WO2006022118A1 - 滑水性被膜を得るための処理剤及び滑水性被膜の作製法 - Google Patents
滑水性被膜を得るための処理剤及び滑水性被膜の作製法 Download PDFInfo
- Publication number
- WO2006022118A1 WO2006022118A1 PCT/JP2005/014033 JP2005014033W WO2006022118A1 WO 2006022118 A1 WO2006022118 A1 WO 2006022118A1 JP 2005014033 W JP2005014033 W JP 2005014033W WO 2006022118 A1 WO2006022118 A1 WO 2006022118A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- slidable
- primer layer
- fluoroalkylsilane
- treatment agent
- Prior art date
Links
Classifications
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials 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
-
- 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
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
-
- 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
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
- C03C2218/33—Partly or completely removing a coating by etching
Definitions
- the present invention relates to a treatment agent for obtaining a water-slidable film capable of being formed on a substrate by drying at room temperature, and a preparation method for obtaining a water-slidable film. Further, the present invention relates to a method for producing a water-slidable article excellent in water repellency and water droplet sliding property, which is preferably used for a vehicle window glass or a side mirror of a motor vehicle or the like.
- Patent Document 1 discloses a vehicle glass surface treatment agent having a perfluoroalkylsilane, an organopolysiloxane, and the like. A coating formed by drying at room temperature with the treatment agent has a water repellency, It has been shown to have excellent water slidability and suppress the occurrence of judder.
- the water repellency, water slidability, and durability of the coating that can provide such a treatment agent force vary greatly depending on the concentration and reactivity of the perfluoroalkylsilane and organopolysiloxane in the treatment agent. To do.
- functional components that give rise to functions such as water repellency and water slidability that are not related to the formation of the film after the treatment are solidified as an excess, so that the resulting film can be transparent. It adversely affects functions such as light, water repellency and water slidability.
- Patent Document 2 discloses a treatment agent obtained by mixing a silicone having a hydrolyzable functional group at the terminal and a fluoroalkyl group at the other end in a solution containing acid, water, and the like. It has been shown that the film obtained with the agent is excellent in water repellency and water slidability. However, since the treatment agent disclosed in Patent Document 2 requires heating at 100 ° C. or higher after being applied to the base material, a coating is formed on the window glass assembled in a vehicle or the like. This method is not suitable for the case where the coating has already been treated or to restore the water repellency and water slidability.
- Patent Document 3 a dimethyl silicone diol having a reactive group in organopolysiloxane is used to form a chemical bond with a base material, thereby improving water repellency and water slidability. It has been disclosed to improve durability while maintaining.
- the water repellency, water slidability, and durability of the resulting coating greatly vary depending on the concentration and reactivity of perfluoroalkylsilane and organopolysiloxane in the treatment agent.
- the tumbling angle the inclination angle at which 501 water drops fall on a window glass, side glass, etc.
- the visibility at the time is exceptionally improved.
- the treatment agent disclosed in Patent Document 1 has advantages such as easy formation of a film, but the water repellency and water slidability of the film and the durability of the film are in a trade-off relationship. For this reason, it is not easy to achieve a film that satisfies both.
- an alkoxysilane-based water repellent having a base film of tetraisocyanate silane formed on a glass substrate and having at least one side chain having a fluorocarbon group thereon. It is disclosed that a water-repellent article having excellent durability can be obtained by applying a coating liquid comprising (Patent Document 4 by the present applicant).
- Patent Document 5 a substrate treatment liquid obtained by dissolving a substance having a chlorosilyl group in a molecule in an alcohol solvent and reacting it on the surface of a substrate such as glass, ceramics, plastic, or metal is dried.
- An undercoat film, that is, a primer layer is formed, and this primer layer.
- a functional thin film such as water repellency, oil repellency, hydrophilicity, and anti-fogging is formed on the substrate to firmly bond the functional thin film to a substrate via a primer layer.
- the efficiency of the formation of silanol groups in the primer layer is improved by applying to the substrate within 30 minutes immediately after mixing the substance having a chlorosilyl group in the molecule and the alcohol solvent. It is illustrated.
- Patent Document 1 JP-A-2-233535
- Patent Document 2 JP 2000-144056 (US Pat. No. 6,403,225)
- Patent Document 3 Japanese Patent Laid-Open No. 2001-026463
- Patent Document 4 JP-A-9 194237
- Patent Document 5 Pamphlet of International Publication 1998Z40323
- a film excellent in water repellency, water slidability and durability by applying a treatment agent without performing a heating step, such that a film can be formed later on an existing vehicle window or the like. It is a first object to provide a treatment agent that can be formed and that can easily remove excess dry solids with functional components that cause functions such as water repellency and water slidability that are not involved in film formation after treatment. And
- a second object of the present invention is to provide a method for producing a water-slidable article that can obtain a water-slidable article that has excellent water-sliding properties and is excellent in muddy water abrasion resistance and light resistance.
- the treating agent for obtaining the water-slidable coating of the present invention has at least two or three hydrolyzable functional groups at one end, and dimethyl Linear polydimethylsiloxane having 30 to 400 siloxane units (Si (CH) O), and
- It has a hydrolyzable functional group and has a fluorocarbon unit (CF or CF).
- a treatment agent comprising a mixture of a fluoroalkylsilane having 2 3 number of 6 to 12 and an organic solvent, an acid, and water is provided.
- This treatment agent is 0.2 to 3.0% by weight of the above-mentioned linear polydimethylsiloxane in a weight concentration with respect to the total amount of the treatment agent.
- Kill silane is mixed in an amount of 0.2 to 2.0% by weight, and the total amount of the linear polydimethylsiloxane and the fluoroalkylsilane is mixed in an amount of 0.5 to 3.5% by weight.
- a method for producing a water-slidable article in which a water-slidable coating is formed on a substrate is provided.
- a solution to which a key compound having four functional groups was added was applied to a base material, and the key compound and the base material were bonded together, and a silanol group derived from the key compound was formed.
- Linear polydimethylsiloxane having an average number of repeating units of 20 to 50 (common logarithm of 1.3 to 1.7), a hydrolyzable functional group, and a fluorocarbon unit
- a treatment agent formed by mixing a solution containing an acid and water is applied to the primer layer and solidified to form a water slidable film.
- first and second problems are solved by the first and second features of the present invention, respectively.
- the first and second features of the present invention may be combined.
- the treatment agent according to the first feature may be used in the method of making the water-slidable article according to the second feature in order to form the water-slidable coating.
- FIG. 1 is a diagram showing a preparation procedure for a treatment agent in Example 1 according to the first aspect of the present invention.
- FIG. 2 is a diagram showing the preparation procedure of the treatment agent and the mixing ratio (weight ratio) of each chemical solution in Example 1 according to the second feature of the present invention.
- the linear polydimethylsiloxane is excellent in lubricity and has a dimethylsiloxane chain. Therefore, the water slidability of the resulting coating is improved. On the other hand, since the fluoroalkylsilane has a fluoroalkyl chain having excellent durability, the durability of the resulting film is improved.
- the linear polydimethylsiloxane has two or three hydrolyzable functional groups at at least one terminal, and the fluoroalkylsilane also has a hydrolyzable functional group.
- the hydrolyzable functional group is hydrolyzed by the acid and water contained in the treating agent to form a highly reactive silanol group.
- the acid and water have an effect of hydrolyzing a hydrolyzable functional group of the linear polydimethylsiloxane or the fluoroalkylsilane to produce a silanol group capable of binding to a substrate.
- the treatment method for obtaining the water-slidable coating of the present invention includes a step of applying a treatment agent to a substrate, a step of drying the substrate coated with the treatment agent, and a coating in a free state after drying. It is characterized by having a step of removing unreacted, hydrolyzed or condensed functional components (hereinafter referred to as “surplus”) that are not involved in the formation.
- surplus unreacted, hydrolyzed or condensed functional components
- the treatment agent for obtaining the water-slidable coating of the present invention exhibits excellent water repellency, water slidability and durability by treating the substrate and then drying it. For this reason, it is optimal as a treating agent for treating base materials that cannot be heat-treated, such as window glass and side mirrors assembled in vehicles. Furthermore, it is easy to remove the surplus after processing, so the work load is small.
- linear polydimethylsiloxane used in the treatment agent of the present invention has 30 to 400 dimethylsiloxane units (Si (CH) 2 O).
- the dimethylsiloxane unit number power of the linear polydimethylsiloxane exceeds 00, the number of hydrolyzable functional groups of the linear polydimethylsiloxane decreases relative to the dimethylsiloxane unit. As a result, the reactivity of polydimethylsiloxane decreases. As a result, the resulting coating is weakly bonded to the substrate, and the light resistance of the coating The muddy water abrasiveness is lowered, and the resulting water-slidable coating is rapidly deteriorated.
- Substrates having a water slidable coating prepared using the treatment agent of the present invention are often used outdoors and are often exposed to sunlight. And since there are many occasions when dust adheres, muddy water is polished when wiping with a rag or wiper during cleaning. Formation of a film with excellent light resistance and muddy water resistance is very important from a practical point of view, and these are particularly important when forming a film on a vehicle window.
- the linear polydimethylsiloxane has two or three hydrolyzable functional groups at at least one end.
- the number of hydrolyzable functional groups at both ends is 1 or less, the reactivity of the polydimethylsiloxane is greatly lowered and the bond with the base material is weakened. This is preferable because the light resistance of the resulting water-slidable film is lowered and the deterioration of the film is accelerated.
- linear polydimethylsiloxane is mixed in an amount of 0.2 to 3.0% by weight based on the total amount of the treating agent.
- perfluoroalkyl silane is used as a functional ingredient as a water repellent, but this is the minimum inclination angle at which 501 water droplets with low sliding properties can slide (hereinafter referred to as the falling angle). Is also 25 ⁇ 27 °.
- the concentration of the linear polydimethylsiloxane with respect to the total amount of the treatment agent is 3.0% by weight or less, the treatment agent can be obtained in consideration of the above points. Wow.
- the above-described removal process is performed in a shorter time. Specifically, the removal process is performed within 3 minutes. Considering this point, the linear polydimethylsiloxane is preferably 2.5% by weight or less based on the total amount of the treating agent.
- polydimethylsiloxane represented by the following general formula [1] is preferably used.
- X 1 and X 2 are each a monovalent hydrolyzable functional group
- a 1 and A 2 are each a divalent hydrocarbon group, one (CH 3) —NH—CO—O —Group ([i] is an integer from 0 to 9) Or oxygen.
- [N] is an integer of 30 to 400 and represents the number of dimethylsiloxane units.
- [a] and [b] are each an integer from 0 to 3, and at least one of [a] or [b] must be 2 or 3.
- a 1 and A 2 of the polydimethylsiloxane represented by the general formula [1] are sites that connect a hydrolyzable functional group and a dimethylsiloxane chain that exhibits water repellency and water slidability. Therefore, when the stability of this part is lowered, the dimethylsiloxane chain easily falls off from the water-slidable film, and the durability of the film is lowered. Therefore, A 1 and A 2 of the polydimethylsiloxane represented by the general formula [1] are preferably a divalent hydrocarbon group or oxygen having excellent stability.
- the fluoroalkylsilane used in the treatment agent of the present invention has a hydrolyzable functional group, and the number of fluorocarbon units (CF or CF) in the molecule is six.
- Fluorocarbon unit (CF or C
- t and U represent integers.
- the light resistance of the coating film obtained is improved in the muddy water abrasion resistance, the coating of the treatment agent is facilitated, and the surplus after drying is facilitated, so that the surplus in the front window of a normal passenger car is achieved. It is important that the number of fluorocarbon units be between 6 and 12 in order to reduce the time required for removal of carbon to 6 minutes or less.
- the fluoroalkylsilane is mixed in an amount of 0.2 to 2.0% by weight with respect to the total amount of the treating agent. If it is less than 0.2% by weight, the light resistance and mud-water polishing resistance are significantly reduced. On the other hand, if it exceeds 2.0% by weight, the sliding property is greatly reduced, and the sliding angle exceeds 20 °. And in order to obtain higher water slidability (falling angle: 18 ° or less) and durability, the mixing amount is preferably 0.5 to 1.6% by weight.
- fluoroalkylsilane examples include a fluoroalkylsilane having a hydrolyzable functional group at one end represented by the following general formula [2] and both ends represented by the following general formula [3].
- a fluoroalkylsilane having a hydrolyzable functional group is preferably used.
- CF 3 (CF 2) m. 1 CH 2 CH 2 Si (CH 3) 3.
- Y 2 and Y 3 are each monovalent Is a hydrolyzable functional group.
- [M] is an integer of 6 to 12, and represents the number of fluorocarbon units.
- [q] and [r] are each an integer of 1 to 3.
- fluoroalkylsilane CF (CF) CHCHSi (OCH), CF (CF) CH2 is a fluoroalkylsilane having a hydrolyzable functional group at one end.
- fluoroalkylsilanes having functional groups include (CH 2 O) SiCH 2 CH 3 (CF 3)
- HCI C1 (CH) SiCHCH (CF) CHCHSi (CH) CI, etc. can be used.
- a fluoroalkylsilane having a hydrolyzable functional group at both ends has a hydrolyzable functional group at both ends, so that the condensation proceeds immediately and therefore a treatment agent is applied. Tend to be difficult. Furthermore, when it becomes surplus, it tends to become a condensed surplus, so that the surplus is firmly fixed to the substrate, and it becomes difficult to remove the surplus after drying. Considering this point, it is preferable to use a fluoroalkylsilane having a hydrolyzable functional group only at one end.
- an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group, a black mouth group, or an isocyanate group may be used. It can.
- the hydrolyzable functional group is too high, the handling of the treatment agent is difficult to handle, and the pot life of the treatment agent is shortened. On the other hand, if the reactivity is too low, the hydrolysis reaction will not proceed sufficiently, and the amount of silanol groups produced will not be sufficient, so the bond between the substrate and the resulting water slidable film will not be sufficient.
- alkoxy groups are preferred as the hydrolyzable functional groups, and methoxy groups and ethoxy groups are particularly preferred.
- the total amount of the functional components is mixed in a concentration of 0.5 to 3.5% by weight with respect to the total amount of the treatment agent. If it is less than 5% by weight, the light resistance and muddy water resistance of the resulting coating will be reduced. On the other hand, if it exceeds 3.5% by weight, the removal of excess will be reduced, and in the removal process of surplus after applying treatment agent and drying, manual wiping with paper towel, cloth, wiper, etc. Time usually exceeds 6 minutes in the front window of a passenger car. In order to further improve the durability of the coating and to facilitate removal of the surplus after coating and drying of the treatment agent, the content is preferably 0.8 to 3.0% by weight.
- the polydimethylsiloxane may have two or three hydrolyzable functional groups at least at one end.
- the hydrolyzable functional group may be provided on one side.
- Those having only terminal ends or those having hydrolyzable functional groups at both ends can be used.
- the other end is an alkyl group having high hydrophobicity, so that the fallability can be further improved.
- the number of silanol groups produced is small and the reactivity is low. For this reason, there is little production of the condensed surplus, and as a result, there is a tendency that it is easy to remove the surplus after application and drying with less production of dried solids firmly fixed to the film. Both will react.
- the amount of the polydimethylsiloxane or the fluoroalkylsilane in the treatment agent is preferable to increase the amount of the polydimethylsiloxane or the fluoroalkylsilane in the treatment agent.
- 5-2 is the total amount of the treatment agent, the mixing amount, the linear polydimethylsiloxane in weight concentration 0.5. 5 wt 0/0, full O b alkyl silane from 0.6 to 1.6 weight 0/0, further, the total amount of functional ingredients from 1.2 to 3. it is preferably 0% by weight.
- the amount of mixing is 0.2 to 2.0% by weight of linear polydimethylsiloxane in terms of weight concentration, and fluoroalkylsilane is the total amount of treatment agent. It is preferable that the content is 0.5 to 1.4% by weight, and the total amount of functional components is 0.8 to 2.5% by weight.
- an organic solvent in which other components (linear polydimethylsiloxane, fluoroalkylsilane, water, acid) are dissolved can be used.
- these include ethyl alcohol, isopropyl alcohol and the like.
- Lower alcohols ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, toluene, benzene and xylene, ethers such as jetyl ether and diisopropyl ether It is preferable to use a kind or a mixture thereof.
- a mixed solvent of at least one solvent selected from methyl ethyl ketone, ethyl acetate, hexane, jetyl ether and diisopropyl ether and a lower alcohol such as ethyl alcohol or isopropyl alcohol is linear polydimethylsiloxane, This is particularly preferable since the solubility of fluoroalkylsilane, water and acid is high, and the coating property of the processing agent (ease of spreading) and the drying time (working time) of the processing agent become appropriate.
- the water used in the treatment agent of the present invention has a molecular number relative to the number of hydrolyzable functional groups of the linear polydimethylsiloxane and the fluoroalkylsilane.
- the acid used for the treating agent plays a catalytic role for promoting the hydrolysis reaction of the functional component, and nitric acid, hydrochloric acid, acetic acid, sulfuric acid, and other organic acids can be used. And it is mixed so that it may become pH value power ⁇ 5, preferably 0-2 in the state mixed with the water.
- the treating agent is composed of the linear polydimethylsiloxane and the fluoroalkyl. It is obtained by hydrolyzing the linear polydimethylsiloxane and the fluoroalkylsilane by adding and mixing water and an acid for causing a hydrolysis reaction to a mixture of rusilane and a solvent.
- the reason why the linear polydimethylsiloxane and the fluoroalkylsilane are mixed first is to uniformly mix both components in the treatment agent.
- acid, water, linear polydimethylsiloxane and fluoroalkylsilane may be mixed at the same time.
- Examples of coating methods for applying the coating solution obtained above onto the substrate surface include hand coating, nozzle flow coating method, dating method, spray method, reverse coating method, flexo method, printing method, flow coating method, spin coating method.
- Various coating formation methods such as a coating method and a combination thereof can be appropriately employed.
- the base material to which the treatment agent is applied is not particularly limited.
- a float plate glass usually used for a window glass for a building or a mirror, or Inorganic transparent plate glass such as soda lime glass manufactured by the peel-out method can be used.
- the plate glass both colorless and colored ones can be used, and the combination with other functional films, the shape of the glass and the like are not particularly limited.
- various types of tempered glass such as air-cooled tempered glass and chemically tempered glass can be used.
- Sarakuko can use various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass.
- the glass substrate can be used as a single plate, and can also be used as a multi-layer glass, a laminated glass, and the like.
- the coating may be formed on one side or both sides of the base material, or may be the entire surface or a part of the base material surface.
- the coating obtained from the treatment agent of the present invention can be used even in applications that do not require visible light transmission, which is excellent in visible light transmission.
- a base material such as may be used.
- the treatment agent of the present invention does not require any particular heating, polycarbonate, polyethylene It is possible to use terephthalate, polymethylmethacrylate, polyethylene, polyvinyl chloride, and other plastic substrates.
- a primer layer derived from the above key compound was formed by applying a solution to which the key compound having four functional groups was added to the base material and then solidifying the base material. May be used.
- the primer layer can increase the number of sites for binding to the coating, that is, the number of silanol groups, as compared with the substrate itself.
- the water-slidable coating formed using the substrate on which the primer layer is formed can be expected to further improve durability.
- the primer layer may be a monomolecular layer.
- Examples of the key compound having four functional groups include tetraisocyanate silane, tetrano, logene silane, tetramethoxysilane, and tetraethoxysilane. And these chemical species are added to a solvent, and the solution for apply
- the solvent include alcohols such as lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol, or general organic solvents such as paraffinic hydrocarbons and aromatic hydrocarbons such as n-hexane and toluene. , Black benzene, etc., or a mixture thereof.
- the chemical species which may be an acid such as hydrochloric acid, nitric acid, or acetic acid. May be.
- the chemical species is used in an amount of 0.5 to 2% by weight, preferably 0.7 to 1.5% by weight, based on the solvent. More preferably, 0.9 wt% to 1.2 wt% is added to prepare the solution.
- a method for applying the coating solution to the surface of the glass substrate known means such as a spray coating method, a bar coating method, a roll coating method, a spin coating method, a brush coating method, or a dip coating method may be used. it can.
- a spray coating method a bar coating method, a roll coating method, a spin coating method, a brush coating method, or a dip coating method
- the solution may be baked at 50 ° C to 350 ° C, preferably 100 ° C to 300 ° C, after being applied to the substrate. Then, immediately after the formation of the primer layer, the treatment agent of the present invention may be applied to form a water slidable film. Also, a substrate on which a primer layer is formed When the treatment agent of the present invention is applied to a substrate after storage, distribution, etc., the silanol groups on the primer layer may disappear due to the influence of organic matter, moisture present in the atmosphere, etc. Since this may occur, it is preferable to restore the silanol group by bringing the deactivated primer layer into contact with the acidic solution or irradiating with ultraviolet rays, and to make the primer layer active again.
- the polydimethylsiloxane and the fluoroalkylsilane are bonded to the substrate by applying a treatment agent to the substrate and then drying it.
- the drying means is simply air-dried at room temperature, for example, in an environment of 15 ° C. to 30 ° C. and a relative humidity of 30% to 60%.
- heating may be performed at 80 ° C. to 250 ° C. in an environment where the base material can be heated by blowing hot air with a general-purpose dryer or the like.
- the sliding property in the first and second characteristics of the present invention is evaluated by a method as described in the evaluation method of the example. After dropping 50 1 pure water on the sample surface, This sample is evaluated by gradually tilting the sample and measuring the tilt angle when the water droplet starts to move. The tilt angle was defined as the falling angle (°), and the falling angle was measured in the atmosphere (about 25 ° C) using CA-A type manufactured by Kyowa Interface Science.
- the angle formed between the water droplet and the sample surface when pure water of about 21 was placed on the sample surface having the water slidable coating was measured with a contact angle meter.
- the contact angle meter was CA-X type manufactured by Kyowa Interface Science, and measured in the atmosphere (about 25 ° C).
- the tilt angle at the time when the water droplet started to move was defined as the tumbling angle (°).
- the sliding angle was measured in the atmosphere (about 25 ° C) using Kyowa Interface Science CA-A type. When the initial performance of the sliding angle is 20 ° or less, it is acceptable (indicated in the table 1 or 2) as the slipperiness index, and when it is 18 ° or less, it is particularly excellent (in Table 1 or 2). (Indicated as ⁇ ). In addition, those exceeding 20 ° were rejected and indicated as X in Table 1 or Table 2.
- Glass polishing agent Mireku A (manufactured by Mitsui Mining and Smelting) with a cotton cloth impregnated ceria suspension prepared by dispersing in tap water (10 wt%), a sample surface of about 1. 5 kg / cm 2 intensity Well polished. The number of polishing times (reciprocation) until 70% of the polishing area became hydrophilic was evaluated.
- pass 40 times or more (indicated in Table 1 or 2 in Table 2), pass 50 or more in good (indicated in Table 1 or 2), excellent in 60 or more (Table 1 or 2) (Indicated as ⁇ +). Those less than 40 times were rejected and indicated as X in Table 1 or Table 2.
- the sample was evaluated by measuring the contact angle (°) after irradiating the sample with the powerful UV light of a metalno or ride lamp for 2 hours under the following conditions.
- the contact angle of water drops after the test passed 70 ° or more (shown as ⁇ in Table 1), 80 ° or more was good (shown as ⁇ in Table 1 or Table 2), and 100 ° or more was excellent (table) 1 or in Table 2).
- those less than 70 ° were rejected and indicated as X in Table 1.
- ⁇ Lamp MO 15—L312 from Eye Graphics
- UV intensity meter Minolta, UM-10
- the substrate coated with the water-slidable coating treated with the treatment agent of the present invention is often used outdoors and exposed to sunlight. Also, since dust easily adheres, the surface is polished by dust or wiping wipes when cleaning, raising or lowering the glass when used for vehicle glass, and dry or dust containing water when wiping wipers. Considering this, it is important to improve the light resistance and muddy water polishability to extend the life of the coating.
- the treating agent was obtained by adding an acidic aqueous solution to a mixture obtained by mixing linear polydimethylsiloxane and fluoroalkylsilane and stirring the mixture.
- Figure 1 shows the procedure for preparing treatment agents and the mixing ratio (weight ratio) of each chemical solution.
- Table 1 shows the sample preparation conditions and the results of the evaluation.
- the weight concentration of the linear polydimethylsiloxane mixed (hereinafter referred to as “polydimethylsiloxane concentration”) is 0.5% by weight with respect to the total amount of the processing agent.
- the weight concentration of the mixed fluoroalkyl silane (hereinafter referred to as “fluoroalkyl silane concentration”) is 0.8% by weight. A treating agent was obtained.
- the surface of 300 mm X 300 mm X 2 mm thick float glass or the front window of an ordinary automobile was polished with a polishing liquid, washed with water and dried.
- the polishing liquid used here was a 2 wt% ceria suspension prepared by mixing glass abrasive Mille A (T) (Mitsui Metal Mining) with water.
- Fluoroalkylsilane with 10 fluorocarbon units (CF (CF) CH CH
- Fluoroalkylsilane with 6 fluorocarbon units (CF (CF) CH CH
- Example 2 The same as Example 1 except that the polydimethylsiloxane concentration was 1.3% by weight.
- the polydimethylsiloxane concentration is 1.0% by weight and the fluoroalkylsilane concentration is 1.6% by weight, that is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is the total amount of processing agent. 2. All were the same as Example 6 except 6 wt%.
- Example 6 The same as Example 6 except that the polydimethylsiloxane concentration was 2.5% by weight.
- the physical properties were good as shown in Table 1.
- the initial drop angle is 13 °, which indicates good drop dropability.
- 45 reciprocations are required to make 70% hydrophilic, and in the light resistance test, the contact angle after irradiation for 2 hours is 82 °. Excellent durability.
- Example 2 All were the same as Example 1 except that the polydimethylsiloxane concentration was 0.25% by weight.
- the polydimethylsiloxane concentration is 1.0% by weight and the fluoroalkylsilane concentration is 1.6% by weight, that is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is the total amount of processing agent. 2. All were the same as Example 1 except 6% by weight.
- the polydimethylsiloxane concentration is 0.25% by weight and the fluoroalkylsilane concentration is 0.4% by weight. That is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is the total amount of treating agent. All were the same as Example 1 except for 0.6 wt%.
- Example 2 The procedure was the same as Example 1 except that a substrate having a primer layer formed thereon was used. The method for forming the primer layer on the base material is described next.
- a solution to which 1.0% by weight of tetraisocyanate silane was added was obtained.
- the solution was soaked in a cotton cloth (trade name: Bencott), and the glass substrate that had been ceria-polished with the cotton cloth was wiped off so as not to be applied twice. Then, after drying for about 5 minutes at room temperature, heat treatment is performed in a furnace at 180 ° C for 13 minutes (plate temperature 150 ° C when discharged from the furnace) to obtain a glass substrate with a silica film primer layer formed. It was.
- Example 1 Thereafter, the treatment agent was applied and wiped off in the same manner as in Example 1 to obtain a transparent sample.
- the removability of the excess was good.
- the initial drop angle is 20 °, which indicates good drop dropability.
- 70 reciprocations are required to make the 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is Durability was as high as 108 °.
- Table 2 shows the preparation conditions of the sample formed using the base material on which the primer layer was formed and the evaluation result of the resulting product.
- Example 18 is the same as Example 18 except that the heat treatment for obtaining the primer layer was carried out at 300 ° C for 13 minutes (plate temperature at furnace exit: 250 ° C). The results show that the initial drop angle is 17 °, which is a good drop drop property. In the ceria polishing test, it takes 75 reciprocations to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation is Excellent durability with a high 102 °.
- Example 18 After forming the primer layer, it was left in the atmosphere for 3 hours. Otherwise, this is the same as Example 18.
- the results show that the initial drop angle is 18 °, which is a good drop drop property.In the ceria polishing test, it takes 65 reciprocations to hydrophilize 70%, and in the light resistance test, the contact angle after 2 hours of irradiation. However, the durability was as high as 108 °.
- Example 18 After forming the primer layer, it was left in the atmosphere for 4 days. Thereafter, the substrate was immersed in 0.5 N nitric acid for 2 hours. Otherwise, this is the same as Example 18. As a result, it took 65 reciprocations to make 70% hydrophilic in the ceria polishing test, and in the light resistance test, the contact angle after irradiation for 2 hours was 106 ° and the durability was excellent.
- Example 18 After forming the primer layer, it was left in the atmosphere for 4 days. Thereafter, UV irradiation was performed using a corona discharge device. Otherwise, this is the same as Example 18. As a result, 65 reciprocations were required to make 70% hydrophilic in the ceria polishing test, and in the light resistance test, the contact angle after 2 h irradiation was high at 98 ° and the durability was excellent.
- Example 18 is the same as Example 18 except that CH 2)] is used. The result is a very good fall angle of 15 °.
- Example 18 was the same as Example 18 except that the heat treatment after application of the solution for obtaining the primer layer was not performed. As a result, in the ceria polishing test, the number of times until 70% hydrophilicity was achieved was 45 round trips. The result was almost the same as in Example 1 where the primer layer was not formed.
- Example 18 was the same as Example 18 except that the heat treatment after the primer application was performed at 70 ° C for 13 minutes (plate temperature at furnace exit: 50 ° C). As a result, in the ceria polishing test, the number of times until 70% hydrophilicity was achieved was 55 round trips.
- Example 18 In order to obtain a primer layer, the same procedure as in Example 18 was carried out except that the amount of tetraisocyanate silane added to the coating solution was 0.5% by weight. As a result, in the ceria polishing test, the number of times until 70% hydrophilicity was achieved was 40 round trips.
- Example 18 After forming the primer layer, it was left in the atmosphere for 4 days. Otherwise, this is the same as Example 18. As a result, in the ceria polishing test, it was 50 reciprocations to make 70% hydrophilic, and in the light resistance test, the contact angle after 2 h irradiation was 90 °.
- Example 1 The same as Example 1 except that the fluoroalkylsilane concentration was 2.5% by weight. [0129] As a result, as shown in Table 1, the initial falling angle was 25 ° and the water droplet falling property was low.
- Fluoroalkylsilane with 1 fluorocarbon unit CF CH CH Si (OC
- Example 2 The same as Example 1 except that the polydimethylsiloxane concentration was 3.5% by weight.
- Example 2 The same as Example 1 except that the polydimethylsiloxane concentration was 0.1% by weight.
- the polydimethylsiloxane concentration is 2.0% by weight, and the fluoroalkylsilane concentration is 2.0% by weight. That is, the total amount of linear polydimethylsiloxane and fluoroalkylsilane is the total amount of treating agent. 4. All were the same as Example 1 except 0% by weight.
- Polydimethylsiloxane concentration is 0.2 wt%
- fluoroalkylsilane concentration is 0.2 All the same as Example 1 except that the total amount of linear polydimethylsiloxane and fluoroalkylsilane was 0.4% by weight with respect to the total amount of the processing agent.
- Example 2 The same as Example 1 except that a trimethyl-blocked linear polydimethylsiloxane (CH ⁇ Si (CH) O ⁇ Si (CH)) having 250 dimethylsiloxane units was used.
- a trimethyl-blocked linear polydimethylsiloxane CH ⁇ Si (CH) O ⁇ Si (CH)
- the solidification according to the second feature of the present invention described in the summary of the invention means that the applied treatment agent is dried and the primer layer and the linear polydimethylsiloxane or the fluoroalkylsilane are mixed. It means that it is combined scientifically.
- the linear polydimethylsiloxane mainly imparts water slidability to the article, and the difference in chemical species greatly affects the characteristics of the article.
- the article when the water-slidable article is applied to a window glass or a side glass for a vehicle, even in an environment where water comes into contact with the article, the article has a water-sliding property that reduces adverse effects on visibility through the article. In other words, it is an object to obtain an article having a sliding property with a falling angle of 15 ° or less.
- the hydrolyzable group at the end is formed in another chemical species, in the case of the present invention, in the primer layer. Since the silanol group and the linear polydimethylsiloxane are chemically bonded, they are provided to improve the durability of the product. Then, when the hydrolyzable group at the end is only on one side of the linear polydimethylsiloxane, the number of hydrolyzable functional groups is at least 2, and the adhesiveness between the film and the primer layer is taken into consideration, it should be 3 to 9. It is even more preferable to have 4 to 9, and so on.
- the average number of repeating units of dimethylsiloxane units (Si (CH) O) is 20 to 50 (normally
- linear polydimethylsiloxane a fluoroalkylsilane having a hydrolyzable functional group and having 1 to 12 fluorocarbon units (CF or CF)
- CF or CF fluorocarbon units
- a treatment agent which is a mixture of organic solvent, acid, and water, onto the primer layer on which silanol groups are formed and solidifying it to form a coating film, water and water repellency, mud resistance
- a treatment agent which is a mixture of organic solvent, acid, and water
- the fluoroalkylsilane contributes to the improvement of the water repellency and mud-water polishing property of the coating, it has a hydrolyzable functional group, so that the silanol group formed in the primer layer, Alternatively, a chemical bond is formed with the linear polydimethylsiloxane.
- the fluoroalkylsilane has a hydrolyzable functional group, and the molecule has 1 to 12 perfluorocarbon units (CF or CF) in the molecule.
- the light resistance of the water-slidable article is improved in the muddy water abrasion resistance.
- t and U represent integers.
- the number of fluorocarbon units increases, the freezing point of the fluoroalkylsilane increases to room temperature or higher, which makes it difficult to apply the treatment agent containing the fluoroalkylsilane. Therefore, it is not preferable. Therefore, the light resistance of the coating film obtained is improved, the mud water polishing property is improved, the coating of the treatment agent on the base material is facilitated, and further, a component that does not form a coating film from the dried film, that is, In order to make it easier to remove the surplus, the number of fluorocarbon units should be 1 to 12, improving the muddy water polishability of the coating. In order to make it 6 to 12, it is preferable.
- the durability of the water-slidable article such as the mud water resistance and light resistance is also affected by the adhesion between the substrate and the coating.
- a solution in which a key compound having four functional groups is added on a base material is applied to the base material, the key compound and the base material are bonded, and the silanol derived from the key compound is combined. Since the groups are formed, the number of silanol groups can be increased from the base material. Therefore, the number of bonding sites with the linear polydimethylsiloxane and the fluoroalkylsilane can be increased. As a result, the adhesion between the coating and the substrate is improved, and the muddy water abrasion resistance and light resistance of the water-slidable article can be improved.
- the primer layer is preferably a monomolecular layer.
- the bond between the silicon compound and the substrate may be performed in a room temperature of 10 ° C to 40 ° C or an environment close to room temperature after the solution is applied to the substrate.
- the primer layer may be formed by heating at 50 ° C to 350 ° C. By performing the heating, the binding time can be shortened, the surface of the primer layer is less affected by external force stains, lint, and moisture, and it is easy to generate silanol groups.
- the key compound having four functional groups for forming the primer layer is preferably a tetrisocyanate silane. Since the chemical species is highly reactive, it is possible to reliably form a siloxane bond with the silanol group on the substrate.
- the number of hydrolyzable functional groups of the linear polydimethylsiloxane should be 4 to 9 so that the bond with the silanol group of the primer layer can be increased. Is preferred.
- the linear polydimethylsiloxane preferably has the following structural formula:
- n represents the average number of repeating dimethylsiloxane units.
- X represents a hydrolyzable functional group, h and i are integers from 0 to 3, and j is an integer from 1 to 3. However, when i is 0, h is 2 or 3. The sum of h and i is an integer of 3 or less. For example, if i and j are 3, nine hydrolyzable functional groups can be provided at one end of the linear dimethylsiloxane.
- the method for producing a water-slidable article by the above method has a water-sliding property that reduces adverse effects on the visibility through the article even in an environment where the article is in contact with water, and is resistant to muddy water polishing.
- a water-slidable article excellent in light resistance and to provide a water-slidable article excellent in various performances as described above at low cost.
- the method for producing a water-slidable article of the second feature of the present invention makes it easy to form a water-slidable film.
- the resulting article has excellent water slidability, and has such effects as excellent durability such as muddy water abrasion resistance and light resistance.
- a solution to which a key compound having four functional groups is added is applied to a base material, the key compound and the base material are bonded, and the key A step of forming a primer layer in which silanol groups derived from an element compound are formed, having at least 3 functional groups that can be hydrolyzed only at one end, and dimethylsiloxane units (Si (CH
- It is characterized by comprising a step of forming a water-slidable film by applying a treatment agent obtained by mixing a solution containing a solvent, an acid, and water to the primer layer and solidifying it.
- tetraisocyanate silane As the key compound having four functional groups, tetraisocyanate silane, tetrano, logene silane, tetramethoxysilane, tetraethoxysilane and the like can be used. These Among them, it is preferable to use tetraisocyanate silane, tetrahalogenated silane, particularly tetraisocyanate silane having a high hydrolysis rate.
- the chemical species are added to a solvent to prepare a solution to be applied to the surface of the substrate.
- the solvent include alcohols, for example, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol, acetones such as acetone and methyl ethyl ketone, ethers such as ethyl ether and ethyl acetate, esters, Alternatively, general organic solvents such as norafine hydrocarbons and aromatic hydrocarbons, such as n-hexane, toluene, black benzene, etc., or a mixture thereof can be used.
- the chemical species which may be an acid such as hydrochloric acid, nitric acid, and acetic acid. May be.
- the chemical species is 0.5% to 2% by weight, preferably 0.7% to 1.5% by weight, and more preferably based on the solvent. It is preferable to add 0.9 wt% to 1.2 wt% to prepare the solution.
- the solution may be fired at 50 ° C to 350 ° C, preferably 100 ° C to 300 ° C after application to the base material. preferable. Then, immediately after the formation of the primer layer, the treatment agent of the present invention may be applied to form a water-slidable film. Further, when the treatment agent of the present invention is applied to the base material after the base material on which the primer layer is formed is stored and distributed, silanol groups on the primer layer are present in organic matter or in the atmosphere such as moisture.
- the silanol group may be revived by bringing the deactivated primer layer into contact with an acidic solution or by irradiating with ultraviolet rays, and the primer layer may be activated again. I like it.
- Examples of the functional group capable of hydrolyzing the linear dimethylsiloxane or fluoroalkylsilane include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Or an alkoxy group, an isocyanate group, or the like can be used.
- the hydrolyzable functional group is too high, the pot life of the treating agent is shortened just because it becomes difficult to handle when preparing the treating agent.
- the hydrolysis reaction will not proceed sufficiently and the amount of silanol groups produced will not be sufficient, so that the bonding between the primer layer and the film will not be sufficient.
- pot life of the treatment agent and durability of the resulting water slidable coating film methoxy and ethoxy groups are particularly preferred among the hydrolyzable functional groups, although alkoxy groups are preferred.
- fluoroalkylsilane examples include a fluoroalkylsilane having a hydrolyzable functional group at one end represented by the following general formula [2] and both ends represented by the following general formula [3].
- a fluoroalkylsilane having a hydrolyzable functional group is preferably used.
- CF 3 (CF 2) m. 1 CH 2 CH 2 Si (CH 3) 3.
- fluoroalkylsilane those exemplified in the first feature of the present invention can be used as the fluoroalkylsilane having a hydrolyzable functional group at one end.
- fluoroalkylsilane having a hydrolyzable functional group at both ends those exemplified in the first feature of the present invention can be used.
- fluoroalkylsilanes having hydrolyzable functional groups at both ends are Because of having a hydrolyzable functional group at the side end, the condensation tends to proceed and this tends to make it difficult to apply the treatment agent. In addition, when it becomes a surplus that is not bonded to the base material after it has been formed into a film, it may adhere firmly to the article as a condensed surplus and it may be difficult to remove the surplus after drying. Considering this point, it is preferable to use a fluoroalkylsilane having a hydrolyzable functional group only at one end.
- the linear polydimethylsiloxane is 0.2 to 3.0% by weight, preferably in a weight concentration with respect to the total amount of the treating agent.
- the phenolic silane is 0.2 wt% to 2.0 wt%, preferably 0 wt%.
- the treating agent is a mixture of an organic solvent, an acid, and water.
- the organic solvent includes functional components, that is, linear polydimethylsiloxane and fluoroalkylsilane, and And organic solvents that dissolve acid can be used. These include lower alcohols such as ethyl alcohol and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate and the like.
- esters hydrocarbon solvents such as hexane, toluene, benzene and xylene, ethers such as jetyl ether and diisopropyl ether, and mixtures thereof are preferably used.
- a mixed solvent of at least one solvent selected from methyl ethyl ketone, ethyl acetate, hexane, jetyl ether, and diisopropyl ether and a lower alcohol such as ethyl alcohol or isopropyl alcohol is linear polydimethylsiloxane, fluorine. This is particularly preferable since the solubility of chloroalkylsilane, water and acid is high, and the coating property of the treatment agent becomes appropriate.
- the water used in the treatment agent of the present invention has a molecular number relative to the number of hydrolyzable functional groups of the linear polydimethylsiloxane and the fluoroalkylsilane.
- the acid used in the treating agent plays a catalytic role in promoting the hydrolysis reaction of functional components, that is, linear polydimethylsiloxane and fluoroalkylsilane, and includes nitric acid, hydrochloric acid, acetic acid, sulfuric acid, Other organic acids can be used. Then, the mixture is mixed so that the pH value is 0 to 5, preferably 0 to 2, in the state of being mixed with the water. In such an acidic region, when the acid used is a strong acid, the reaction rate of the functional component, that is, the linear polydimethylsiloxane and the fluoroalkylsilane increases, resulting in a short pot life of the treatment agent. Become. On the other hand, a weak acid is not preferable because hydrolysis of functional components, that is, linear polydimethylsiloxane and fluoroalkylsilane does not proceed sufficiently.
- the substrate used in the method for producing a water-slidable article of the present invention is not particularly limited.
- the substrate exemplified in the first feature of the present invention can be used.
- the measurement was performed by the same method as the first feature of the present invention.
- the measurement was performed by the same method as the first feature of the present invention.
- Polishing was performed by the same method as the first feature of the present invention. The number of times of polishing (reciprocation) until 70% of the polished area became hydrophilic was evaluated. In this test, if it was 40 times or more, it was considered to be practically durable, 40 times or more was acceptable, and 45 times or more was non-defective.
- the sample was evaluated by measuring the contact angle (°) after irradiating the sample with the powerful UV light of a metal halide lamp for 2 hours under the following conditions. After irradiation, those with a contact angle of 95 ° or more are considered to have excellent durability.
- This light resistance test was performed under the same conditions as the weather resistance test in the first feature of the present invention.
- the water-slidable article according to the second feature of the present invention is exposed to sunlight, which is often used outdoors. In addition, since dust easily adheres, the surface is often polished by wiping off dust when cleaning, raising or lowering the glass when used for vehicle glass, and dry or wet dust when wiping the wiper. . Considering this, light resistance and muddy water abrasion resistance are important indicators when considering the practical use of water-slidable articles.
- the treating agent was obtained by adding an acidic aqueous solution to a mixture obtained by mixing linear polydimethylsiloxane and fluoroalkylsilane and stirring the mixture.
- Figure 2 shows the preparation procedure and the mixing ratio (weight ratio) of each chemical solution.
- the number of dimethylsiloxane units is 30 (the common logarithm is 1.5), and a linear polydimethylsiloxane [(CH) SiCH with nine methoxy groups only on one end via a branched structure.
- polydimethylsiloxane concentration the weight concentration of mixed linear polydimethylsiloxane (hereinafter referred to as “polydimethylsiloxane concentration”) is 2.0% by weight with respect to the total amount of the processing agent, A treating agent having a weight concentration of mixed fluoroalkylsilane (hereinafter referred to as “fluoroalkylsilane concentration”) of 0.8% by weight was obtained.
- a float glass of 300 mm X 300 mm X 2 mm thickness was polished with a polishing liquid, washed with water and dried.
- the polishing liquid used here was a 2% by weight ceria suspension obtained by mixing glass abrasive Mille A (T) (manufactured by Mitsui Metal Mining) with water.
- a water-slidable article was obtained by the same procedure as in 1. The results are shown in Table 3. It always shows a good value, it is a good product that requires 50 reciprocations to make 70% hydrophilic in the ceria polishing test, and in the light resistance test it has excellent durability with a contact angle of 97 ° after 2 h irradiation It was.
- a water-slidable article was obtained in the same procedure as in Example 1 except that the primer layer was not formed. As shown in Table 3, the contact angle was 110 ° and the sliding angle was 13 °, but in the ceria polishing test, it was 35 reciprocations to hydrophilize 70%, and in the light resistance test, contact after 2h irradiation. The angle was 70 ° and the durability was poor.
- a water-slidable article was obtained in the same procedure as in Example 2 except that the primer layer was not formed. As shown in Table 3, the contact angle was 109 ° and the sliding angle was 12 °. However, in the ceria polishing test, it was 30 reciprocations to hydrophilize 70%, and in the light resistance test, contact after 2h irradiation. The angle was 78 ° and the durability was poor.
- a straight-chain polydimethylsiloxane is mixed with a trialkoxy-type straight-chain polydimethylsiloxane [(CH 2 O) Si] having both ends at 250 dimethylsiloxane units (2.4 in common logarithm).
- a water-slidable article was obtained by the same procedure as described above. The results are shown in Table 3.
- the contact angle was 112 °, in the abrasive polishing test it was 70 reciprocations to hydrophilize 70%, and in the light resistance test, the contact angle after 2h irradiation was 108 °. Was as strong as 19 °.
- the acidity of pHO to 4 is applied to the primer layer after the primer layer is formed. Any treatment selected from the group of solution contact, corona discharge, and ultraviolet irradiation may be performed. Hereinafter, this process is referred to as a primer layer process.
- this primer layer treatment by performing any of the above treatments on the primer layer, it is ensured that a silanol group is present in the primer layer, that is, an active state. can do. Even if the number of silanol groups decreases due to the adsorption of methane or carbon dioxide in the atmosphere or the influence of water, lint, etc., the primer layer is formed. Thereafter, the primer layer is reactivated by performing any of the above treatments before the formation of the water slidable coating.
- the primer layer can always be activated by the primer layer treatment, the water-slidable coating can be stably formed with high adhesion to the substrate. This greatly contributes to the stable production of water-slidable articles.
- the above treatment is preferably performed immediately before the formation of the water-slidable film.
- Performing the above treatment in any state of the primer layer contributes to leveling of the production of the water-slidable article.
- the above treatment is preferably performed only when the silanol group of the primer layer disappears, that is, when the primer layer is deactivated.
- the production method is carried out by a method that does not carry out the above treatment. If the above treatment is applied only to the primer layer that has been deactivated due to adsorption of methane or carbon dioxide gas during production or water or lint in the atmosphere, loss of the substrate This is preferable because production efficiency can be improved.
- silanol groups on the surface of the primer layer can always be present, so that the water-slidable film can be stably formed with high adhesion to the substrate. This greatly contributes to the stable production of water slidable articles.
- the primer layer is formed by, for example, applying a solution to which a key compound having four functional groups is added to a base material to bond the key compound and the base material, and It is obtained by forming a silanol group derived from a compound.
- the primer layer [base 1 Si-OH; in this case, -Si OH Is a primer layer, and the remaining Si bond is an OH group or forms an O—Si bond].
- the primer layer is preferably a monomolecular layer.
- the bonding between the silicon compound and the substrate may be performed in a room temperature of 10 ° C to 40 ° C or an environment close to room temperature after the solution is applied to the substrate.
- the primer layer can be formed by heating at 50 ° C to 350 ° C. Good. By performing the heating, the binding time is shortened, and the surface of the primer layer is less affected by dirt, methane and carbon dioxide adsorbed by external force, lint and moisture, and silanol groups are generated. Prefer, easy ,.
- tetraisocyanate silane As the key compound having four functional groups, tetraisocyanate silane, tetrano, logene silane, tetramethoxysilane, tetraethoxysilane and the like can be used. Among these, it is preferable to use tetraisocyanate silane, tetrahalogenated silane, particularly tetraisocyanate silane having a high hydrolysis rate. Tetraisocyanate silane is excellent in the formation of a single layer of the primer, the solution preparation, and the number of silanol groups formed.
- the chemical species is added to a solvent to prepare a solution for application to the surface of the substrate.
- the solvent the solvent exemplified in the second feature of the present invention can be used.
- the chemical species In order to adjust the pH of the solution to 0 to 5, a small amount of water is introduced to accelerate the hydrolysis reaction of the chemical species, which may be introduced with an acid such as hydrochloric acid, nitric acid, and acetic acid. May be.
- the chemical species In order to efficiently form the primer layer, the chemical species is 0.5% to 2% by weight, preferably 0.7% to 1.5% by weight, and more preferably based on the solvent. It is preferable to add 0.9 wt% to 1.2 wt% to prepare the solution.
- a method for applying the coating solution to the surface of the glass substrate known means such as hand coating, brush coating, spray coating method, bar coating method, roll coating method, dip coating method, spin coating method, and the like can be used. Can be used. These methods have low man-hours and high productivity.
- the solution is applied to the substrate after the application.
- Baking is preferably performed at ° C to 350 ° C, preferably 100 ° C to 300 ° C.
- the primer layer is contacted with an acidic solution of pHO to 4, ultraviolet irradiation, , Do any processing.
- the acidic solution having pHO to 4 can be contacted by means of, for example, immersing the base material on which the primer layer is formed in the acidic solution.
- the acid used here is hydrochloric acid, sulfuric acid, nitric acid, or the like, and the pH value of the acidic solution is set to 0 to 4 in order to ensure the presence of silanol groups on the primer layer. There must be.
- the interval is preferably 1 minute to 2 hours, and the substrate or primer layer is preferably washed with water after the contact.
- Irradiation with ultraviolet rays can be performed by means such as irradiating the substrate on which the primer layer is formed directly with ultraviolet rays having an intensity of 0.01 W to 1 W.
- a metal halide lamp, a mercury lamp, or the like is used as the light source used here.
- the irradiation time is preferably 3 seconds to 30 minutes. Further, after irradiation with ultraviolet rays, the substrate or primer layer can be washed with water or the like.
- the corona discharge can be performed by means such as discharging the base material on which the primer layer is formed so as to be sandwiched between a grounded wire and an electrode. It is desirable that the output of the oscillator used here is 0.1 lkW to 4kW. In order to activate the silanol group on the primer layer, the treatment time is preferably about 1 to 10 seconds.
- any treatment selected from the group consisting of contact with an acidic solution of pHO to 4, corona discharge, and ultraviolet irradiation may be carried out even if the silanol group has disappeared, that is, the primer layer has been deactivated. It is also possible to reactivate the group, so that even if the primer layer is deactivated by adsorption of atmospheric methane or carbon dioxide gas, water, lint, etc., the primer layer may be activated again. Is possible. Accordingly, it is possible to reduce the waste of the base material.
- the water-slidable film formed by the method for producing a water-slidable article of the present invention undergoes a condensation reaction with a silanol group in the primer layer at the time of film formation so that the water-slidable film is firmly bonded to the substrate via the primer layer.
- the water-slidable article having a water-repellent coating was measured by the same method as the first feature of the present invention.
- Polishing was performed by the same method as the first feature of the present invention. The number of times of polishing (reciprocation) until 70% of the polished area became hydrophilic was evaluated. In this test, if it was 60 times or more, the article was excellent in durability.
- the sample was evaluated by measuring the contact angle (°) after irradiating the sample with the powerful UV light of a metal halide lamp for 2 hours under the following conditions.
- This light resistance test was performed under the same conditions as the weather resistance test in the first feature of the present invention. In this test, an article with a contact angle of 95 ° or more after the test was an article with high light resistance.
- the glass substrate was cleaned by the same method as in the second feature of the present invention.
- a glass substrate on which a primer layer was formed was obtained in the same manner as in the second aspect of the present invention.
- the glass substrate on which the primer layer was formed was left in the air in the laboratory for 4 days to deactivate the primer layer. Then, the primer layer was reactivated by immersing it in a 0.5N nitric acid aqueous solution for 1 hour.
- the coating solution was obtained by adding an acidic aqueous solution to a mixture obtained by mixing linear polydimethylsiloxane and fluoroalkylsilane and stirring the mixture.
- Fluoroalkylsilane having a number of 8 [CF (CF) CH CH i (OCH)]; 0.80 g
- Pill alcohol 48. 85 g was mixed and stirred for about 5 minutes. Then 0.5N aqueous nitric acid solution; 1. Og was added and stirred for about 2 hours at room temperature. The coating liquid was obtained by the above method. [0226] 5. Formation of water-repellent coating
- Example 1 was the same as Example 1 except that corona discharge was used as a method for reactivating the primer layer.
- corona discharge a corona discharge treatment machine manufactured by Sink Engineering Co., Ltd. was used.
- the corona output was 0.4kw
- the distance between the wire and the glass surface was 2 to 2.5mm
- 300 X 300mm was applied for 20 minutes.
- the contact angle was 108 °, indicating good water repellency
- 65 reciprocations were required to hydrophilize 70%.
- the contact angle after irradiation for 2 hours was as high as 98 °, indicating excellent durability.
- Example 2 Same as Example 1 except that UV irradiation was used for the primer layer reactivation method. .
- a mercury lamp was used as the light source, and when the primer layer was reached, ultraviolet light with an intensity of 128 mW was irradiated for 25 minutes.
- the contact angle was as good as 106 °, and in the ceria polishing test, it took 65 reciprocations to make 70% hydrophilic, Furthermore, in the light resistance test, the contact angle after 2h irradiation was as high as 97 ° and the durability was excellent.
- Example 1 was the same as Example 1 except that the primer layer was not left and the primer layer was not regenerated.
- the comparative example is an example showing a conventional method for forming a water-slidable coating immediately after the primer layer is formed.
- the contact angle was 109 °, 70% in the ceria polishing test to make 70% hydrophilic, and the contact angle after 2h irradiation in the light resistance test was 100 °.
- Example 1 was the same as Example 1 except that the primer layer was not reactivated.
- the contact angle was less than 99 ° and 100 °, and in the ceria polishing test, 45 reciprocations were made to make 70% hydrophilic, and light resistance was further improved.
- the contact angle after 2h irradiation was 90 ° and the durability was poor.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05767109A EP1792963A4 (en) | 2004-08-27 | 2005-08-01 | TREATMENT AGENTS AND METHOD FOR PRODUCING FILMS WITH GOOD ROLLING BEHAVIOR OF WATER DROPS |
US11/630,687 US20080026163A1 (en) | 2004-08-27 | 2005-08-01 | Treatment For Forming Waterdrop Slidable Films And Process For Forming Waterdrop Slidable Films |
KR1020077003343A KR100894079B1 (ko) | 2004-08-27 | 2005-08-01 | 활수성 피막을 얻기 위한 처리제 및 활수성 피막의 제조방법 |
CN200580025049.1A CN101098945B (zh) | 2004-08-27 | 2005-08-01 | 用于得到滑水性被膜的处理剂及滑水性被膜的制作方法 |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004247756 | 2004-08-27 | ||
JP2004-247756 | 2004-08-27 | ||
JP2005-043682 | 2005-02-21 | ||
JP2005043682 | 2005-02-21 | ||
JP2005109348A JP4876424B2 (ja) | 2005-04-06 | 2005-04-06 | 滑水性物品の製法 |
JP2005-109348 | 2005-04-06 | ||
JP2005127385A JP2006306631A (ja) | 2005-04-26 | 2005-04-26 | 機能性物品の製法及びプライマー層の再活性化方法 |
JP2005-127385 | 2005-04-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006022118A1 true WO2006022118A1 (ja) | 2006-03-02 |
Family
ID=35967337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/014033 WO2006022118A1 (ja) | 2004-08-27 | 2005-08-01 | 滑水性被膜を得るための処理剤及び滑水性被膜の作製法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080026163A1 (ja) |
EP (1) | EP1792963A4 (ja) |
KR (1) | KR100894079B1 (ja) |
CN (1) | CN101098945B (ja) |
TW (1) | TW200617152A (ja) |
WO (1) | WO2006022118A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007119630A1 (en) * | 2006-03-30 | 2007-10-25 | Fujifilm Corporation | Planing coat and method for producing the same |
CN100429009C (zh) * | 2006-09-27 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | 一种可在多种基材表面形成疏水透明薄膜的方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8411766B2 (en) * | 2008-04-09 | 2013-04-02 | Wi-Lan, Inc. | System and method for utilizing spectral resources in wireless communications |
JP5083342B2 (ja) * | 2010-02-25 | 2012-11-28 | トヨタ自動車株式会社 | 内燃機関用構成部材、及び撥水撥油性被膜の形成方法 |
JP2015205973A (ja) * | 2014-04-18 | 2015-11-19 | キヤノンファインテック株式会社 | 撥水撥油性組成物、及びそれを用いて形成した撥水膜 |
WO2016052495A1 (ja) * | 2014-10-03 | 2016-04-07 | 住友化学株式会社 | シリコーン樹脂、uv-led用封止材組成物、硬化物及びuv-led用封止材 |
EP3292529B1 (en) * | 2015-05-04 | 2022-07-13 | OnePin, Inc. | Automatic aftercall directory and phonebook entry advertising |
CN113710471A (zh) * | 2019-04-04 | 2021-11-26 | 格雷斯公司 | 用于疏水性膜的涂料组合物和具有疏水性表面的制品 |
US20220267640A1 (en) | 2019-08-02 | 2022-08-25 | 3M Innovative Properties Company | Composition including a polyorganosiloxane and an amino-functional silane and method of using the same |
CN110982318A (zh) * | 2019-12-20 | 2020-04-10 | 苏州浩纳新材料科技有限公司 | 一种可实现玻璃疏水的湿巾及制备方法和应用方法 |
CN110981225A (zh) * | 2019-12-20 | 2020-04-10 | 苏州浩纳新材料科技有限公司 | 一种玻璃疏水防雨涂料及制备方法和应用方法 |
CN116867856A (zh) | 2020-11-10 | 2023-10-10 | 3M创新有限公司 | 用于制备涂覆制品的方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02233535A (ja) * | 1989-03-06 | 1990-09-17 | Three Bond Co Ltd | 車両ガラス用表面処理剤 |
JPH0812375A (ja) * | 1994-06-30 | 1996-01-16 | Nippon Sheet Glass Co Ltd | 撥水性物品及びその製造方法 |
JPH08209118A (ja) * | 1994-08-12 | 1996-08-13 | Shin Etsu Chem Co Ltd | 撥水処理剤 |
JPH09255941A (ja) * | 1996-03-26 | 1997-09-30 | Nippon Sheet Glass Co Ltd | 撥水処理剤およびその製造方法 |
WO1998040323A1 (en) * | 1997-03-11 | 1998-09-17 | Nippon Sheet Glass Co., Ltd. | A substrate having a treatment surface |
JP2000144056A (ja) * | 1998-11-10 | 2000-05-26 | Ikuo Narisawa | 水滴滑落性に優れた表面処理基材及びその製造方法 |
JP2002012452A (ja) * | 2000-06-28 | 2002-01-15 | Central Glass Co Ltd | 高滑水性基板およびその製造方法 |
JP2002166506A (ja) * | 2000-11-30 | 2002-06-11 | Asahi Glass Co Ltd | 疎水性基材およびその製造方法 |
JP2002226838A (ja) * | 2001-02-01 | 2002-08-14 | Asahi Glass Co Ltd | 撥水性組成物、表面処理された基材、その製造方法および輸送機器用物品 |
WO2002092945A1 (fr) * | 2001-05-17 | 2002-11-21 | Sekisui Jushi Kabushiki Kaisha | Structure d'exterieur, couverture faisant glisser la neige et la glace, et procede de production |
JP2003064309A (ja) * | 2001-08-30 | 2003-03-05 | Central Glass Co Ltd | 高滑水性被膜およびその被覆方法 |
JP2003113371A (ja) * | 2001-10-05 | 2003-04-18 | Toyo Riken Kk | 撥水処理剤組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69507551T2 (de) * | 1994-08-12 | 1999-07-15 | Shinetsu Chemical Co | Wasserabstossende Zusammensetzung |
EP0891953B1 (en) * | 1997-07-15 | 2006-01-11 | Central Glass Company, Limited | Glass plate with water-repellent film and method for producing same |
JPH11300270A (ja) * | 1998-04-27 | 1999-11-02 | Matsushita Electric Ind Co Ltd | 撥水性被膜とその製造方法及び撥水性塗料組成物 |
US6479157B1 (en) * | 1999-11-16 | 2002-11-12 | Asahi Glass Company, Limited | Substrate having treated surface layers and process for producing it |
CN1151226C (zh) * | 2000-03-29 | 2004-05-26 | 中国科学院化学研究所 | 一种超双疏(疏水、疏油)表面处理剂和用途 |
EP1398362A1 (en) * | 2001-03-30 | 2004-03-17 | Central Glass Company, Limited | Hydrophobic article |
KR100802519B1 (ko) * | 2002-07-30 | 2008-02-12 | 샌트랄 글래스 컴퍼니 리미티드 | 물품의 표면에서 물방울을 슬립다운시키는데 우수한 물품 및 그 물품을 제조하기 위한 방법 |
-
2005
- 2005-08-01 US US11/630,687 patent/US20080026163A1/en not_active Abandoned
- 2005-08-01 EP EP05767109A patent/EP1792963A4/en not_active Withdrawn
- 2005-08-01 CN CN200580025049.1A patent/CN101098945B/zh not_active Expired - Fee Related
- 2005-08-01 WO PCT/JP2005/014033 patent/WO2006022118A1/ja active Application Filing
- 2005-08-01 KR KR1020077003343A patent/KR100894079B1/ko not_active IP Right Cessation
- 2005-08-12 TW TW094127571A patent/TW200617152A/zh not_active IP Right Cessation
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02233535A (ja) * | 1989-03-06 | 1990-09-17 | Three Bond Co Ltd | 車両ガラス用表面処理剤 |
JPH0812375A (ja) * | 1994-06-30 | 1996-01-16 | Nippon Sheet Glass Co Ltd | 撥水性物品及びその製造方法 |
JPH08209118A (ja) * | 1994-08-12 | 1996-08-13 | Shin Etsu Chem Co Ltd | 撥水処理剤 |
JPH09255941A (ja) * | 1996-03-26 | 1997-09-30 | Nippon Sheet Glass Co Ltd | 撥水処理剤およびその製造方法 |
WO1998040323A1 (en) * | 1997-03-11 | 1998-09-17 | Nippon Sheet Glass Co., Ltd. | A substrate having a treatment surface |
JP2000144056A (ja) * | 1998-11-10 | 2000-05-26 | Ikuo Narisawa | 水滴滑落性に優れた表面処理基材及びその製造方法 |
JP2002012452A (ja) * | 2000-06-28 | 2002-01-15 | Central Glass Co Ltd | 高滑水性基板およびその製造方法 |
JP2002166506A (ja) * | 2000-11-30 | 2002-06-11 | Asahi Glass Co Ltd | 疎水性基材およびその製造方法 |
JP2002226838A (ja) * | 2001-02-01 | 2002-08-14 | Asahi Glass Co Ltd | 撥水性組成物、表面処理された基材、その製造方法および輸送機器用物品 |
WO2002092945A1 (fr) * | 2001-05-17 | 2002-11-21 | Sekisui Jushi Kabushiki Kaisha | Structure d'exterieur, couverture faisant glisser la neige et la glace, et procede de production |
JP2003064309A (ja) * | 2001-08-30 | 2003-03-05 | Central Glass Co Ltd | 高滑水性被膜およびその被覆方法 |
JP2003113371A (ja) * | 2001-10-05 | 2003-04-18 | Toyo Riken Kk | 撥水処理剤組成物 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007119630A1 (en) * | 2006-03-30 | 2007-10-25 | Fujifilm Corporation | Planing coat and method for producing the same |
CN100429009C (zh) * | 2006-09-27 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | 一种可在多种基材表面形成疏水透明薄膜的方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20070035075A (ko) | 2007-03-29 |
US20080026163A1 (en) | 2008-01-31 |
CN101098945A (zh) | 2008-01-02 |
TWI300439B (ja) | 2008-09-01 |
TW200617152A (en) | 2006-06-01 |
EP1792963A1 (en) | 2007-06-06 |
EP1792963A4 (en) | 2010-04-21 |
KR100894079B1 (ko) | 2009-04-21 |
CN101098945B (zh) | 2014-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006022118A1 (ja) | 滑水性被膜を得るための処理剤及び滑水性被膜の作製法 | |
EP0966410B1 (en) | A substrate having a treatment surface | |
WO2004011380A1 (ja) | 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 | |
JP2000144056A (ja) | 水滴滑落性に優れた表面処理基材及びその製造方法 | |
JP4826226B2 (ja) | 滑水性被膜を得るための処理剤及び滑水性被膜の作製法 | |
JP4876424B2 (ja) | 滑水性物品の製法 | |
JP4522357B2 (ja) | 滑水性ガラス物品の製法 | |
JP4014532B2 (ja) | 高滑水性被膜及びその形成方法 | |
JP3961349B2 (ja) | 高耐久性滑水被膜及びその製造方法 | |
JP3929321B2 (ja) | 高滑水性被膜及びその製造方法 | |
JPH09255941A (ja) | 撥水処理剤およびその製造方法 | |
JP4152769B2 (ja) | 高耐久な滑水性被膜の製造方法 | |
JP4265925B2 (ja) | 滑水性被膜の製造方法および滑水性被膜形成用塗布液 | |
JP3744736B2 (ja) | 高滑水性基材およびその製造方法 | |
JP3929313B2 (ja) | 高滑水性被膜及びその被覆方法 | |
KR100492396B1 (ko) | 표면 처리된 기판 및 기판의 표면 처리방법 | |
JP4093987B2 (ja) | 表面処理された基材の製造方法 | |
AU736054C (en) | A substrate having a treatment surface | |
JP2003064309A (ja) | 高滑水性被膜およびその被覆方法 | |
JP2003252650A (ja) | 高滑水性被膜及びその被覆法 | |
JP2000063153A (ja) | 撥水性基板およびその製造方法 | |
JP2002294151A (ja) | 高滑水性被膜およびその被覆方法 | |
JP2006306631A (ja) | 機能性物品の製法及びプライマー層の再活性化方法 | |
JP2001026463A (ja) | 高滑水性表面被膜形成用処理剤 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 11630687 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005767109 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200580025049.1 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077003343 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWP | Wipo information: published in national office |
Ref document number: 1020077003343 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2005767109 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11630687 Country of ref document: US |