WO2004011380A1 - 物品の表面から水滴を滑落させることに優れた物品及びそのような物品を製造するための方法 - Google Patents
物品の表面から水滴を滑落させることに優れた物品及びそのような物品を製造するための方法 Download PDFInfo
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- WO2004011380A1 WO2004011380A1 PCT/JP2003/009565 JP0309565W WO2004011380A1 WO 2004011380 A1 WO2004011380 A1 WO 2004011380A1 JP 0309565 W JP0309565 W JP 0309565W WO 2004011380 A1 WO2004011380 A1 WO 2004011380A1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface 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
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- 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
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- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/211—SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- the present invention relates to an article having a functional (water-slidable) coating excellent in sliding water droplets off the surface of the article.
- This article can be used for architectural and vehicle windows, mirrors, and industrial glass.
- compositions including silicone waxes, luganopolysiloxanes, and surfactants have been proposed for improving water slip performance.
- U.S. Pat. No. 3,579,540 corresponding to Japanese Patent Publication No. 50-15473, discloses a water-repellent composition containing an alkylpolysiloxane and a mineral acid.
- Japanese Patent Application Laid-Open No. 5-310174 discloses a water repellent for window glass for automobiles.
- This water repellent contains an amino-modified silicone oil and a surfactant.
- Japanese Patent Application Laid-Open No. H11-118184 discloses a surface treating agent containing a component which is a fluorine-containing silicone compound and / or a partially hydrolyzed product thereof. This component is
- Example:-(CH 2 ) 3 (CF 2 ) 7 CH 3 and-(CH 2 ) 3 (CF 2 ) 7 CF 3 ) are the first essential unit directly bonded to the silicon atom of the organosiloxane unit.
- Certain groups eg,-(CH 2 ) 3 S i CI 3 ) contain a second essential unit that is directly bonded to the silicon atom of the organosiloxane unit.
- Japanese Patent Application Laid-Open No. 2000-144440 discloses a surface treatment liquid which is a mixture of (a) a first or second silicone compound, (b) an acid, and (c) a solvent containing dissolved water. ing.
- the first silicone compound has a hydrolyzable functional group at a terminal.
- the second silicone compound has a hydrolyzable functional group at one end and a fluorinated alkyl group at the other end.
- Japanese Patent Application Laid-Open No. 8-123375 discloses a water-repellent article prepared by applying a coating solution to a substrate.
- This coating solution comprises: (a) a first solution obtained by hydrolyzing a fluorinated alkyl group-containing silane compound and another compound (polydimethylsiloxane and / or polydimethylsiloxane derivative) in a solvent; (B) melting It is produced by mixing a second solution obtained by hydrolyzing an alkoxylan compound in a medium.
- Japanese Patent Application Laid-Open No. 2000-266758 describes that as essential components (A) a hydroxyl group-containing vinyl polymer, (B) an epoxy-terminated siloxane polymer, (C) a sulfonic acid compound, (D) a crosslinking agent component, E) discloses a coating composition comprising a surfactant.
- Japanese Unexamined Patent Publication No. Hei 6-262 943 discloses an automotive windshield system having a front windshield covered with two layers and a wiper covered with resin.
- Japanese Patent Application Laid-Open No. H8-26882324 discloses a windshield wiper system for a vehicle with a pressure regulator for adjusting the wiper pressure on the front windshield.
- An object of the present invention is to provide an article that is excellent in sliding water droplets off the surface of the article and that is excellent in abrasion resistance against driving of a wiper.
- an article excellent in sliding water droplets off the surface of the article is made from the first method, which includes the following steps:
- each of A 1 and A 2 is independently a divalent hydrocarbon group, or a — (CH 2 ) i-NH—C00— group (i is an integer from 0 to 9), or oxygen; R is a monovalent hydrocarbon group; n is an integer of 2000 or less and represents the average degree of polymerization; each of p and q is independently an integer from 0 to 3; The sum is 3 or more.
- B is a —CF 3 group or —CH 2 CH 2 S i (CH 3 ) 3 _ group ( ⁇ represents a hydrolyzable group, t is an integer from 1 to 3);
- X is a hydrolyzable group Represents, r is an integer from 0 to 12; s is an integer from 1 to 3.
- an article excellent in sliding water droplets off the surface of the article is made from a second method that includes the following steps:
- FIG. 1 is a graph showing the change in the contact angle of a water drop in the wiper abrasion test of Example 1-12 and Comparative Example 13;
- the present invention has been made in view of the above-mentioned problems, and the present inventors provide a silica precursor to be a silica matrix, an alkoxy-terminated dimethyl silicone of a water-sliding component, and durability.
- functional coatings ie, high water-sliding coatings
- functional coatings made with full-alkyl roalkylsilanes, and are colorless and transparent, and have excellent water-sliding properties and durability, especially muddy water abrasion resistance and abrasion resistance with wipers. Functional coating was developed.
- the above article (highly water-slidable article) is manufactured by the above first or second method.
- the total amount of silica in the first or second method refers to the amount of silica obtained from a silica precursor sol (hereinafter referred to as “silica sol J”), which is uniquely derived from the amount of alkoxy silane as a starting material of the silica sol. It is.
- the average degree of polymerization n is particularly preferably from 5 to 1000.
- the alkoxy group-terminated dimethyl silicone represented by the general formula [1] has an alkoxy group at the terminal, hydrolysis and polycondensation reactions occur in the alkoxy group when the functional film is formed, and the silicidity as a matrix and chemical Can be combined.
- fluoroalkylsilane represented by the general formula [2] has a hydrolyzable group at the terminal, hydrolysis and polycondensation reaction occur in the hydrolyzable group when the functional coating is formed, and the matrix is used as a matrix. Can chemically bond with silica.
- the functional coating of the present invention is a coating liquid in which a silica sol serving as a silica matrix is mixed with an alkoxy-terminated dimethyl silicone serving as a water-sliding component, and a fluorinated roalkylsilane serving as a component for imparting durability. It is manufactured from.
- the alkoxy-terminated dimethylsilicone and the fluoroalkylsilane are hydrolyzed and polycondensed at the alkoxy group of the alkoxy-terminated dimethylsilicone and the hydrolyzable group of the fluoroalkylsilane when the coating is formed from the coating solution.
- a reaction occurs and chemically bonds with the silica matrix.
- Silica as a matrix which is a component forming a functional coating, is obtained from a silicic acid sol formed by advancing hydrolysis and polycondensation reaction of alkoxysilane.
- Preparation of the silica sol for example, alkoxysilane (e.g., Te Bok Rae Bok Kishishiran [S i (OC 2 H s) 4 ]) and the solvent a predetermined quantity mixing, stirring (e.g., about 3 about 0 minutes) Solution A Get.
- the solvent is preferably a lower alcohol such as ethyl alcohol or isopropyl alcohol, or a mixed solvent thereof.
- alcohols, ethers and ketones can also be used.
- the acidic aqueous solution and the solvent are mixed and stirred to obtain a solution B. Then, after mixing the solution A and the solution B, the mixture is stirred at room temperature to proceed the hydrolysis and polycondensation reaction of the alkoxysilane to obtain a silica sol.
- the stirring time is preferably from 10 minutes to several days, and particularly preferably from 30 minutes to 1 day. However, when stirring is performed at a temperature other than room temperature, the stirring time is not limited thereto.
- the hydrolysis of alkoxysilane can be performed by adding a small amount of water and an acid catalyst such as hydrochloric acid, nitric acid, and acetic acid using the alkoxysilane as a starting material.
- a silicic acid sol By re-polycondensation by stirring while heating, a silicic acid sol can be obtained.
- the method for preparing the silica sol is not limited to the above method, but the method of gradually mixing the above-mentioned alkoxysilane diluted with a solvent and an acidic aqueous solution diluted with a solvent is as follows. This is preferable because a rapid reaction can be avoided and a more homogeneous reaction can be obtained.
- alkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutyloxysilane, and other tetraalkoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, and the like.
- trialkoxysilanes such as ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and dialkoxysilanes.
- alkoxysilanes tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like are preferable.
- the alkoxy group-terminated dimethylene represented by the general formula ⁇ ] mixed with the silica sol It is important that the number (p + q) of alkoxy groups contained in the silicone is three or more. If the number of the alkoxy groups in the hydrolyzable group is less than 3, the solubility in the silica sol as a silica matrix component obtained by hydrolyzing and polycondensing the alkoxysilane is reduced, and the film forming property is reduced. In addition, the bond between the dimethylsilicone at the end of the alkoxy group and the silicic power, which is a matrix component of the coating, becomes insufficient, and the durability of the functional coating is significantly reduced. + q) must be at least 3.
- the alkoxy-terminated dimethyl silicone represented by the general formula [1] is used in an amount of 0.1% by weight to 10% by weight based on the amount of silica generated from the silicic acid sol. It is important to be mixed.
- the dimethyl silicone content of the functional coating is 0.1% by weight to 10% by weight based on the total amount of silica (100% by weight).
- the amount is less than 0.1% by weight, the coating does not show sufficient water-sliding property.
- the amount exceeds 10% by weight the compatibility with the silica sol is reduced, and the film-forming property is significantly reduced.
- the average polymerization degree n of the alkoxy group-terminated dimethyl silicone represented by the general formula [1] or the dimethyl silicone represented by the general formula [A] exceeds 2000, the solubility in the silica sol becomes remarkable. The insolubles which are reduced and are difficult to separate remain, and the film forming property is remarkably deteriorated. Therefore, it must be not more than 2000, and particularly preferably 5 to 100. If it is less than 5, the volatility of the alkoxy group-terminated dimethyl silicone will be high, and it will be difficult to introduce it into the functional coating. On the other hand, if it exceeds 1000, the compatibility with the silica sol decreases, so that the average degree of polymerization n is more preferably 100 or less.
- the ratio of the full-length loalkylsilane represented by the general formula [2] to 3% by weight to 20% by weight with respect to the total amount of the silylation force generated from the silylation sol. are preferably mixed. If the content is less than 3% by weight, the durability of the coating film is significantly reduced, and if it exceeds 20% by weight, the compatibility with the silica sol serving as a matrix is reduced, and the film forming property is significantly reduced.
- the concentration of the silica precursor in terms of silica in the coating solution may be 0.05 to 0.3% by weight.
- the fluoroalkylsilane represented by the general formula [2] is preferably present in a ratio of 20 to 200 mol per 1 mol of the dimethyl silicone terminated with an alkoxy group. If the amount is less than 20 mol, the content of fluoroalkylsilane at the end of the alkoxy group-terminated dimethylsilicone is low, and it may not be possible to obtain a coating having excellent durability.Thus, it is possible to prevent the occurrence of judder when the wiper slides. However, film peeling due to wiper wiping may occur.
- Examples of the full-length alkyl silane represented by the general formula [2] include CF 3 (CF 2 ) plausibleCH 2 CH 2 Si (OCH 3 ) 3 and CF 3 (CF 2 ) complicat CH 2 CH 2 S i CH 3 (OCH 3 ) 2 , CFJ (CF 2 ) u CH 2 CH 2 S i (CH 3 ) 2 OCH 3 , CF 3 (CF 2 ) 9 CH 2 CH 2 S i (OCH 3 ) 3 , CF 3 (CF 2 ) 9 CH 2 CH 2 S i C 'H 3 (OCH 3 ) 2 , CF 3 (CF 2 ) 9 CH 2 CH 2 S i (CH 3 ) 2 OCH 3 , CF 3 (CF 2 ) 7 CH 2 CH 2 S i (OCH 3 ) 3 , CF 3 (CF 2 ) 7 CH 2 CH 2 S i CH 3 (OCH 3 ) 2 , CF 3 (CF 2 ) 7 CH 2 CH 2 S i (OCH 3 ) 2
- Examples of the hydrolyzable group represented by X or Y in the general formula [2] include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group; And an isocyanate group.
- hydrolysis and polycondensation reactions occur in the alkoxy group portion of the alkoxy-terminated dimethyl silicone and the hydrolyzable group portion of the fluoroalkylsilane, so that when a functional film is formed,
- the dimethyl silicone and the fluoroalkyl silane are chemically bonded to silica as a matrix, and a coating having excellent durability can be obtained.
- the alkoxy group and the hydrolyzable group that do not form a chemical bond with the silica matrix react with the alkoxy group of another dimethyl silicone terminated with an alkoxy group or the hydrolyzable group of a full-length alkylsilane to form a bond. It can be caused.
- the dimethyl silicone and the fluoroalkylsilane may be bonded to the silica matrix via another dimethylsilicone and another fluoroalkylsilane.
- the functional coating that prevents the occurrence of judder is defined as the wiper blade chattering when the wiper is wiped by the wiper when the wiper blade is slid while water is sprinkled on the coating with water drops or raindrops. This is a level that does not hinder driving and does not cause any trouble.
- a natural rubber-based rubber coated with fluorine resin, nylon resin, polyisoimide, graphite, or the like can be used as the wiper rubber to be attached to the wiper blade.
- the functional film of the present invention preferably has a thickness of 1 O nm to OO nm. If it is less than 1 O nm, the durability is reduced due to the influence of diffusing components such as alkalis present in the substrate when the substrate is soda lime silicate glass, which is widely used, which is preferable. Absent.
- the concentration of silica in the coating solution must be increased. If the concentration of silica in the coating solution is increased, silica and alkoxy-terminated dimethyl silicone The compatibility with the orchid is reduced, and it is difficult to obtain a homogeneous film having excellent transparency, which is not preferable. This is particularly important when applied to automotive window glass, which requires excellent transparency.
- a film thickness of up to 30 nm can also be used.
- the coating solution for a functional film is obtained by adding the above-mentioned silica sol to be a silica matrix to an alkoxy-terminated dimethyl silicone represented by the above general formula [ ⁇ ] and a full-thickness resin represented by the above general formula [2]. And a low alkyl silane. Subsequently, it can be obtained by hydrolyzing the above-mentioned alkoxy-terminated dimethylsilicone and the above-mentioned fluoroalkylsilane, and further bonding them to the above-mentioned sol by a polycondensation reaction. At this time, it is preferable to mix the alkoxy group-terminated dimethyl silicone and the full-colored alkyl silane beforehand, since both components can be homogeneously mixed in the coating solution.
- the second method is based on a composition obtained by hydrolyzing and polycondensing an alkoxy group-terminated dimethyl silicone represented by the general formula [1] and a full-length loalkylsilane represented by the general formula [2]. And a step of mixing the solution with a solution obtained by hydrolyzing and polycondensing alkoxysilane to obtain a coating solution.
- the polycondensation composition obtained by previously hydrolyzing and polycondensing the alkoxy group-terminated dimethyl silicone and the fluorinated alkyl silane the chemical bond between the two is strengthened, and the water-sliding property is improved.
- Solvents used in the first or second method include lower alcohols such as ethyl alcohol and isopropyl alcohol, ketones such as methylethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and toluene. , Benzene, xylene and other aromatic hydrocarbon solvents, getyl ether, diisopropyl ether It is preferable to use ethers such as toluene, chlorinated solvents such as chloroform and carbon tetrachloride, and mixtures thereof.
- the obtained coating liquid is applied to the surface of a substrate.
- Various coating methods such as hand coating, nozzle flow coating, divebing, spraying, reverse coating, flexo, printing, flow coating, spin coating, and a combination of these methods are used as appropriate. I can do it. It can also be used as a simple type of spray-type water-repellent agent.
- a heat treatment is carried out to cause a polycondensation reaction between the silica sol and the alkoxy-terminated dimethylsilicone and the fluoroalkylsilane to combine the dimethylsilicone and the fluoroalkylsilane with the silica matrix.
- a functional coating is fixed on the substrate surface.
- the heat treatment temperature is preferably from 80 ° C to 600 ° C. If the heat treatment temperature is lower than 80 ° C., not only the polycondensation reaction becomes insufficient, but also the functional coating does not sufficiently adhere to the base material, and as a result, the durability decreases, which is not preferable. On the other hand, when the temperature exceeds 600 ° C., dimethyl silicone and fluorinated alkyl silane are thermally decomposed and the slipperiness is remarkably reduced.
- the base material is not particularly limited, such as glass and plastic.
- a float glass or a float glass commonly used for architectural window glass, automotive window glass, or the like is used.
- Inorganic and transparent plate glass such as soda-lime silicate glass manufactured by the mouth-flow method is preferable, and is colorless or colored, and its type or color, combination with other functional films, glass shape It is not particularly limited to flat glass and bent glass, but also various types of tempered glass such as tempered glass, chemically strengthened glass, etc., meshed glass, and phosphate glass, and low expansion. Glass, Zero-expansion glass, Low-expansion crystallized glass, Zero-expansion crystallized glass, Glass for TFT, Glass for PDP, Base glass for optical filter Can With various glass.
- Glass can be used as a single plate, or as double glazing or laminated glass.
- the coating may be formed on one side or both sides of the substrate, or may be formed on the entire surface or a part of the surface of the substrate.
- the functional coating of the present invention has high water slippage and durability, especially muddy water abrasion resistance, wipers, etc.
- the highly durable functional film of the present invention has high water repellency and lubricity. It is excellent in water resistance and abrasion resistance due to wipers, etc.
- Examples 11-1 to 13 and Examples 2-1 to 2-13 correspond to the first method.
- Examples 3-1 to 3-5 correspond to the second method.
- the coating solution consists of alkoxy-terminated dimethyl silicone and The mixture was obtained by adding and mixing the above-mentioned silylation sol X to the mixture obtained by mixing.
- Table 1 shows the sample preparation conditions.
- silica concentration 0.1% by weight
- silica concentration the weight ratio of the alkoxy-terminated dimethyl silicone to the silica conversion amount of the silica sol (hereinafter referred to as “silicon concentration”) is 1% by weight
- silica sol is calculated as silica.
- a coating liquid having a weight ratio of the full-silylalkyl silane to the amount (hereinafter referred to as “full-silylalkylsilane concentration”) of 10% by weight was obtained.
- polishing solution a suspension (1% by weight) of glass polishing agent MIRAKE A (T) (manufactured by Mitsui Mining & Smelting) dispersed in tap water was used.
- the coating solution prepared in (2) was applied onto the glass substrate prepared in (3) by a spin coat method. First, place the above glass substrate on the spinco all day long, drop approximately 200 ml of coating solution while rotating at a rotation speed of 80 rpm, and maintain the rotation speed for 30 seconds to coat the coating film. Drying was performed to obtain a transparent gel film having good film-forming properties. Next, a heat treatment was performed at 280 ° C. for 10 minutes, and the resultant was cooled to room temperature to obtain a glass sample with a functional coating having a film thickness of 20 nm (highly water-slidable article).
- the slipperiness in the present invention is evaluated by a method as described in the evaluation method of Examples. After dropping 50 nI of pure water onto the sample surface, the sample is gradually tilted, and the evaluation is made by measuring the tilt angle at the time when the water droplet starts to move.
- the inclination angle was defined as a falling angle (°), and the falling angle was measured in the atmosphere (about 25 ° C.) using a CA-A type manufactured by Kyowa Interface Science.
- the obtained functional coating was evaluated by the following evaluation methods. The results are shown in Table 2.
- the angle between the water droplet and the sample surface when about 2 ⁇ I of pure water was placed on the sample surface having the functional coating was measured with a contact angle meter.
- the contact angle was measured in the atmosphere (approximately 25 ° C) using a CA-X model manufactured by Kyowa Interface Science.
- the angle of inclination at which the water droplet began to move was defined as the falling angle (°).
- the falling angle was measured in the air (about 25 ° C) using CA-A type manufactured by Kyowa Interface Science.
- the sample surface is about 1.5 kg / cm 2 with a cotton cloth impregnated with a suspension (10% by weight) of glass polishing agent MIRAKE A (T) (manufactured by Mitsui Mining & Smelting) in tap water. Polished. The number of polishings (reciprocation) until 70% of the polishing area became hydrophilic was evaluated.
- the thickness of the functional film was measured by Surfcorder-1 (Kosaka Laboratories, ET 4000A).
- Alkoxy group-terminated dimethyl silicone having an average polymerization degree n is 300 [(C 2 H 5 0) 3 S i CH 2 CH 2 [S i (CH 3) 2 O] 300 S i (CH 3) 2 CH 2 CH 2 S i (OC 2 H 5 ) 3 ] except that i was used as in Example 1-1.
- Alkoxy-terminated dimethyl silicone having an average degree of polymerization n of 500 [(CH 30 ) 3 S i CH 2 CH 2 [S i (CH 3 ) 2 O] 500 S i (CH 3 ) 2 CH 2 CH 2 S i ( All were the same as Example 11 except that OCH 3 ) 3 ] was used.
- Alkoxy-terminated dimethyl silicone having an average degree of polymerization n of 50 [(CH 3 ⁇ ) 3 Si CH 2 CH 2 [Si (CH 3 ) 2 O] 50 Si (CH 3 ) 2 CH 2 CH Z Si ( All were the same as Example 11 except that OCH 3 ) 3 ] was used.
- Alkoxy-terminated dimethyl silicone having an average degree of polymerization ⁇ of 150 [(CH 30 ) 3 S i 0 [S i (CH 3 ) 20 ], 5 . All were the same as Example 1-1 except that S i (OCH 3 ) 3 ] was used.
- Example 1-1 All were the same as Example 1-1 except that the silicone concentration was 0.5% by weight.
- Example 11 All were the same as Example 1-2 except that the silicone concentration was 1.5% by weight and the concentration of full-colored loalkylsilane was 1ii:%.
- Example 11 Except that the heat treatment was performed at 150 ° C. for 10 minutes, the same operation as in Example 11 was performed.
- Example 11-11 Except that the fluoroalkylsilane concentration was set to 0% by weight, all were the same as in Example 11-11. That is, in this comparative example, a coating film containing no full-length roalkylsilane was prepared.
- Example 1-1 All were the same as Example 1-1 except that the silicone concentration was 50.0% by weight and the concentration of full-colored loalkylsilane was 3% by weight.
- Figure 3 and Table 3 show the results of the wiper wear test.
- the contact angle in the area (overlapping area) to be wiped by both the driver's side and the passenger's side wipers is as low as 60 ° after 330,000 times wiping, and the upper reversing part of the passenger side wiper also deteriorates in a wide range. And the durability was bad.
- Alkoxy-terminated dimethyl silicone having an average degree of polymerization n of 2500 [(CH 30 ) 2 (CH 3 ) Si CH 2 CH 2 [Si (CH 3 ) 2 O] 2500 Si (CH 3 ) 2 CH 2 CH 2 S i (CH 3 ) (OCH 3) 2 ] except that was used.
- Example 1-1 All were the same as Example 1-1 except that the silicone concentration was 20% by weight.
- Comparative Example 11-6 All were the same as in Example 1-1, except that the concentration of the full-length alkyl silane was 30% by weight.
- silica concentration in the coating solution was set to 1.0% by weight, all were the same as in Example 1-1.
- Example 1-1 All were the same as Example 1-1 except that the heat treatment of the obtained coating film was omitted.
- Example 11 A silylation sol was obtained in the same manner as in the method of 1.
- the coating liquid was obtained by adding and mixing the above silica sol to a mixture obtained by mixing alkoxy group-terminated dimethylsilicone and fluorenealkylalkylsilane.
- Table 4 shows the sample preparation conditions.
- silica concentration was 0.1% by weight
- silica concentration was 2.5% by weight
- alkoxy group-terminated was 2.5% by weight
- a coating liquid having a molar ratio of FAS to dimethyl silicone ((the number of moles of fluoroalkylsilane) / (the number of moles of dimethyl silicone having an alkoxy group), hereinafter referred to as “FAS mole ratio”) of 81 was obtained.
- the float glass surface of the windshield size of the actual vehicle (about 150 Omm X 100 Omm) was polished with a polishing solution, and then washed and dried. The same polishing liquid as in Example 11 was used.
- the coating solution prepared in (2) was applied onto the glass substrate prepared in (3) by spin coating.
- a glass substrate is placed on a spin coater, and approximately 300 ml of coating solution is dropped while rotating at a rotation speed of 80 rpm, and the coating film is dried while maintaining the rotation speed for 30 seconds.
- a good transparent gel film was obtained.
- heat treatment was performed at 370 ° C. for 7 minutes, and the mixture was cooled to room temperature to obtain a colorless, transparent and highly durable glass sample with a functional coating film.
- Example 11 The contact angle was measured by the same method as in the method of Example 1.
- the falling angle was measured by the same method as in Example 1-1.
- the coating on the driver's seat side was evaluated before contact and after the wiper was slid 270,000 times, and the contact angle and judder were evaluated. Judder evaluation was conducted by visually observing the state of run-out (chatter) at the lower end of the wiper blade. Levels that hinder driving
- Example 2 Colorless and transparent I I I 8 o
- Example 2- Colorless and transparent 1 U O Example 2-k Colorless and transparent 1 Uo 1 I Example Colorless and transparent 1 Uol 4
- Example Z ll Colorless and transparent 1 U o IU Example 2M Colorless and transparent 11 ⁇ u Example, 13 Colorless and transparent 1 0 8 1 1 Comparative example 1 Colorless and transparent 1 0 5 8 Comparative example Colorless and transparent 1 1 1 2 0 Compare Example 1 Spotted 1 1 3 2 7 Comparative Example 2 Colorless and transparent 7 8 2 0 Table 6
- Example 2-1 The same procedures as in Example 2-1 were performed except that 0.47 g of the 8FAS solution and 0.0 g of the dimethylsilicone-terminated dimethylsilicone solution were used.
- Example 8 All were the same as Example 2-1 except that 0.49 g of the 83 solution was used and 0.0 g of the dimethyl silicone solution having an alkoxy group terminated.
- Example 2-4 All were the same as Example 2-1 except that 0.49 g of the 83 solution was used and 0.0 g of the dimethyl silicone solution having an alkoxy group terminated.
- Example 2-4 All were the same as Example 2-1 except that 0.49 g of the 83 solution was used and 0.0 g of the dimethyl silicone solution having an alkoxy group terminated.
- Example 2-4 All were the same as Example 2-1 except that 0.49 g of the 83 solution was used and 0.0 g of the dimethyl silicone solution having an alkoxy group terminated.
- Example 2-1 was the same as Example 2-1 except that 0.51 g of the C8 FAS solution and 0.49 g of the alkoxy group-terminated dimethyl silicone solution were used.
- the average degree of polymerization of the alkoxy-terminated dimethyl silicone is 150 C (CH 3 0) 3 Si CH 2 CH 2 ⁇ Si (CH 3 ) 20 ⁇ 150 Si (CH 3 ) 2 CH 2 CH 2 Si ( OCH 3 ) 3 ]]], except that OCH 3 ) 3 ] was used.
- the average degree of polymerization of the alkoxy-terminated dimethyl silicone is 300 [(CH 30 ) 3 Si CH 2 CH 2 ⁇ Si (CH 3 ) 20 ] 300 Si (CH 3 ) 2 CH 2 CH 2 Si (OC H 3 ) 3 ], except that it was the same as Example 2-1.
- Example 21 The procedure was the same as Example 21 except that 0.27 g of the C8 FAS solution and 0.88 g of an alkoxy-terminated dimethyl silicone (average degree of polymerization 250) solution diluted to 4% by weight were added.
- Example 2-1 All were the same as Example 2-1 except that the average degree of polymerization of the alkoxy group-terminated dimethyl silicone was 200 and the amount of the solution added was 0.18 g.
- Example 2-1 All were the same as Example 2-1 except that the silicone concentration was 0% by weight. That is, in this comparative example, a coating film containing only fluoroalkylsilane without containing an alkoxy group-terminated dimethyl silicone in a silica matrix was prepared. As a result, spot marks were generated on the entire surface of the coating.
- Example 2-1 was the same as Example 2-1 except that the silica concentration was 0% by weight. That is, in this comparative example, a film containing no siri force as a matrix component was prepared.
- Example 11 A silica sol was obtained in the same manner as in the method of Example 11.
- the coating solution was obtained by mixing a solution obtained by previously hydrolyzing and polycondensing an alkoxy-terminated dimethyl silicone and a fluoroalkylsilane with the silica sol.
- heptane decaflurode rodecyl trimethoxysilane diluted to 1% by weight with ethyl acetate [CF 3 (CF 2 ) 7 CH 2 CH 2 S i (OCH 3 ) or later “C 8 F AS ⁇ Solution; 3.60 g, alkoxy-terminated dimethyl silicone with an average weight of 200, diluted to 0.1% by weight with ethyl acetate [(CH 30 ) 3 Si CH 2 CH 2 [Si (CH 3) 2 0] 2. .
- the concentration of silica is 0.1% by weight
- the concentration of alkoxy-terminated dimethyl silicone with respect to silica (hereinafter referred to as “silicone concentration”) is 1% by weight
- a coating solution having a concentration (hereinafter abbreviated as “FAS concentration J”) of 10% by weight was obtained.
- the coating solution prepared in (2) was applied onto the glass substrate prepared in (3) by spin coating.
- a glass substrate was placed on a spin coater, and about 30 ml of coating liquid was dropped while rotating at a rotation speed of 80 rpm, and the coating film was dried while maintaining the rotation speed for 30 seconds. A good transparent gel film was obtained.
- heat treatment was performed at 280 ° C. for 10 minutes, and the mixture was cooled to room temperature to obtain a colorless, transparent, highly durable glass with a functional coating having a thickness of 20 nm.
- Example 11 The contact angle was measured by the same method as in the method of Example 1.
- the falling angle was measured by the same method as in Example 1-1.
- the thickness of the functional film was measured with an ellipsometer (DVA-FL3G, manufactured by Mizojiri Optical Industrial Co., Ltd.). Films that were not optically transparent and could not be measured all over the ellipsometer were measured with a surface roughness meter (Solantech, DEKTAK2A).
- a cotton cloth is pasted on a piece of metal that is 20 mm wide (20 mm long) and has a curved surface of R45 in the length direction, and the glass polishing agent MIRAKE A (T) (manufactured by Mitsui Mining & Smelting) is supplied to the tap water.
- the suspension impregnated with a ceria suspension (10% by weight) was used as a friction element. At this time, the load on the friction element was 3 kg.
- This friction element is polished in an area of 10 OmmX 20 mm at a sliding speed of 60 times, and the number of times of sliding until the area of 70 mm X 15 mm in the center of the polished part becomes hydrophilic (reciprocating) was measured.
- Example 3-2 The procedure was the same as Example 3-1 except that CF 3 (CF 2 ) 7 CH 2 CH 2 Si CI 3 , hereinafter referred to as “C 8 FAS CJ” was used.
- the average degree of polymerization is 300 [(CH 30 ) 3 Si CH 2 CH 2 [Si (CH 3 ) 2 O] 300 Si (CH 3 ) 2 CH 2 CH 2 Si (OC H 3 ) 3 ], and as a full-radioalkyl silane, a helicosaful rhododecyl trimethoxysilane CC F 3 (CF 2 ) 9 CH 2 CH 2 S i (OCH 3 ) 3 , hereinafter referred to as “C 10 FAS
- the FAS concentration was 10% by weight and the silicon concentration was 1.5% by weight.
- the preparation method of the coating solution was the same as in Example 3-1.
- Example 3-1 All were the same as Example 3-1 except that the heat treatment was performed at 150 for 10 minutes.
- Polydimethylsiloxane having an average degree of polymerization of 50 with one hydroxyl group at each end as a silicone component! : H ⁇ [S i (CH 3 ) 2 O] 50 S i (CH 3 ) 2 OH]] was used in the same manner as in Example 3-1.
- Example 3-1 Except that the heat treatment of the obtained coating film was omitted, the same procedure was performed as in Example 3-1.
- Example 3-1 All were the same as Example 3-1 except that the silicone concentration was 0% by weight. That is, in this comparative example, a film containing only a full-grown loalkylsilane in a matrix made of silica without containing an alkoxy-terminated dimethyl silicone was prepared.
- Example 3 was the same as Example 3 except that the silica concentration was 0% by weight. That is, in this comparative example, a coating film containing no silica component as a matrix was prepared.
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Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020047019558A KR100802519B1 (ko) | 2002-07-30 | 2003-07-29 | 물품의 표면에서 물방울을 슬립다운시키는데 우수한 물품 및 그 물품을 제조하기 위한 방법 |
EP03771394A EP1526119A4 (en) | 2002-07-30 | 2003-07-29 | SUBJECT TO EXCELLENT WATER DROP BING FROM THE SURFACE OF THE SUBJECT AND METHOD FOR PRODUCING SUCH A SUBJECT |
MXPA05001036A MXPA05001036A (es) | 2002-07-30 | 2003-07-29 | Articulo excelente para el resbalamiento de la gota de agua desde la superficie del articulo y proceso para producir tal articulo. |
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JP2002220665 | 2002-07-30 | ||
JP2002-220665 | 2002-07-30 | ||
JP2003-40237 | 2003-02-18 | ||
JP2003-40238 | 2003-02-18 | ||
JP2003040238A JP4152769B2 (ja) | 2003-02-18 | 2003-02-18 | 高耐久な滑水性被膜の製造方法 |
JP2003040237 | 2003-02-18 | ||
JP2003-113085 | 2003-04-17 | ||
JP2003113085A JP4014532B2 (ja) | 2002-07-30 | 2003-04-17 | 高滑水性被膜及びその形成方法 |
JP2003-155171 | 2003-05-30 | ||
JP2003155171A JP4014538B2 (ja) | 2003-02-18 | 2003-05-30 | 高耐久な滑水性被膜及びその形成方法 |
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PCT/JP2003/009565 WO2004011380A1 (ja) | 2002-07-30 | 2003-07-29 | 物品の表面から水滴を滑落させることに優れた物品及びそのような物品を製造するための方法 |
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US (1) | US6884512B2 (ja) |
EP (1) | EP1526119A4 (ja) |
KR (1) | KR100802519B1 (ja) |
CN (1) | CN1301226C (ja) |
MX (1) | MXPA05001036A (ja) |
TW (1) | TWI227706B (ja) |
WO (1) | WO2004011380A1 (ja) |
Cited By (2)
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JP2006290923A (ja) * | 2005-04-06 | 2006-10-26 | Central Glass Co Ltd | 滑水性物品の製法 |
CN1982392B (zh) * | 2005-12-15 | 2011-07-13 | 赢创德固赛有限责任公司 | 赋予光滑无机表面以耐磨和耐气候的“易清洁”涂层的贮存稳定性涂层组合物 |
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RU2007109491A (ru) * | 2004-08-16 | 2008-09-27 | Хонейвелл Интернэшнл Инк. (Us) | Способы предотвращения образования инея и облегчения удаления зимних осадков с передних стекол автомобилей и композиции для защиты от зимних осадков |
KR100894079B1 (ko) * | 2004-08-27 | 2009-04-21 | 샌트랄 글래스 컴퍼니 리미티드 | 활수성 피막을 얻기 위한 처리제 및 활수성 피막의 제조방법 |
US7879449B2 (en) * | 2006-03-14 | 2011-02-01 | Cerasol Hong Kong Ltd. | Non-stick ceramic coating composition and process |
CA2581474A1 (en) * | 2006-03-14 | 2007-09-14 | Cerasol Hong Kong Limited | Non-stick ceramic coating composition and process |
DE102008002250A1 (de) * | 2008-06-06 | 2009-12-10 | Robert Bosch Gmbh | Beschichtungsmaterial für Elastomermaterialien |
DE102009026746A1 (de) * | 2009-06-04 | 2010-12-09 | Sensient Imaging Technologies Gmbh | Sprühgetrocknete Farbstoffkomposite, Verfahren zu ihrer Herstellung und ihre Verwendung |
KR102291408B1 (ko) * | 2014-02-26 | 2021-08-18 | 쇼와덴코머티리얼즈가부시끼가이샤 | 에어로겔 |
JP6704854B2 (ja) | 2014-10-31 | 2020-06-03 | 住友化学株式会社 | 透明皮膜 |
WO2016068103A1 (ja) | 2014-10-31 | 2016-05-06 | 住友化学株式会社 | 撥水撥油コーティング組成物 |
WO2016068118A1 (ja) | 2014-10-31 | 2016-05-06 | 住友化学株式会社 | 透明皮膜 |
TWI689560B (zh) * | 2014-11-12 | 2020-04-01 | 日商住友化學股份有限公司 | 透明皮膜 |
JP6705752B2 (ja) | 2014-11-12 | 2020-06-03 | 住友化学株式会社 | 撥水撥油コーティング組成物及び透明皮膜 |
WO2017056116A1 (en) * | 2015-09-29 | 2017-04-06 | Csi Nanotechnology S.R.L. | Composition useful as a hydrophobic agent |
CN109988310B (zh) * | 2017-12-29 | 2022-04-29 | 乳源东阳光氟有限公司 | 一种氟硅硫化合物及其制备方法和应用 |
JP6683983B2 (ja) * | 2018-09-27 | 2020-04-22 | 大和製罐株式会社 | 撥液性の膜 |
CN113015581A (zh) * | 2018-11-13 | 2021-06-22 | 巴斯夫欧洲公司 | 易清洁的涂层 |
CN109868652A (zh) * | 2019-03-07 | 2019-06-11 | 扬州金泉旅游用品有限公司 | 一种制备疏水和防污的织物和布料的方法 |
WO2023198748A1 (en) * | 2022-04-14 | 2023-10-19 | Optitune Oy | Process for preparing an abrasion resistant coating |
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- 2003-07-29 WO PCT/JP2003/009565 patent/WO2004011380A1/ja active Application Filing
- 2003-07-29 MX MXPA05001036A patent/MXPA05001036A/es active IP Right Grant
- 2003-07-29 US US10/628,566 patent/US6884512B2/en not_active Expired - Fee Related
- 2003-07-29 EP EP03771394A patent/EP1526119A4/en not_active Withdrawn
- 2003-07-29 KR KR1020047019558A patent/KR100802519B1/ko not_active IP Right Cessation
- 2003-07-29 CN CNB038154900A patent/CN1301226C/zh not_active Expired - Fee Related
- 2003-07-30 TW TW92120887A patent/TWI227706B/zh not_active IP Right Cessation
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CN1982392B (zh) * | 2005-12-15 | 2011-07-13 | 赢创德固赛有限责任公司 | 赋予光滑无机表面以耐磨和耐气候的“易清洁”涂层的贮存稳定性涂层组合物 |
Also Published As
Publication number | Publication date |
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KR100802519B1 (ko) | 2008-02-12 |
CN1665752A (zh) | 2005-09-07 |
TWI227706B (en) | 2005-02-11 |
EP1526119A1 (en) | 2005-04-27 |
TW200403194A (en) | 2004-03-01 |
EP1526119A4 (en) | 2009-12-30 |
US20040076840A1 (en) | 2004-04-22 |
CN1301226C (zh) | 2007-02-21 |
MXPA05001036A (es) | 2005-05-16 |
US6884512B2 (en) | 2005-04-26 |
KR20050014847A (ko) | 2005-02-07 |
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