showing considerably superior water repellency after weathering.

io Example 4 shows a comparison of the durability of a water repellent film formed on a first set of glass coupons which were not acid activated with a second set of glass coupons which were acid activated with a hydrochloric acid solution. In this example, the water repellent composition is included an integral primer. Subsets were selected to provide a comparison of polished versus unpolished glass coupons. None of the glass coupons of Example 4 included a heating treatment prior to or after coating the glass coupon with the water repellent composition.
2o Twelve glass coupons of 0.182 inch (0.46 cm) thick clear uncoated float glass measuring 2 inches (5.08 cm) in width by 6 inches (15.24 cm) in length were selected.
The twelve glass coupons were cleaned with deionized water and a paper towel. The glass coupons were divided into 2s four groups of three coupons each, described herein as. Groups J, K, L, and M.
The coupons of Group J were not acid activated or polished.
The coupons of Group K were acid activated with a 1 3o Normal hydrochloric acid solution as described in the foregoing examples but were not subjected to a polishing operation. The glass coupons of Group K were then washed with deionized water and dried as described in the foregoing examples.
The coupons of Group L were polished as described in the prior examples with an aluminum oxide slurry as described s in previous examples but were not acid activated.
The coupons of Group M were both polished and acid activated. Polishing was performed in the same manner as described with respect to the Group L coupons and acid activated in the same manner as described with respect to the io Group K coupons.
The glass coupons of Groups J, K, L and M were then treated with a solution of: 1) 0.5 wt% of perfluoroalkylethyltrichlorosilane (perfluoroalkyl moieties comprised CSF1~); and 2) 0.5 wto silicon tetrachloride in is Isopar° L, a hydrocarbon solvent produced by Exxon Corporation of Houston, TX, to deposit a perfluoroalkylalkyl silane water repellent composition having an integral primer layer on the coupons.
The glass coupons of Groups J, K, L and M were not 2o cured, but were weathered in the CCC weathering cabinet as described in the foregoing examples.
The water repellency of the water repellent film was measured by the contact angle of a sessile drop of water as described in the foregoing examples. Coupons of Groups J, K, L
2s and M were prepared in triplicate and the contact angles from each group were averaged. The averaged results are shown in the following table:

Contact Angle () Unpolis hed Poli shed Group J Group Group L Group K M

s Hours w/o Acid HC1 Jo Acid HC1 1o 658 56 75 53 71 As shown in Table 7, after 824 hours of weathering, is the coupons of Groups J and L, without acid activation, maintained a contact angle of only 47 and 46 degrees respectively, whereas the acid activated coupons of Groups K
and M maintained respective contact angles of 63 and 64 degrees. The results clearly demonstrate that the acid 2o activated surface used with a water repellent film having integral primer improves durability of the water repellency of the film. A comparison of the Group K and Group M coupons demonstrate that at 824 hours, the polishing operation did not significantly affect the contact angle of the Group M coupons.
The above examples are offered to illustrate the present invention. Additional examples were prepared and tested, and the foregoing result is a representative subset of all the prepared examples. Various perfluoroalkylalkyl 3o silanes, hydrolyzable silanes, solvents and concentrations may be applied by any conventional technique, and optionally cured at suitable temperatures for adequate times to provide durable non-wetting surfaces on a variety of substrates.
As can be appreciated, the foregoing disclosure is not limiting to the invention and was presented to provide an s appreciation of the invention. The scope of the present invention is defined by the following claims.

Claims (21)

CLAIMS:
1. A method for increasing the durability of a water-repellent film formed on a non-metallic surface of a substrate, comprising the steps of:
contacting the surface of the substrate with an acid solution selected from the group consisting of solutions of hydrochloric acid, sulfuric acid, tartaric acid, phosphoric acid, hydrobromic acid, nitric acid, acetic acid, trifluoroacetic acid and citric acid;
removing the acid solution from the surface of the substrate to provide a surface that is free of said acid solution and residue of the acid solution; and applying a water-repellent layer on the surface of the substrate after removing the acid to form the water-repellent film.
2. The method of claim 1 wherein the water-repellent layer is a silicon compound.
3. The method of claim 2 wherein said silicon compound is a perfluoroalkylalkyl silane.
4. The method of claim 3 wherein said perfluoroalkylalkyl silane is selected from the group consisting of compounds having the general formula R m R'm SiX4-m-n, wherein R is a perfluoroalkylalkyl radical; m is 1, 2 or 3; n is 0, 1 or 2; and m+n is less than 4; R' is a vinyl radical or an alkyl radical; and X is a radical which is selected from the group consisting of halogen, acyloxy, alkoxy and mixtures thereof.
5. The method of claim 4 wherein R' is methyl, ethyl, vinyl or propyl.
6. The method of claim 4 or 5 wherein R is a perfluoroalkylalkyl radical comprising a perfluoroalkyl moiety of the formulae CF3 to C30F61.
7. The method of any one of claims 1 to 6 wherein said water-repellent layer includes a fluorinated olefin compound.
8. The method of claim 7 wherein said fluorinated olefin compound is selected from the group consisting of compounds which are derived from monomers having the general formula C m F2m+1CH=CH2, where m is from 1 to 30.
9. The method of claim 8 wherein m is from 1 to 16.
10. The method of claim 8 wherein m is from 4 to 10.
11. The method of any one of claims 1 to 10 wherein said step of applying said water-repellent layer comprises applying a primer integral with said water-repellent layer.
12. The method of claim 11 wherein said primer is selected from the group consisting of silanes and siloxanes which are capable of hydrolytic condensation to form a silica gel which functions as the primer integral with said water-repellent product without requiring a separate primer layer.
13. The method of any one of claims 1 to 10, further comprising the step of applying a primer layer to the surface of the substrate after removing the acid and prior to applying the water-repellent layer.
14. The method of claim 13 wherein the primer layer comprises a silica layer.
15. The method of any one of claims 1 to 14 wherein said hydrochloric acid solution has a concentration of about 0.5 to 30 wt% hydrochloric acid in deionized water, wherein said sulfuric acid solution has a concentration of about 0.5 to 30 wt%
sulfuric acid in deionized water, and wherein said tartaric acid solution has a concentration of 1 to 40 wt%
tartaric acid in deionized water.
16. The method of any one of claims 1 to 15 wherein said non-metallic surface is selected from the group consisting of glass, plastic, enamel and ceramic.
17. The method of any one of claims 1 to 15 wherein the non-metallic surface is an inorganic oxide coated surface of the substrate.
18. The method of claim 17 wherein said inorganic oxide is selected from the group consisting of antimony-tin oxide, doped tin oxide and transition metal oxides.
19. The method of any one of claims 1 to 18 wherein the non-metallic surface is a major surface of the substrate.
20. The method of any one of claims 1 to 19, wherein the substrate is non-metallic.
21. The method of claim 20 wherein the substrate is a glass substrate.
CA002202673A 1996-06-07 1997-04-14 Water repellent surface treatment with acid activation Expired - Lifetime CA2202673C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/660,352 US5707740A (en) 1990-04-03 1996-06-07 Water repellent surface treatment with acid activation
US08/660,352 1996-06-07

Publications (2)

Publication Number Publication Date
CA2202673A1 CA2202673A1 (en) 1997-12-07
CA2202673C true CA2202673C (en) 2004-06-22

Family

ID=24649183

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002202673A Expired - Lifetime CA2202673C (en) 1996-06-07 1997-04-14 Water repellent surface treatment with acid activation

Country Status (10)

Country Link
US (2) US5707740A (en)
EP (1) EP0811430B1 (en)
JP (1) JPH1057885A (en)
KR (1) KR100209392B1 (en)
AT (1) ATE223262T1 (en)
CA (1) CA2202673C (en)
DE (1) DE69715093T2 (en)
DK (1) DK0811430T3 (en)
ES (1) ES2183045T3 (en)
MX (1) MX9704190A (en)

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5707740A (en) * 1990-04-03 1998-01-13 Ppg Industries, Inc. Water repellent surface treatment with acid activation
US6025025A (en) * 1990-04-03 2000-02-15 Ppg Industries Ohio, Inc. Water-repellent surface treatment
JPH10259038A (en) * 1997-01-24 1998-09-29 Samsung Corning Co Ltd Durable water-repelling glass and its production
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
US6210750B1 (en) * 1997-06-26 2001-04-03 Samsung Corning Co., Ltd. Water-repellent glass and process for preparing same
JP3605512B2 (en) * 1998-05-29 2004-12-22 本田技研工業株式会社 Combustion chamber component for an internal combustion engine having a water / oil repellent film and a method of forming the film
GB9821984D0 (en) * 1998-10-08 1998-12-02 Thorstone Business Man Ltd Adhesive promotion
WO2000027772A1 (en) * 1998-11-12 2000-05-18 S. C. Johnson Commercial Markets, Inc. Glass surface protective-treating method and glass cleaning agent
US6277480B1 (en) * 1999-05-03 2001-08-21 Guardian Industries Corporation Coated article including a DLC inclusive layer(s) and a layer(s) deposited using siloxane gas, and corresponding method
FR2801582B1 (en) * 1999-11-25 2002-02-01 Daniel Samain PROCESS FOR THE SURFACE TREATMENT OF SILICON PLATES WITH A VIEW TO PROVIDING IMPROVED SURFACE PROPERTIES OF HYDROPHOBIA AND / OR OLEOPHOBIA AND PRODUCTS THUS OBTAINED
FR2816622A1 (en) * 2000-11-15 2002-05-17 Atofina Cationic, fluorinated acrylic copolymers used to impregnate building materials to prevent corrosion and abrasion comprise four or more monomers, including a silane and a fluoromonomer
DE10106494B4 (en) * 2001-02-13 2005-05-12 Papierfabrik Schoeller & Hoesch Gmbh & Co. Kg Self-cleaning and anti-adhesive papers and paper-like materials, process for their preparation and their use
US6890345B2 (en) 2001-09-27 2005-05-10 Tyco Healthcare Group Lp Pretreatment for lubricated surgical needles
JP2003166924A (en) * 2001-11-29 2003-06-13 Nippon Sheet Glass Co Ltd Reciprocating abrasion tester
GB0206930D0 (en) * 2002-03-23 2002-05-08 Univ Durham Method and apparatus for the formation of hydrophobic surfaces
US7202321B2 (en) * 2002-06-07 2007-04-10 The Boeing Company Method and composition for sealing components and components sealed thereby
US7910683B2 (en) * 2002-06-07 2011-03-22 The Boeing Company Tough and strongly-adherent anti-icing coatings
US6811884B2 (en) * 2002-12-24 2004-11-02 Ppg Industries Ohio, Inc. Water repellant surface treatment and treated articles
US7096712B2 (en) * 2003-04-21 2006-08-29 Conocophillips Company Material testing system for turbines
US20050008784A1 (en) * 2003-06-27 2005-01-13 3M Innovative Properties Company Removal and replacement of antisoiling coatings
FR2869604B1 (en) * 2004-04-28 2006-06-23 Saint Gobain ACTIVATION OF A GLASS SURFACE
US20060204766A1 (en) * 2005-03-14 2006-09-14 Jds Uniphase Corporation Anti-moisture and soil-repellent coatings
DE102005045350B4 (en) * 2005-09-22 2009-07-16 Siemens Ag Print template of an SMT process
US8158207B2 (en) * 2007-05-21 2012-04-17 Cal-West Specialty Coatings, Inc. Durable modification of the wetting properties of a surface
EP2077132A1 (en) 2008-01-02 2009-07-08 Boehringer Ingelheim Pharma GmbH & Co. KG Dispensing device, storage device and method for dispensing a formulation
CN102015290B (en) * 2008-03-12 2013-11-13 纳幕尔杜邦公司 Durable automotive windshield coating and the use thereof
WO2009113979A1 (en) * 2008-03-12 2009-09-17 E. I. Du Pont De Nemours And Company Durable coating composition
US8286561B2 (en) 2008-06-27 2012-10-16 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US11786036B2 (en) 2008-06-27 2023-10-17 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly
WO2010042668A1 (en) 2008-10-07 2010-04-15 Ross Technology Corporation Spill resistant surfaces having hydrophobic and oleophobic borders
WO2010112358A2 (en) * 2009-03-31 2010-10-07 Boehringer Ingelheim International Gmbh Method for coating a surface of a component
EP2496886B1 (en) 2009-11-04 2016-12-21 SSW Holding Company, Inc. Cooking appliance surfaces having spill containment pattern and methods of making the same
US10016568B2 (en) 2009-11-25 2018-07-10 Boehringer Ingelheim International Gmbh Nebulizer
EP2504051B1 (en) 2009-11-25 2019-09-04 Boehringer Ingelheim International GmbH Nebulizer
US8022025B1 (en) 2010-01-27 2011-09-20 Nanophase Technologies Corporation Heterocoagulate, and compositions and method for polishing and surface treatment
WO2011116005A1 (en) 2010-03-15 2011-09-22 Ross Technology Corporation Plunger and methods of producing hydrophobic surfaces
JP5874724B2 (en) 2010-06-24 2016-03-02 ベーリンガー インゲルハイム インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツング Nebulizer
EP2678400A4 (en) 2011-02-21 2015-11-18 Ross Technology Corp Superhydrophobic and oleophobic coatings with low voc binder systems
US9827384B2 (en) 2011-05-23 2017-11-28 Boehringer Ingelheim International Gmbh Nebulizer
DE102011085428A1 (en) 2011-10-28 2013-05-02 Schott Ag shelf
WO2013090939A1 (en) 2011-12-15 2013-06-20 Ross Technology Corporation Composition and coating for superhydrophobic performance
WO2013152894A1 (en) 2012-04-13 2013-10-17 Boehringer Ingelheim International Gmbh Atomiser with coding means
BR112014032676A2 (en) 2012-06-25 2017-06-27 Ross Tech Corporation elastomeric coatings that have hydrophobic and / or oleophobic properties
ES2836977T3 (en) 2013-08-09 2021-06-28 Boehringer Ingelheim Int Nebulizer
US11292920B2 (en) 2015-06-10 2022-04-05 Ppg Industries Ohio, Inc. Water repellant surface treatment for aircraft transparencies and methods of treating aircraft transparencies
CN105521934B (en) * 2016-02-02 2018-05-15 浙江大学 A kind of preparation method of aluminum surface super hydrophobic coating
EP4317098A1 (en) 2022-08-01 2024-02-07 Papadopoulos Nikolaos-Xafakis Sotirios G.P. Durable protective easy-to-clean nano-coating systems

Family Cites Families (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB353911A (en) * 1929-06-08 1931-07-29 Electrical Res Prod Inc Improvements in or relating to method of coating articles
US2526431A (en) * 1948-04-07 1950-10-17 Us Rubber Co Method of making rubber coated fabric articles
US2699403A (en) * 1952-05-24 1955-01-11 Emmett J Courts Means and methods for cleaning and polishing automobiles
NL202040A (en) * 1954-11-15
US2923608A (en) * 1956-04-13 1960-02-02 Fmc Corp Method of improving the bonding properties of steel surfaces
NL259958A (en) * 1960-01-25 1964-04-27
US3481756A (en) * 1965-03-02 1969-12-02 Celanese Corp Method of coating with an oxymethylene polymer
FR1498087A (en) * 1966-11-01 1967-10-13 Dow Chemical Co Process for treating metals to cause adhesion of polyolefins
DE1596873B2 (en) * 1967-02-23 1971-06-16 F Kuppersbusch & Sohne AG, 4650 Gelsenkirchen PROCESS FOR COATING ENAMEL SURFACES WITH POLYTETRAFLUORAETHYLENE OR SIMILAR ADHESIVE PLASTICS
JPS4930343B1 (en) * 1969-12-27 1974-08-12
US3758284A (en) * 1970-12-17 1973-09-11 W Haller Porous material and method of making the same
US3950588A (en) * 1974-11-01 1976-04-13 Minnesota Mining And Manufacturing Company Coating of silanol-reactive surfaces with di-silyl poly(perfluorooxyalkylenes)
US4529657A (en) * 1978-05-30 1985-07-16 Ppg Industries, Inc. Method for lowering the surface energy of glass
US4263371A (en) * 1978-10-25 1981-04-21 Ppg Industries, Inc. Organotin treatment for reducing the reactivity of a glass surface
US4276350A (en) * 1979-08-13 1981-06-30 Ppg Industries, Inc. Fluorocarbon treatment for reducing the reactivity of a glass surface and product
US4301197A (en) * 1979-12-03 1981-11-17 Ppg Industries, Inc. Siloxane release surfaces on glass
US4381204A (en) * 1980-05-22 1983-04-26 The General Tire & Rubber Company Adhesion of rubber to brass
JPS58172245A (en) * 1982-04-02 1983-10-11 Asahi Glass Co Ltd Surface treating agent for glass
JPS58172244A (en) * 1982-04-02 1983-10-11 Asahi Glass Co Ltd Surface treating agent for glass
JPS58211701A (en) * 1982-06-04 1983-12-09 Asahi Glass Co Ltd Low reflectance glass
JPS59222272A (en) * 1983-06-02 1984-12-13 Showa Denko Kk Coating method
DE3583707D1 (en) * 1984-06-26 1991-09-12 Asahi Glass Co Ltd TRANSPARENT HEAVY DIRTING ITEM WITH LOW REFLECTION.
US4617057A (en) * 1985-06-04 1986-10-14 Dow Corning Corporation Oil and water repellent coating compositions
FR2598520B1 (en) * 1986-01-21 1994-01-28 Seiko Epson Corp MINERAL PROTECTIVE FILM
US4724022A (en) * 1986-02-28 1988-02-09 Libbey-Owens-Ford Co. Method of preparing a glass release surface employing a perfluorosilane for manufacturing an anti-lacerative window assembly
JPS62252120A (en) * 1986-04-24 1987-11-02 Takahashi Denki Kk Winding method for coil frame
JPH0759699B2 (en) * 1987-10-05 1995-06-28 ダイキン工業株式会社 Water and oil repellent composition
JPH01154533A (en) * 1987-12-11 1989-06-16 Nec Corp Semiconductor integrated circuit device
JP2631224B2 (en) * 1988-04-27 1997-07-16 関西ペイント株式会社 Anti-icing paint composition
US4879345A (en) * 1988-07-27 1989-11-07 Ppg Industries, Inc. Fluoropolymer based coating composition for adhesion direct to glass
GB2230260B (en) * 1989-01-17 1992-05-06 United Glass Ltd Strengthening of glass containers
JPH02311332A (en) * 1989-05-26 1990-12-26 Sekisui Chem Co Ltd Preparation of water-repellent glass
US5328768A (en) * 1990-04-03 1994-07-12 Ppg Industries, Inc. Durable water repellant glass surface
US5308705A (en) * 1990-04-03 1994-05-03 Ppg Industries, Inc. Water repellent surface treatment
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
US5523162A (en) * 1990-04-03 1996-06-04 Ppg Industries, Inc. Water repellent surface treatment for plastic and coated plastic substrates
US4983459A (en) * 1990-04-03 1991-01-08 Ppg Industries, Inc. Chemically reacted glass surface
US4997684A (en) * 1990-07-19 1991-03-05 Ppg Industries, Inc. Method of using perfluoroalkylsilanes to lower the surface energy of glass
JPH04124047A (en) * 1990-09-17 1992-04-24 Nissan Motor Co Ltd Method for water repellent treatment of glass surface
EP0492545B1 (en) * 1990-12-25 1998-03-25 Matsushita Electric Industrial Co., Ltd. Transparent substrate with monomolecular film thereon and method of manufacturing the same
JP2555797B2 (en) * 1991-05-13 1996-11-20 トヨタ自動車株式会社 Water repellent glass and method for manufacturing the same
US5424130A (en) * 1991-05-13 1995-06-13 Toyota Jidosha Kabushiki Kaisha Water repellent glass and process for producing the same
DE69217574T2 (en) * 1991-05-17 1997-06-12 Asahi Glass Co Ltd Surface treated substrate
JP2874391B2 (en) * 1991-06-05 1999-03-24 日産自動車株式会社 Manufacturing method of water-repellent glass
JPH0524886A (en) * 1991-07-15 1993-02-02 Nissan Motor Co Ltd Water-repellent treatment of glass
US5221371A (en) * 1991-09-03 1993-06-22 Lockheed Corporation Non-toxic corrosion resistant conversion coating for aluminum and aluminum alloys and the process for making the same
JPH05170486A (en) * 1991-12-25 1993-07-09 Central Glass Co Ltd Water repellent for glass surface and water-repellent glass
US5413865A (en) * 1992-01-31 1995-05-09 Central Glass Company, Limited Water-repellent metal oxide film and method of forming same on glass substrate
US5368892A (en) * 1992-04-10 1994-11-29 Saint-Gobain Vitrage International Non-wettable glass sheet
JPH0753743A (en) * 1993-08-11 1995-02-28 Nippon Parkerizing Co Ltd Surface preparation agent for resin molding
US5425804A (en) * 1993-11-23 1995-06-20 Taiho Industries Co., Ltd. Water-repellent glazing agent
US5576109A (en) * 1994-04-20 1996-11-19 Asahi Glass Company Ltd. Surface treating agent and surface-treated substrate
US5421866A (en) * 1994-05-16 1995-06-06 Dow Corning Corporation Water repellent compositions
US5599893A (en) * 1994-08-12 1997-02-04 Shin-Etsu Co., Ltd. Water repellent composition

Also Published As

Publication number Publication date
KR980000895A (en) 1998-03-30
EP0811430B1 (en) 2002-09-04
CA2202673A1 (en) 1997-12-07
DE69715093D1 (en) 2002-10-10
ATE223262T1 (en) 2002-09-15
MX9704190A (en) 1998-04-30
US5707740A (en) 1998-01-13
KR100209392B1 (en) 1999-07-15
US5980990A (en) 1999-11-09
JPH1057885A (en) 1998-03-03
DK0811430T3 (en) 2003-01-06
ES2183045T3 (en) 2003-03-16
EP0811430A1 (en) 1997-12-10
DE69715093T2 (en) 2003-05-28

Similar Documents

Publication Publication Date Title
CA2202673C (en) Water repellent surface treatment with acid activation
MXPA97004190A (en) Surface treatment repellent to water conactivation ac
US6025025A (en) Water-repellent surface treatment
EP1583615B1 (en) Water repellent surface treatment and treated articles
EP0810186B1 (en) Water-repellent glass plate
EP0825157B1 (en) Water-repellent glass pane and method for producing same
WO2009043122A1 (en) Coated substrate, composition for treating a substrate and process of treatment
EP3307841B1 (en) Water repellant surface treatment for aircraft transparencies and methods of treating aircraft transparencies
WO1999028534A1 (en) Process for the production of articles covered with silica-base coats
KR100194250B1 (en) Water repellent surface treatment with integrated primer
JPH11322368A (en) Solution for forming water repellent film
JPH09309745A (en) Water-repellent and oil-repellent article and its production
JP2001205187A (en) Method for manufacturing silica-base film coated article and silica-base film coated article
JP2758330B2 (en) Water-repellent agent, water-repellent substrate and method for producing the same
CN115368762A (en) Hydrophobic and oleophobic coating, preparation method and application thereof
JP2000336334A (en) Production of silicaceous film-coated article and functional film-coated article
EP1103531B1 (en) Substrate having treated surface layers and process for producing it
WO2018051958A1 (en) Antifouling article
JPH05319868A (en) Water repellent for glass substrate and treatment for water repellency
MXPA00012112A (en) Water-repellent surface treatment
JP3672688B2 (en) Water repellent glass manufacturing method
EP4317098A1 (en) Durable protective easy-to-clean nano-coating systems
EP1101747A1 (en) Substrate having treated surface layers and process for producing it
JPH09286639A (en) Production of water repellent glass for automobile

Legal Events

Date Code Title Description
EEER Examination request
MKEX Expiry

Effective date: 20170418