WO2010134545A1 - Waterdrop slidable article and method for producing same - Google Patents

Waterdrop slidable article and method for producing same Download PDF

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Publication number
WO2010134545A1
WO2010134545A1 PCT/JP2010/058447 JP2010058447W WO2010134545A1 WO 2010134545 A1 WO2010134545 A1 WO 2010134545A1 JP 2010058447 W JP2010058447 W JP 2010058447W WO 2010134545 A1 WO2010134545 A1 WO 2010134545A1
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WO
WIPO (PCT)
Prior art keywords
water
fluoroalkylsilane
mass
treatment agent
linear polydimethylsiloxane
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Application number
PCT/JP2010/058447
Other languages
French (fr)
Japanese (ja)
Inventor
創一 公文
滋生 濱口
真規 斎藤
敏裕 平野
Original Assignee
セントラル硝子株式会社
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Publication of WO2010134545A1 publication Critical patent/WO2010134545A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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
    • 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
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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

Definitions

  • the present invention relates to a water-slidable article having good water drop sliding properties and a method for producing the same.
  • Patent Document 1 and Non-Patent Document 1 the present applicant has provided a treating agent capable of exhibiting good water slidability on a substrate such as glass.
  • the water-slidable article obtained with this treatment agent was not only excellent in water slidability but also excellent in removing dirt due to the difficulty of adhering scale or oil film.
  • the water-slidable articles disclosed in Patent Document 1 and Non-Patent Document 1 have good weather resistance and durability, but the number of [m] is small, for example, fluoroalkyl having 4 to 6 [m]
  • a silane is used as a treatment agent and a water-slidable article is washed with an alkaline cleaner using this, the water-sliding property may be lowered.
  • Some detergents for automobiles and living environments are alkaline, and it is preferable that the alkali resistance is improved for long-term use of the water-slidable article.
  • An object of the present invention is to improve the alkali resistance and wear resistance of a water-slidable article obtained using a treating agent using a fluoroalkylsilane having a small number of [m].
  • Linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane having 4 to 6 fluorocarbon units (CF 2 or CF 3 ) Each of these is chemically bonded to the surface of the substrate to form a water slidable layer.
  • the method for producing a water slidable article of the present invention comprises a step of applying a treatment agent to the surface of the article and 50 articles coated with the treatment agent.
  • the treatment agent has two or three hydrolyzable functional groups at at least one end, and has a dimethylsiloxane unit (—Si (CH 3 ) 2 O— ) And a fluoroalkylsilane represented by the general formula [1]
  • Y 1 is a monovalent hydrolyzable functional group.
  • [m] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ).
  • p] is an integer of 1 to 3 and represents the number of hydrolyzable functional groups)
  • a treatment agent having an organic solvent, an acid, and water, and the total amount of the treatment agent before the hydrolysis reaction.
  • the linear polydimethylsiloxane is 0.2 to 3.0% by mass
  • the fluoroalkylsilane is 0.4 to 2.5% by mass
  • the linear polydimethylsiloxane and the fluoroalkylsilane Is a treating agent having a total amount of 0.7 to 4.5% by mass and a mass ratio of the linear polydimethylsiloxane to the fluoroalkylsilane of 7.5: 1 to 1: 12.5.
  • the linear polydimethylsiloxane has a dimethylsiloxane chain having excellent water slidability, the water slidability of the resulting water slidable layer is improved.
  • the fluoroalkylsilane has a fluoroalkyl chain having excellent durability, it improves the durability of the resulting water slidable layer.
  • the length of the fluorocarbon chain of the fluoroalkylsilane that is, the number of [m] also affects the alkali resistance and wear resistance.
  • the number of [m] is 4-6. This is very important.
  • the method for producing a water-slidable article includes a step of applying a treating agent formed by mixing the linear polydimethylsiloxane, a solution containing the fluoroalkylsilane, an organic solvent, an acid, and water onto the article surface, and the treating agent. And heating the article coated with 50 to 250 ° C., and in the heat treatment, the polycondensation reaction of the linear polydimethylsiloxane and the fluoroalkylsilane proceeds and chemically binds to the surface of the article. . When the heat treatment temperature is low, the polycondensation reaction tends to be insufficient, and the alkali resistance and wear resistance of the water-sliding layer tend to decrease.
  • the heating temperature after coating is 50 to 250 ° C., and 80 to 200 ° C. It is particularly preferable that
  • the water-slidable article of the present invention comprises the steps of applying a treatment agent for forming a slidable layer on the surface of a substrate to the article surface, and heating the article coated with the treatment agent at 50 to 250 ° C.
  • a treatment agent for forming a slidable layer on the surface of a substrate to the article surface
  • heating the article coated with the treatment agent at 50 to 250 ° C.
  • Linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane having 4 to 6 fluorocarbon units (CF 2 or CF 3 ) Each of these is chemically bonded to the surface of the substrate to form a water slidable layer.
  • the method for producing a water slidable article of the present invention comprises a step of applying a treatment agent to the surface of the article and 50 articles coated with the treatment agent.
  • the treatment agent has two or three hydrolyzable functional groups at at least one end, and has a dimethylsiloxane unit (—Si (CH 3 ) 2 O— ) And a fluoroalkylsilane represented by the general formula [1]
  • Y 1 is a monovalent hydrolyzable functional group.
  • [m] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ).
  • p] is an integer of 1 to 3 and represents the number of hydrolyzable functional groups)
  • a treatment agent having an organic solvent, an acid, and water, and the total amount of the treatment agent before the hydrolysis reaction.
  • the linear polydimethylsiloxane is 0.2 to 3.0% by mass
  • the fluoroalkylsilane is 0.4 to 2.5% by mass
  • the linear polydimethylsiloxane and the fluoroalkylsilane Is a treating agent having a total amount of 0.7 to 4.5% by mass and a mass ratio of the linear polydimethylsiloxane to the fluoroalkylsilane of 7.5: 1 to 1: 12.5.
  • the number of dimethylsiloxane units (—Si (CH 3 ) 2 O—) is 30 to 400.
  • the number of dimethylsiloxane units of the linear polydimethylsiloxane exceeds 400, the number of hydrolyzable functional groups of the linear polydimethylsiloxane decreases relative to the dimethylsiloxane unit, Reactivity of dimethylsiloxane is reduced.
  • the resulting water slidable layer is weakly bonded to the substrate, and the wear resistance of the water slidable layer is reduced.
  • the surface of the water-sliding layer produced using the treatment agent of the present invention may be rubbed with a rag during cleaning by wiping. Therefore, the formation of a film having excellent wear resistance as well as water slidability is important from a practical viewpoint.
  • a functional group in the treatment agent that can be hydrolyzed reacts with a reactive group such as a hydroxyl group represented by a silanol group present on the surface of the base material.
  • a reactive group such as a hydroxyl group represented by a silanol group present on the surface of the base material.
  • the functional component is fixed to the substrate. Therefore, when the number of units decreases, the number of dimethylsiloxane units fixed on the substrate decreases.
  • the wear resistance of the formed sliding layer is affected by the number of units. When the number of units is 30 or more, these characteristics are remarkably improved.
  • the linear polydimethylsiloxane has two or three hydrolyzable functional groups at at least one terminal.
  • the number of hydrolyzable functional groups at both ends is 1 or less, the reactivity of the polydimethylsiloxane is greatly reduced, and the bond with the substrate is weakened. Since the durability of the water slidable layer obtained by this decreases, it is not preferable.
  • the linear polydimethylsiloxane is mixed in an amount of 0.2 to 3.0% by mass based on the total amount of the treating agent.
  • perfluoroalkylsilane is generally used as a functional component, but this has a low water slidability and a minimum inclination angle (hereinafter referred to as a tumbling angle) of 25 that allows 50 ⁇ l of water droplets to slide down. It is as large as ⁇ 27 °.
  • the falling angle which is an index of sliding
  • the falling angle is around 20 °, and it is felt that there is a difference in the sliding property or scattering property of water droplets from the sliding layer.
  • this is noticeable.
  • the surplus becomes a dry solid and remains on the base material.
  • concentration of the linear polydimethylsiloxane with respect to the total amount of the treatment agent exceeds 3.0% by mass, the amount of dried solids increases during the formation of the water slidable layer. It will take. This long-time wiping increases the possibility of physical wear and increases the risk of adverse effects on water slidability, durability, and the like.
  • the linear polydimethylsiloxane is more preferably 2.5% by mass or less based on the total amount of the treating agent.
  • polydimethylsiloxane represented by the following general formula [2] 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, — (CH 2 ) i —NH—CO.
  • —O— group ([i] is an integer of 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 of 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 [2] are sites that connect a hydrolyzable functional group and a dimethylsiloxane chain that exhibits water repellency and water slidability. Accordingly, when the durability of this portion is lowered, the dimethylsiloxane chain easily falls off from the water sliding layer, and the durability of the water sliding layer is lowered. Therefore, A 1 and A 2 of the polydimethylsiloxane represented by the general formula [2] are preferably a divalent hydrocarbon group or oxygen having excellent durability.
  • fluoroalkylsilane used in the treatment agent of the present invention a fluoroalkylsilane represented by the following general formula [1] is preferably used.
  • Y 1 is a monovalent hydrolyzable functional group.
  • [M] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ).
  • [P] is an integer of 1 to 3, and represents the number of functional groups that can be hydrolyzed.
  • the number of fluorocarbon units is 4. It is important to set to 6.
  • the fluoroalkylsilane is mixed in an amount of 0.4 to 2.5% by mass with respect to the total amount of the processing agent. If it is less than 0.4% by mass, alkali resistance and wear resistance are remarkably lowered. On the other hand, if it exceeds 2.5% by mass, the water slidability is greatly reduced, and the falling angle exceeds 22 °. In order to obtain higher sliding properties (falling angle: 20 ° or less) and alkali resistance, the mixing amount is preferably 0.6 to 2.0% by mass.
  • fluoroalkylsilane examples include CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 5 CH 2 CH 2 SiCH 3 (OCH 3 ) 2 , and CF 3 (CF 2 ).
  • an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group, a chloro group, or an isocyanate group
  • the hydrolyzable functional group is preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
  • the total amount of the linear polydimethylsiloxane and the fluoroalkylsilane is 0.7 to 4.5% by mass. If it is less than 0.7% by mass, alkali resistance and wear resistance are remarkably lowered. On the other hand, if it exceeds 4.5% by mass, the surplus becomes a dry solid and the amount remaining on the substrate increases, and it becomes difficult to wipe it transparent with a paper towel or the like. As a result, the surplus component remains white and mottled by visual observation, causing a problem in appearance. Therefore, the mixing amount is preferably 0.9 to 4.5% by mass in terms of mass concentration.
  • the mass ratio of the linear polydimethylsiloxane and the fluoroalkylsilane is 7.5: 1 to 1: 12.5 before the hydrolysis reaction.
  • excellent water slidability (falling angle: 20 ° or less) and alkali resistance can be obtained, and 4.2: 1 to 1:10 is more preferable.
  • the solvent used for the treating agent can be an organic solvent that dissolves other components (linear polydimethylsiloxane, fluoroalkylsilane, water, acid), and these include lower alcohols such as ethyl alcohol and isopropyl alcohol. , 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 diethyl ether and diisopropyl ether, and mixtures thereof It is preferable.
  • a mixed solvent of at least one solvent selected from methyl ethyl ketone, ethyl acetate, hexane, diethyl ether and diisopropyl ether and a lower alcohol such as ethyl alcohol or isopropyl alcohol is linear polydimethylsiloxane, fluoroalkylsilane, water.
  • the solubility of the 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 treating agent of the present invention is 1 to 100 times in terms of the number of molecules relative to the number of hydrolyzable functional groups of the linear polydimethylsiloxane and the fluoroalkylsilane. Is preferred. If it is less than 1 time, the hydrolysis reaction does not proceed sufficiently, silanol groups are hardly generated sufficiently, and the durability of the resulting water slidable layer is lowered, which is not preferable. Moreover, when it exceeds 100 times, it becomes difficult for the said linear polydimethylsiloxane, the said fluoroalkylsilane, and water to melt
  • 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, sulfuric acid, other organic acids, and the like can be used. Then, the mixture is mixed so that the pH value becomes 0 to 5, preferably 0 to 3, in the state of being mixed with the water.
  • the treatment agent for forming the water slidable layer is a mixture of the linear polydimethylsiloxane, the fluoroalkylsilane, and a solvent, and water and an acid for causing a hydrolysis reaction are added and mixed. It can be obtained by hydrolyzing the polydimethylsiloxane and the fluoroalkylsilane.
  • the reason why the linear polydimethylsiloxane and the fluoroalkylsilane are mixed first is to mix both components homogeneously in the treating agent.
  • acid, water, linear polydimethylsiloxane and fluoroalkylsilane may be mixed simultaneously.
  • Application methods for applying the treatment agent obtained above to the substrate surface include brush coating, hand coating, robot coating, nozzle flow coating method, dipping method, spray method, reverse coating method, flexo method, printing method, flow
  • Various film forming methods such as a coating method, a spin coating method, a roll coating method, and a combination thereof can be appropriately employed.
  • the treatment agent of the present invention is heated at 50 to 250 ° C. after coating, but the substrate to which the treatment agent is applied is not particularly limited as long as it has a heat resistance temperature higher than the heating temperature.
  • the substrate to which the treatment agent is applied is not particularly limited as long as it has a heat resistance temperature higher than the heating temperature.
  • a plate glass having an inorganic transparency such as a float plate glass usually used for a window glass for a building or a mirror, or soda lime glass produced by a roll-out method.
  • a translucent to opaque glass substrate such as a reflective substrate such as a mirror formed by using these plate glasses, rubbed glass, or glass with a pattern engraved thereon can be used.
  • substrates made of ceramic materials used for tiles, tiles, sanitary ware, tableware, frames such as glass windows, cookers, scalpels, medical instruments such as scalpels, injection needles, sinks, automobiles
  • Metal materials such as stainless steel, aluminum, steel, etc. used in the body of plastics
  • plastic base materials such as polycarbonate resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polyethylene resin, polyvinyl chloride resin, other plastics A substrate may be used.
  • the treatment after applying the treatment agent to the substrate will be described.
  • the polydimethylsiloxane and the fluoroalkylsilane are bonded to the substrate by heating at 50 to 250 ° C. Heating may be performed under normal pressure, increased pressure, reduced pressure, or an inert atmosphere. Microwave heating is also effective.
  • the surplus is dried and remains on the sliding layer, the surplus is wiped with a paper towel or cloth dampened with an organic solvent and / or a dry paper towel or cloth. A substrate on which a layer has been formed is obtained.
  • the water slidability is evaluated by a method as described in the evaluation method of the example. After dropping 50 ⁇ l of pure water on the sample surface, the sample is gradually tilted, and the water droplets move. It is evaluated by measuring the tilt angle at the start. The inclination angle was defined as a sliding angle (°), and the sliding angle was measured in the atmosphere (about 25 ° C.) using a CA-A type manufactured by Kyowa Interface Science.
  • Abrasion resistance A cotton cloth impregnated with a ceria suspension (10% by mass) in which abrasive for glass EmiraT E40T (Mitsui Mining & Mining) is dispersed in tap water, and about 1.5 kg / cm 2 on the sample. was applied by sliding from the peripheral edge of the coating to the peripheral edge of the coating on the opposite side through the central portion of the coating. In this sliding operation, the time when the cotton cloth returned to the original position was defined as the number of times of polishing, and the number of times of polishing until the entire region of the polishing region became hydrophilic (a state in which the ceria suspension was not repelled) was evaluated. 40 times or more was regarded as acceptable (indicated as “ ⁇ ” in Table 2).
  • Example 1 (1) Preparation of treatment agent Table 1 shows sample preparation conditions. First, both terminal trialkoxy type linear polydimethylsiloxane having 250 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 ⁇ Si (CH 3 ) 2 O ⁇ 250 Si (CH 3 ) 2 CH 2 CH 2 Si (OCH 3) 3]; 0.40 g, methyl ethyl ketone; 48.85G, fluoroalkyl silanes having fluorocarbon units 6 [CF 3 (CF 2) 5 CH 2 CH 2 Si (OCH 3) 3 ]; 0.60 g and isopropyl alcohol; 48.85 g were mixed and stirred for about 5 minutes.
  • both terminal trialkoxy type linear polydimethylsiloxane having 250 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 ⁇ Si (CH 3 ) 2 O ⁇ 250 Si (CH 3 ) 2 CH 2 CH 2 Si (OCH 3) 3]; 0.40 g, methyl
  • the mass concentration of the linear polydimethylsiloxane mixed (described as “polydimethylsiloxane concentration”) is 0.4 mass% with respect to the total amount of the processing agent, and is mixed with respect to the total amount of the processing agent.
  • a treating agent having a mass concentration of fluoroalkylsilane (referred to as “fluoroalkylsilane concentration”) of 0.6% by mass was obtained.
  • the surface of 300 mm ⁇ 300 mm ⁇ 2 mm thick float glass 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 abrasives, Miraku A (T) (manufactured by Mitsui Kinzoku Mining Co., Ltd.) with water.
  • the initial falling angle was 20 °, indicating a good water droplet falling property. Furthermore, in the visual observation after the alkali resistance test, there was no change in the transparency of the sample, and the contact angle was 90 ° or more. Further, in the visual observation after the water resistance test, there was no change in the transparency of the sample, the contact angle was 90 ° or more, and the durability was excellent. Further, in the evaluation of wear resistance, 50 reciprocations were required to make the entire polishing region hydrophilic, and the wear resistance was excellent.
  • Example 2 Except that the fluoroalkylsilane concentration was 1.5% by mass, everything was the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 20 °, showing good water droplet falling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 3 As the linear polydimethylsiloxane, a trialkoxy type linear polydimethylsiloxane having 50 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 ⁇ Si (CH 3 ) 2 O ⁇ 50 Si ( Except for using CH 3 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 ], all were the same as in Example 1, and a transparent sample with no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 20 °, showing good water droplet falling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 4 As the linear polydimethylsiloxane, both terminal trialkoxy type linear polydimethylsiloxane having 400 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 ⁇ Si (CH 3 ) 2 O ⁇ 400 Si ( Except for using CH 3 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 ], all were the same as in Example 1, and a transparent sample with no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 21 ° and the water droplet falling property was good, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 5 Except that the concentration of the linear polydimethylsiloxane was 2.5% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 20 °, showing good water droplet falling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 6 Except for the fluoroalkylsilane concentration of 2.0% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial tumbling angle was 22 °, showing good water droplet tumbling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 7 Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then heat-treated at 80 ° C., everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 21 ° and the water droplet falling property was good, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 8 Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then heat-treated at 220 ° C., everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial tumbling angle was 22 °, showing good water droplet tumbling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
  • Example 1 Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then was not heat-treated, everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial sliding angle and water resistance were good as shown in Table 2, but the alkali resistance and wear resistance were insufficient.
  • Example 2 Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then heat-treated at 320 ° C., everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial falling angle and the initial contact angle were insufficient.
  • Example 7 All were the same as Example 1 except that the concentration of the linear polydimethylsiloxane was 3.5% by mass. Attempts were made to wipe off the excess water-repellent component that remained visually mottled after heat treatment with a paper towel moistened with isopropyl alcohol, but could not be completely removed. As a result of visual observation, the surplus components remained white and mottled, and there was a problem in appearance.
  • Example 11 All were the same as Example 1 except that the concentration of linear polydimethylsiloxane was 3.0% by mass and the concentration of fluoroalkylsilane was 3.0% by mass. Attempts were made to wipe off the excess water-repellent component that remained visually mottled after heat treatment with a paper towel moistened with isopropyl alcohol, but could not be completely removed. As a result of visual observation, the surplus components remained white and mottled, and there was a problem in appearance.

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Abstract

Disclosed is a waterdrop slidable article which is obtained using a treating agent containing a short-chain fluoroalkylsilane, and has improved alkali resistance. Specifically, a treating agent containing a linear polydimethylsiloxane (PDMS) that has 2 or 3 hydrolyzable functional groups at least one end and 30-400 dimethylsiloxane units (-Si(CH3)2O-), a fluoroalkylsilane that has 4-6 fluorocarbon units (CF2 or CF3), an organic solvent, an acid and water, in said treating agent before the hydrolysis reaction, the amount of the PDMS being 0.2-3.0% by mass, the amount of the fluoroalkylsilane being 0.4-2.5% by mass, and the total of the PDMS and the fluoroalkylsilane being 0.7-4.5% by mass relative to the total mass of the treating agent, and the mass ratio of the PDMS to the fluoroalkylsilane being from 7.5:1 to 1:12.5, is applied over the surface of an article, and then the article is heated at 50-250˚C, so that the dimethylsiloxane units and the fluorocarbon units are exposed from the base surface.

Description

滑水性物品及び製法Water-sliding article and manufacturing method
　本発明は、良好な水滴の滑落性を有する滑水性物品とその製法に関する。 The present invention relates to a water-slidable article having good water drop sliding properties and a method for producing the same.
　本出願人は、特許文献１や非特許文献１で開示してきたようにガラス等の基材に良好な滑水性を呈することができる処理剤を提供してきた。また、この処理剤で得られた滑水性物品は、滑水性が良好なだけでなく、水垢や油膜などが付着し難く汚れ除去に優れたものであった。
特開2006-144019号公報 製品カタログ　「ナノハイブリッド　美滑水コート」　＜www.yof-linda.co.jp/semi/car/glass/07.pdf＞2009年5月15日検索 As disclosed in Patent Document 1 and Non-Patent Document 1, the present applicant has provided a treating agent capable of exhibiting good water slidability on a substrate such as glass. In addition, the water-slidable article obtained with this treatment agent was not only excellent in water slidability but also excellent in removing dirt due to the difficulty of adhering scale or oil film.
JP 2006-144019 Product Catalog "Nanohybrid Mizusui Coat" <www.yof-linda.co.jp/semi/car/glass/07.pdf> Search May 15, 2009
　近年、下記一般式［１］で表されるフルオロアルキルシランにおいて、[ｍ]の数が大きなものは入手が難しくなってきており、これら物質を使用してなる処理剤はコストが上昇することが予想されている。そのため、[ｍ]の数の少ないフルオロアルキルシランを用いて滑水性を呈することができる処理剤を提供する必要性が生じている。 In recent years, in fluoroalkylsilanes represented by the following general formula [1], those having a large number of [m] have become difficult to obtain, and the cost of processing agents using these substances may increase. Expected. Therefore, there is a need to provide a treatment agent that can exhibit lubricity using a fluoroalkylsilane having a small number of [m].
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　特許文献１や非特許文献１で開示された滑水性物品は、耐候性や耐久性が良好なものであったが、[ｍ]の数が少ない、例えば[ｍ]が４～６のフルオロアルキルシランを用いて処理剤とし、これを用いて滑水性物品をアルカリ性洗浄剤で洗浄すると滑水性が低下することがある。自動車用、住環境用の洗剤にはアルカリ性のものがあり、このため、滑水性物品の長期使用のために耐アルカリ性も向上されることが好ましい。また、滑水性物品の使用にあたっては、清掃時に布や雑巾で払拭される場合が多く、布や雑巾に対する耐摩耗性も向上されることが好ましい。本発明は、[ｍ]の数が少ないフルオロアルキルシランを用いる処理剤を用いて得られる滑水性物品の耐アルカリ性、耐摩耗性を向上させることを課題とする。 The water-slidable articles disclosed in Patent Document 1 and Non-Patent Document 1 have good weather resistance and durability, but the number of [m] is small, for example, fluoroalkyl having 4 to 6 [m] When a silane is used as a treatment agent and a water-slidable article is washed with an alkaline cleaner using this, the water-sliding property may be lowered. Some detergents for automobiles and living environments are alkaline, and it is preferable that the alkali resistance is improved for long-term use of the water-slidable article. Further, when using the water-slidable article, it is often wiped off with a cloth or a cloth when cleaning, and it is preferable that the wear resistance against the cloth or the cloth is also improved. An object of the present invention is to improve the alkali resistance and wear resistance of a water-slidable article obtained using a treating agent using a fluoroalkylsilane having a small number of [m].
　ジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及びフルオロカーボンユニット（ＣＦ2又はＣＦ3）の数が４～６であるフルオロアルキルシランのそれぞれを、基材表面に化学的に結合せしめて滑水層を形成する本発明の滑水性物品の製法は、処理剤を物品表面に塗布する工程と前記処理剤が塗布された物品を５０～２５０℃で加熱する工程を有し、前記処理剤は、少なくとも一つの末端に加水分解可能な官能基を２個又は３個有し、且つジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及び一般式［１］で表されるフルオロアルキルシラン Linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane having 4 to 6 fluorocarbon units (CF 2 or CF 3 ) Each of these is chemically bonded to the surface of the substrate to form a water slidable layer. The method for producing a water slidable article of the present invention comprises a step of applying a treatment agent to the surface of the article and 50 articles coated with the treatment agent. And the treatment agent has two or three hydrolyzable functional groups at at least one end, and has a dimethylsiloxane unit (—Si (CH 3 ) 2 O— ) And a fluoroalkylsilane represented by the general formula [1]
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（ここで、Ｙ1は１価の加水分解可能な官能基である。さらに、［ｍ］は４～６の整数であり、フルオロカーボンユニット（ＣＦ2又はＣＦ3）の数を表す。さらに、［ｐ］は１～３の整数であり、加水分解可能な官能基の数を表す。）、有機溶媒、酸、及び水を有する処理剤であり、該処理剤の総量に対し、加水分解反応前における質量濃度で前記直鎖状ポリジメチルシロキサンが０．２～３．０質量％、前記フルオロアルキルシランが０．４～２．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとの総量が０．７～４．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランの質量比が７．５：１～１：１２．５である処理剤である。（以降、本明細書において、直鎖状ポリジメチルシロキサン、フルオロアルキルシランの双方を示す場合、「機能成分」と表記する。また、直鎖状ポリジメチルシロキサンとフルオロアルキルシランとの総量を示す場合、「機能成分の総量」と表記する。） (Where Y 1 is a monovalent hydrolyzable functional group. Furthermore, [m] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ). p] is an integer of 1 to 3 and represents the number of hydrolyzable functional groups)), a treatment agent having an organic solvent, an acid, and water, and the total amount of the treatment agent before the hydrolysis reaction. The linear polydimethylsiloxane is 0.2 to 3.0% by mass, the fluoroalkylsilane is 0.4 to 2.5% by mass, the linear polydimethylsiloxane and the fluoroalkylsilane Is a treating agent having a total amount of 0.7 to 4.5% by mass and a mass ratio of the linear polydimethylsiloxane to the fluoroalkylsilane of 7.5: 1 to 1: 12.5. (Hereinafter, in this specification, when both linear polydimethylsiloxane and fluoroalkylsilane are shown, it is expressed as “functional component”. Also, when the total amount of linear polydimethylsiloxane and fluoroalkylsilane is shown. , Written as “total amount of functional ingredients”.)
　前記直鎖状ポリジメチルシロキサンは、滑水性に優れるジメチルシロキサン鎖を有するので、得られる滑水層の滑水性を向上させる。一方、前記フルオロアルキルシランは、耐久性に優れたフルオロアルキル鎖を有するので、得られる滑水層の耐久性を向上させる。 Since the linear polydimethylsiloxane has a dimethylsiloxane chain having excellent water slidability, the water slidability of the resulting water slidable layer is improved. On the other hand, since the fluoroalkylsilane has a fluoroalkyl chain having excellent durability, it improves the durability of the resulting water slidable layer.
　前記フルオロアルキルシランのフルオロカーボン鎖の長さ、すなわち［ｍ］の数も耐アルカリ性、耐摩耗性に影響する。［ｍ］が小さいと耐アルカリ性、耐摩耗性が低下する傾向にあり、[ｍ]の数が大きなものは入手が難しくなってきていることから、係る［ｍ］の数は４～６とすることが重要である。 The length of the fluorocarbon chain of the fluoroalkylsilane, that is, the number of [m] also affects the alkali resistance and wear resistance. When [m] is small, alkali resistance and wear resistance tend to decrease, and those having a large number of [m] are becoming difficult to obtain. Therefore, the number of [m] is 4-6. This is very important.
　上記滑水性物品の製法は、前記直鎖状ポリジメチルシロキサンと、前記フルオロアルキルシランと有機溶媒、酸、及び水を有する溶液を混合してなる処理剤を物品表面に塗布する工程と前記処理剤が塗布された物品を５０～２５０℃で加熱する工程を有し、熱処理では前記直鎖状ポリジメチルシロキサン及び前記フルオロアルキルシランの重縮合反応を進行させるとともに、物品の表面と化学的に結合させる。熱処理温度が低いと前記重縮合反応が不十分となりやすく、滑水層の耐アルカリ性、耐摩耗性が低下する傾向がある。一方、熱処理温度が高いと、前記直鎖状ポリジメチルシロキサンや前記フルオロアルキルシランが熱分解するため、滑水層の撥水性、滑水性および水垢や汚染物の除去性が低下する。滑水層の耐アルカリ性、耐摩耗性、撥水性、滑水性および水垢や汚染物の除去性を考慮すると塗布後の加熱温度は、５０～２５０℃とすることが重要であり、８０～２００℃とすることが特に好ましい。 The method for producing a water-slidable article includes a step of applying a treating agent formed by mixing the linear polydimethylsiloxane, a solution containing the fluoroalkylsilane, an organic solvent, an acid, and water onto the article surface, and the treating agent. And heating the article coated with 50 to 250 ° C., and in the heat treatment, the polycondensation reaction of the linear polydimethylsiloxane and the fluoroalkylsilane proceeds and chemically binds to the surface of the article. . When the heat treatment temperature is low, the polycondensation reaction tends to be insufficient, and the alkali resistance and wear resistance of the water-sliding layer tend to decrease. On the other hand, when the heat treatment temperature is high, the linear polydimethylsiloxane and the fluoroalkylsilane are thermally decomposed, so that the water repellency, water slidability and removal of dirt and contaminants of the water sliding layer are lowered. Considering the alkali resistance, abrasion resistance, water repellency, water slidability, and removal of scales and contaminants of the water sliding layer, it is important that the heating temperature after coating is 50 to 250 ° C., and 80 to 200 ° C. It is particularly preferable that
　本発明の滑水性物品は、基材表面に滑水層を形成せしめる処理剤を物品表面に塗布する工程、及び、該処理剤が塗布された物品を５０～２５０℃で加熱する工程によって、前記特許文献１や非特許文献１と同様に優れた滑水性を得つつ、さらに耐アルカリ性、耐摩耗性の向上が見られたので、水やアルカリ性洗浄剤等が存在する環境や布や雑巾で払拭される環境での使用が好適である。 The water-slidable article of the present invention comprises the steps of applying a treatment agent for forming a slidable layer on the surface of a substrate to the article surface, and heating the article coated with the treatment agent at 50 to 250 ° C. Similar to Patent Document 1 and Non-Patent Document 1, while obtaining excellent water slidability, further improvements in alkali resistance and wear resistance were observed, so wipe with an environment or cloth or rag that contains water or alkaline detergent, etc. It is suitable for use in the environment in which it is used.
　ジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及びフルオロカーボンユニット（ＣＦ2又はＣＦ3）の数が４～６であるフルオロアルキルシランのそれぞれを、基材表面に化学的に結合せしめて滑水層を形成する本発明の滑水性物品の製法は、処理剤を物品表面に塗布する工程と前記処理剤が塗布された物品を５０～２５０℃で加熱する工程を有し、前記処理剤は、少なくとも一つの末端に加水分解可能な官能基を２個又は３個有し、且つジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及び一般式［１］で表されるフルオロアルキルシラン Linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane having 4 to 6 fluorocarbon units (CF 2 or CF 3 ) Each of these is chemically bonded to the surface of the substrate to form a water slidable layer. The method for producing a water slidable article of the present invention comprises a step of applying a treatment agent to the surface of the article and 50 articles coated with the treatment agent. And the treatment agent has two or three hydrolyzable functional groups at at least one end, and has a dimethylsiloxane unit (—Si (CH 3 ) 2 O— ) And a fluoroalkylsilane represented by the general formula [1]
Figure JPOXMLDOC01-appb-C000005
 （ここで、Ｙ1は１価の加水分解可能な官能基である。さらに、［ｍ］は４～６の整数であり、フルオロカーボンユニット（ＣＦ2又はＣＦ3）の数を表す。さらに、［ｐ］は１～３の整数であり、加水分解可能な官能基の数を表す。）、有機溶媒、酸、及び水を有する処理剤であり、該処理剤の総量に対し、加水分解反応前における質量濃度で前記直鎖状ポリジメチルシロキサンが０．２～３．０質量％、前記フルオロアルキルシランが０．４～２．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとの総量が０．７～４．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランの質量比が７．５：１～１：１２．５である処理剤である。
Figure JPOXMLDOC01-appb-C000005
 (Where Y 1 is a monovalent hydrolyzable functional group. Furthermore, [m] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ). p] is an integer of 1 to 3 and represents the number of hydrolyzable functional groups)), a treatment agent having an organic solvent, an acid, and water, and the total amount of the treatment agent before the hydrolysis reaction. The linear polydimethylsiloxane is 0.2 to 3.0% by mass, the fluoroalkylsilane is 0.4 to 2.5% by mass, the linear polydimethylsiloxane and the fluoroalkylsilane Is a treating agent having a total amount of 0.7 to 4.5% by mass and a mass ratio of the linear polydimethylsiloxane to the fluoroalkylsilane of 7.5: 1 to 1: 12.5.
　本発明の処理剤に使用される直鎖状ポリジメチルシロキサンは、ジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数を３０～４００とすることが重要である。前記直鎖状ポリジメチルシロキサンのジメチルシロキサンユニット数が４００を超えると、直鎖状ポリジメチルシロキサンの加水分解可能な官能基の数がジメチルシロキサンユニットに対して相対的に減少することになり、ポリジメチルシロキサンの反応性が低下する。この結果、得られる滑水層は、基材との結合が弱くなり、滑水層の耐摩耗性が低下する。 In the linear polydimethylsiloxane used in the treatment agent of the present invention, it is important that the number of dimethylsiloxane units (—Si (CH 3 ) 2 O—) is 30 to 400. When the number of dimethylsiloxane units of the linear polydimethylsiloxane exceeds 400, the number of hydrolyzable functional groups of the linear polydimethylsiloxane decreases relative to the dimethylsiloxane unit, Reactivity of dimethylsiloxane is reduced. As a result, the resulting water slidable layer is weakly bonded to the substrate, and the wear resistance of the water slidable layer is reduced.
　本発明の処理剤を用いて作製した滑水層は、払拭による清掃時に雑巾などで表面を摩擦される場合もある。従って、滑水性はもちろんのこと耐摩耗性に優れる被膜の形成は、実用の観点から重要である。 The surface of the water-sliding layer produced using the treatment agent of the present invention may be rubbed with a rag during cleaning by wiping. Therefore, the formation of a film having excellent wear resistance as well as water slidability is important from a practical viewpoint.
　一方、本発明の処理剤を基材に処理すると、処理剤中の機能成分の加水分解可能な官能基と基材表面に存在するシラノール基に代表される水酸基等の反応性基が反応して結合することにより機能成分が基材に固定される。従って、該ユニット数が少なくなると、基材上に固定されるジメチルシロキサンユニット数が減少することになる。本発明での検討の結果、形成される滑水層の耐摩耗性は、該ユニット数に影響されることが判明した。そして、該ユニット数を３０以上とするとこれら特性が顕著に向上する。 On the other hand, when the base material is treated with the treatment agent of the present invention, a functional group in the treatment agent that can be hydrolyzed reacts with a reactive group such as a hydroxyl group represented by a silanol group present on the surface of the base material. By bonding, the functional component is fixed to the substrate. Therefore, when the number of units decreases, the number of dimethylsiloxane units fixed on the substrate decreases. As a result of the study in the present invention, it has been found that the wear resistance of the formed sliding layer is affected by the number of units. When the number of units is 30 or more, these characteristics are remarkably improved.
　また、前記直鎖状ポリジメチルシロキサンは、少なくとも一つの末端に加水分解可能な官能基を２個又は３個有することが重要である。両末端の加水分解可能な官能基の数が１個以下である場合、該ポリジメチルシロキサンの反応性が大幅に低下し、基材との結合が弱くなる。これにより得られる滑水層の耐久性が低下するので好ましくない。 Further, it is important that the linear polydimethylsiloxane has two or three hydrolyzable functional groups at at least one terminal. When the number of hydrolyzable functional groups at both ends is 1 or less, the reactivity of the polydimethylsiloxane is greatly reduced, and the bond with the substrate is weakened. Since the durability of the water slidable layer obtained by this decreases, it is not preferable.
　さらに、前記直鎖状ポリジメチルシロキサンは、処理剤の総量に対し０．２～３．０質量％混入されることが重要である。一般的に撥水剤としては、パーフルオロアルキルシランが機能成分に用いられているが、これは滑水性が低く、５０μｌの水滴が滑落できる最小傾斜角度（以降、転落角と表記する）も２５～２７°と大きい。 Furthermore, it is important that the linear polydimethylsiloxane is mixed in an amount of 0.2 to 3.0% by mass based on the total amount of the treating agent. As a water repellent, perfluoroalkylsilane is generally used as a functional component, but this has a low water slidability and a minimum inclination angle (hereinafter referred to as a tumbling angle) of 25 that allows 50 μl of water droplets to slide down. It is as large as ~ 27 °.
　滑水層を実際に使用するにあたり、滑水性の指標となるこの転落角が２０°前後で、水滴の滑水層からの滑落性、又は飛散性に違いがあることが体感される。例えば、滑水層を車両の窓に使用した場合には、このことは顕著に体感される。 In actual use of the sliding layer, the falling angle, which is an index of sliding, is around 20 °, and it is felt that there is a difference in the sliding property or scattering property of water droplets from the sliding layer. For example, when a sliding layer is used for a vehicle window, this is noticeable.
　そして、前記直鎖状ポリジメチルシロキサンが、処理剤の総量に対し０．２質量％未満の場合、得られる滑水層の転落角が２２°を超えるので、滑水層の滑水性が低いものとなる。 And when the said linear polydimethylsiloxane is less than 0.2 mass% with respect to the total amount of a processing agent, since the sliding angle of the obtained sliding layer exceeds 22 degrees, the sliding property of a sliding layer is low It becomes.
　また、処理剤を基材に塗布、そして加熱後には、余剰分が乾固物となって基材上に残留する。処理剤の総量に対する前記直鎖状ポリジメチルシロキサンの濃度が３．０質量％を超えると、滑水層形成の際、乾固物の量が増加し、この除去工程に負荷がかかり、時間を要するようになる。この長時間の払拭は、物理的に摩耗する可能性を高め、滑水性、耐久性等に悪影響を与える危険性を高める。 Also, after the treatment agent is applied to the base material and heated, the surplus becomes a dry solid and remains on the base material. When the concentration of the linear polydimethylsiloxane with respect to the total amount of the treatment agent exceeds 3.0% by mass, the amount of dried solids increases during the formation of the water slidable layer. It will take. This long-time wiping increases the possibility of physical wear and increases the risk of adverse effects on water slidability, durability, and the like.
　さらには、この除去工程の時間（負荷）が大きい場合には、結果として、乾固物を除去しきれず、滑水層上に残留する場合が多くなる。余剰分が残留すると、水滴が余剰分に引っかかりスムーズに移動できなくなるため、滑水性が低下する。さらに、余剰分は白くまだらに滑水層表面に残留するため、滑水層の透光性の低下をもたらす。 Furthermore, when the time (load) of this removal process is large, as a result, the dried solids cannot be completely removed and often remain on the sliding water layer. If the surplus remains, water droplets are caught by the surplus and cannot move smoothly, resulting in a decrease in lubricity. Furthermore, since the surplus remains white and mottled on the surface of the water slide layer, the light transmittance of the water slide layer is reduced.
　検討の結果、処理剤の総量に対する前記直鎖状ポリジメチルシロキサンの濃度を３．０質量％以下とすれば、上記点についても考慮した処理剤とすることができることがわかった。前記直鎖状ポリジメチルシロキサンは、処理剤の総量に対し２．５質量％以下にすることがより好ましい。 As a result of the examination, it was found that when the concentration of the linear polydimethylsiloxane with respect to the total amount of the treatment agent is 3.0% by mass or less, the treatment agent considering the above points can be obtained. The linear polydimethylsiloxane is more preferably 2.5% by mass or less based on the total amount of the treating agent.
　前記直鎖状ポリジメチルシロキサンとしては、下記一般式［２］で示されるポリジメチルシロキサンが好適に用いられる。 As the linear polydimethylsiloxane, polydimethylsiloxane represented by the following general formula [2] is preferably used.
Figure JPOXMLDOC01-appb-C000006
 　ここで、Ｘ1及びＸ2は、それぞれ、１価の加水分解可能な官能基であり、Ａ1及びＡ2は、それぞれ、２価の炭化水素基、-(ＣＨ2)i-ＮＨ-ＣＯ-Ｏ-基（［ｉ］は０～９の整数）、若しくは、酸素である。また、［ｎ］は３０～４００の整数でジメチルシロキサンユニットの数を表す。さらに、［ａ］及び［ｂ］は、それぞれ、０～３の整数であり、［ａ］又は［ｂ］の少なくとも一方は２又は３でなければならない。
Figure JPOXMLDOC01-appb-C000006
 Here, X 1 and X 2 are each a monovalent hydrolyzable functional group, and A 1 and A 2 are each a divalent hydrocarbon group, — (CH 2 ) i —NH—CO. —O— group ([i] is an integer of 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 of 0 to 3, and at least one of [a] or [b] must be 2 or 3.
　また、前記一般式［２］で示されるポリジメチルシロキサンのＡ1及びＡ2は、加水分解可能な官能基と撥水性や滑水性を発現するジメチルシロキサン鎖を繋ぐ部位である。従って、この部位の耐久性が低下すると、滑水層からジメチルシロキサン鎖が容易に脱落するようになり、滑水層の耐久性が低下する。このことから、前記一般式［２］で示されるポリジメチルシロキサンのＡ1及びＡ2は耐久性に優れる２価の炭化水素基や酸素が好ましい。 In addition, A 1 and A 2 of the polydimethylsiloxane represented by the general formula [2] are sites that connect a hydrolyzable functional group and a dimethylsiloxane chain that exhibits water repellency and water slidability. Accordingly, when the durability of this portion is lowered, the dimethylsiloxane chain easily falls off from the water sliding layer, and the durability of the water sliding layer is lowered. Therefore, A 1 and A 2 of the polydimethylsiloxane represented by the general formula [2] are preferably a divalent hydrocarbon group or oxygen having excellent durability.
　また、本発明の処理剤に使用される前記フルオロアルキルシランは、下記一般式［１］で示されるフルオロアルキルシランが好適に用いられる。 Further, as the fluoroalkylsilane used in the treatment agent of the present invention, a fluoroalkylsilane represented by the following general formula [1] is preferably used.
Figure JPOXMLDOC01-appb-C000007
 　ここで、Ｙ1は１価の加水分解可能な官能基である。さらに、［ｍ］は４～６の整数であり、フルオロカーボンユニット（ＣＦ2又はＣＦ3）の数を表す。さらに、［ｐ］は１～３の整数であり、加水分解可能な官能基の数を表す。
Figure JPOXMLDOC01-appb-C000007
 Here, Y 1 is a monovalent hydrolyzable functional group. [M] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ). [P] is an integer of 1 to 3, and represents the number of functional groups that can be hydrolyzed.
　フルオロカーボンユニット（ＣＦ2又はＣＦ3）の数が増加すると、得られる滑水層の耐アルカリ性、耐摩耗性が増加する。しかしながら、 [ｍ]の数が大きなフルオロアルキルシランは入手が難しくなってきており、これら物質を使用してなる処理剤はコストが上昇することが予想されている。 When the number of fluorocarbon units (CF 2 or CF 3 ) is increased, the alkali resistance and wear resistance of the resulting water slidable layer are increased. However, fluoroalkylsilanes having a large number of [m] are becoming difficult to obtain, and it is expected that the cost of treatment agents using these materials will increase.
　従って、得られる滑水層の耐アルカリ性、耐摩耗性を向上させ、且つ処理剤の塗布を容易にせしめ、さらに乾燥後の余剰分の除去を容易にせしめるためには、フルオロカーボンユニットの数は４～６とすることが重要である。 Therefore, in order to improve the alkali resistance and wear resistance of the resulting water-sliding layer, to facilitate the application of the treatment agent, and to facilitate the removal of the excess after drying, the number of fluorocarbon units is 4. It is important to set to 6.
　さらにまた、前記フルオロアルキルシランは、その混入量を、処理剤の総量に対し、質量濃度で０．４～２．５質量％とすることが重要である。０．４質量％未満では耐アルカリ性や耐摩耗性が著しく低下する。また、２．５質量％を超えると滑水性が大幅に低下し、転落角が２２°を超える。そして、より高い滑水性（転落角；２０°以下）と耐アルカリ性を得るためには、その混入量を、質量濃度で０．６～２．０質量％とすることが好ましい。 Furthermore, it is important that the fluoroalkylsilane is mixed in an amount of 0.4 to 2.5% by mass with respect to the total amount of the processing agent. If it is less than 0.4% by mass, alkali resistance and wear resistance are remarkably lowered. On the other hand, if it exceeds 2.5% by mass, the water slidability is greatly reduced, and the falling angle exceeds 22 °. In order to obtain higher sliding properties (falling angle: 20 ° or less) and alkali resistance, the mixing amount is preferably 0.6 to 2.0% by mass.
　前記フルオロアルキルシランとしては、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2ＯＣＨ3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2ＯＣＨ3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣＨ3Ｃｌ2、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2Ｃｌ、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2ＳｉＣＨ3Ｃｌ2、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2Ｃｌ等のものが使用できる。 Examples of the fluoroalkylsilane include CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 5 CH 2 CH 2 SiCH 3 (OCH 3 ) 2 , and CF 3 (CF 2 ). 5 CH 2 CH 2 Si (CH 3 ) 2 OCH 3 , CF 3 (CF 2 ) 3 CH 2 CH 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 3 CH 2 CH 2 SiCH 3 (OCH 3 ) 2 , CF 3 (CF 2) 3 CH 2 CH 2 Si (CH 3) 2 OCH 3, CF 3 (CF 2) 5 CH 2 CH 2 SiCl 3, CF 3 (CF 2) 5 CH 2 CH 2 SiCH 3 Cl 2 CF 3 (CF 2 ) 5 CH 2 CH 2 Si (CH 3 ) 2 Cl, CF 3 (CF 2 ) 3 CH 2 CH 2 SiCl 3 , CF 3 (CF 2 ) 3 CH 2 CH 2 SiCH 3 Cl 2 , CF 3 (CF 2 ) 3 CH 2 CH 2 Si (CH 3 ) 2 Cl or the like can be used.
　また、機能成分での加水分解可能な官能基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等のアルコキシ基、クロロ基又はイソシアネート基等を用いることができる。ただし、加水分解可能な官能基の反応性が高すぎると、処理剤を調合する時の取扱いが難しくなるだけでなく、処理剤のポットライフが短くなる。一方、反応性が低すぎると、加水分解反応が十分進行しなくなり、生成するシラノール基の量が十分でなくなるため、基材と得られる滑水層の結合が十分でなくなり、滑水層の耐久性が低くなる。取扱いの容易さ、処理剤のポットライフ、得られる滑水層の耐久性を考慮すると、加水分解可能な官能基としてはアルコキシ基が好ましく、中でもメトキシ基、エトキシ基が特に好ましい。 As the functional group capable of being hydrolyzed in the functional component, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group, a chloro group, or an isocyanate group can be used. However, if the reactivity of the hydrolyzable functional group is too high, not only is the handling difficult when preparing the treatment agent, but 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, resulting in insufficient bonding between the substrate and the resulting slidable layer, and durability of the slidable layer. Low. In view of ease of handling, pot life of the treatment agent, and durability of the resulting water slidable layer, the hydrolyzable functional group is preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
　また、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとの総量を０．７～４．５質量％とすることが重要である。０．７質量％未満では耐アルカリ性や耐摩耗性が著しく低下する。また、４．５質量％を超えると、余剰分が乾固物となって基材上に残留する量が多くなり、紙タオルなどで透明に拭き上げることが難しくなる。これにより、目視観察で余剰成分が白くまだらに残留しており、外観上の問題が発生する。従って、その混入量を、質量濃度で０．９～４．５質量％とすることが好ましい。 Also, it is important that the total amount of the linear polydimethylsiloxane and the fluoroalkylsilane is 0.7 to 4.5% by mass. If it is less than 0.7% by mass, alkali resistance and wear resistance are remarkably lowered. On the other hand, if it exceeds 4.5% by mass, the surplus becomes a dry solid and the amount remaining on the substrate increases, and it becomes difficult to wipe it transparent with a paper towel or the like. As a result, the surplus component remains white and mottled by visual observation, causing a problem in appearance. Therefore, the mixing amount is preferably 0.9 to 4.5% by mass in terms of mass concentration.
　また、加水分解反応前において、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとの質量比を７．５：１～１：１２．５とすることが重要である。上記範囲内とすることで優れた滑水性（転落角；２０°以下）と耐アルカリ性が得られ、４．２：１～１：１０とすることがより好ましい。 It is also important that the mass ratio of the linear polydimethylsiloxane and the fluoroalkylsilane is 7.5: 1 to 1: 12.5 before the hydrolysis reaction. Within the above range, excellent water slidability (falling angle: 20 ° or less) and alkali resistance can be obtained, and 4.2: 1 to 1:10 is more preferable.
　処理剤に用いる溶媒には、他の成分（直鎖状ポリジメチルシロキサン、フルオロアルキルシラン、水、酸）を溶解させる有機溶媒を用いることができ、これらにはエチルアルコール、イソプロピルアルコール等の低級アルコール、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、ヘキサン、トルエン、ベンゼン、キシレン等の炭化水素溶媒類、ジエチルエーテル、ジイソプロピルエーテル等のエーテル類やそれらの混合物を用いることが好ましい。中でも、メチルエチルケトン、酢酸エチル、ヘキサン、ジエチルエーテル及びジイソプロピルエーテルの中から選ばれる一種以上の溶媒とエチルアルコールやイソプロピルアルコール等の低級アルコールの混合溶媒は、直鎖状ポリジメチルシロキサン、フルオロアルキルシラン、水及び酸の溶解性が高く、さらに、処理剤の塗布性（塗り伸ばしやすさ）や処理剤の乾燥時間（作業時間）が適度になるので特に好ましい。 The solvent used for the treating agent can be an organic solvent that dissolves other components (linear polydimethylsiloxane, fluoroalkylsilane, water, acid), and these include lower alcohols such as ethyl alcohol and isopropyl alcohol. , 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 diethyl ether and diisopropyl ether, and mixtures thereof It is preferable. Among them, a mixed solvent of at least one solvent selected from methyl ethyl ketone, ethyl acetate, hexane, diethyl ether and diisopropyl ether and a lower alcohol such as ethyl alcohol or isopropyl alcohol is linear polydimethylsiloxane, fluoroalkylsilane, water. In addition, the solubility of the 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.
　また、本発明の処理剤に使用される水は、前記直鎖状ポリジメチルシロキサン及び前記フルオロアルキルシランが有する加水分解可能な官能基の数に対して、分子数で１倍～１００倍とするのが好ましい。１倍未満では、加水分解反応が十分に進行せず、シラノール基が十分に生成しにくく、得られる滑水層の耐久性が低下し、好ましくない。また、１００倍を超えると、前記直鎖状ポリジメチルシロキサン、前記フルオロアルキルシラン及び水が処理剤内で均一に溶解することが難しくなり好ましくない。また、水の量が増えると、反応速度が大きくなり、結果として処理剤のポットライフが短くなる。従って、ポットライフを考慮すると５０倍以下であることがより好ましい。 The water used in the treating agent of the present invention is 1 to 100 times in terms of the number of molecules relative to the number of hydrolyzable functional groups of the linear polydimethylsiloxane and the fluoroalkylsilane. Is preferred. If it is less than 1 time, the hydrolysis reaction does not proceed sufficiently, silanol groups are hardly generated sufficiently, and the durability of the resulting water slidable layer is lowered, which is not preferable. Moreover, when it exceeds 100 times, it becomes difficult for the said linear polydimethylsiloxane, the said fluoroalkylsilane, and water to melt | dissolve uniformly in a processing agent, and it is unpreferable. Further, when the amount of water increases, the reaction rate increases, and as a result, the pot life of the treatment agent is shortened. Therefore, considering the pot life, it is more preferably 50 times or less.
　さらに処理剤に使用される酸は、機能成分の加水分解反応を促進させる触媒的な役割をし、硝酸、塩酸、硫酸、その他有機酸等を使用することができる。そして、前記水と混合した状態でｐＨ値が０～５、好ましくは、０～３となるように混合される。 Furthermore, 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, sulfuric acid, other organic acids, and the like can be used. Then, the mixture is mixed so that the pH value becomes 0 to 5, preferably 0 to 3, in the state of being mixed with the water.
　次に本発明の滑水性物品の滑水層を形成せしめるための処理剤の好ましい調製方法について説明する。 Next, a preferred method for preparing the treatment agent for forming the water slidable layer of the water-slidable article of the present invention will be described.
　滑水層を形成せしめるための処理剤は、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランと溶媒の混合物に、加水分解反応を起こさせるための水と酸を添加、混合し、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとを加水分解させることにより得られる。ここで、直鎖状ポリジメチルシロキサンとフルオロアルキルシランとを先に混合するのは、両成分を処理剤中に均質に混合させるためである。しかしながら、酸、水、直鎖状ポリジメチルシロキサン及びフルオロアルキルシランを同時に混合しても良い。 The treatment agent for forming the water slidable layer is a mixture of the linear polydimethylsiloxane, the fluoroalkylsilane, and a solvent, and water and an acid for causing a hydrolysis reaction are added and mixed. It can be obtained by hydrolyzing the polydimethylsiloxane and the fluoroalkylsilane. Here, the reason why the linear polydimethylsiloxane and the fluoroalkylsilane are mixed first is to mix both components homogeneously in the treating agent. However, acid, water, linear polydimethylsiloxane and fluoroalkylsilane may be mixed simultaneously.
　次に、得られた処理剤を使用して、滑水層を得る方法について説明する。 Next, a method for obtaining a sliding layer using the obtained treatment agent will be described.
　上記で得られた処理剤を基材表面に塗布する塗布方法としては、刷毛塗り、手塗り、ロボット塗り、ノズルフローコート法、ディッピング法、スプレー法、リバースコート法、フレキソ法、印刷法、フローコート法、スピンコート法、ロールコート法、それらの併用等各種被膜の形成方法が適宜採用し得る。 Application methods for applying the treatment agent obtained above to the substrate surface include brush coating, hand coating, robot coating, nozzle flow coating method, dipping method, spray method, reverse coating method, flexo method, printing method, flow Various film forming methods such as a coating method, a spin coating method, a roll coating method, and a combination thereof can be appropriately employed.
　本発明の処理剤は塗布後に５０～２５０℃で加熱を行うが、その加熱温度よりも高い耐熱温度を有するものであれば、処理剤が塗布される基材は特に限定されるものではない。例えば、建築物用窓ガラスや鏡に通常使用されているフロ－ト板ガラス、又はロ－ルアウト法で製造されたソーダ石灰ガラス等無機質の透明性がある板ガラスを使用できる。これら板ガラスを用いて形成される鏡等の反射性基材、擦りガラス、模様が刻まれたガラス等の半透明から不透明のガラス基材を使用することができる。 The treatment agent of the present invention is heated at 50 to 250 ° C. after coating, but the substrate to which the treatment agent is applied is not particularly limited as long as it has a heat resistance temperature higher than the heating temperature. For example, it is possible to use a plate glass having an inorganic transparency such as a float plate glass usually used for a window glass for a building or a mirror, or soda lime glass produced by a roll-out method. A translucent to opaque glass substrate such as a reflective substrate such as a mirror formed by using these plate glasses, rubbed glass, or glass with a pattern engraved thereon can be used.
　前記ガラス製基材の他にタイル、瓦、衛生陶器、食器等に使用されるセラミックス材料よりなる基材、ガラス窓等の枠体、調理器、メス、注射針等の医療器具、流し、自動車のボディ等に使用されるステンレス鋼、アルミニウム、鉄鋼等の金属材料、プラスチック製の基材、例えば、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリメチルメタアクリレート樹脂、ポリエチレン樹脂、ポリ塩化ビニル樹脂、その他のプラスチック基材を使用することがある。 In addition to the glass substrate, substrates made of ceramic materials used for tiles, tiles, sanitary ware, tableware, frames such as glass windows, cookers, scalpels, medical instruments such as scalpels, injection needles, sinks, automobiles Metal materials such as stainless steel, aluminum, steel, etc. used in the body of plastics, plastic base materials such as polycarbonate resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polyethylene resin, polyvinyl chloride resin, other plastics A substrate may be used.
　次に処理剤を基材に塗布後の処理について述べる。基材に処理剤を塗布後、５０～２５０℃で加熱させることで、前記ポリジメチルシロキサン及び前記フルオロアルキルシランを基材と結合させる。加熱は、常圧下、加圧下、減圧下、不活性雰囲気下で行っても良い。また、マイクロ波加熱も有効である。 Next, the treatment after applying the treatment agent to the substrate will be described. After the treatment agent is applied to the substrate, the polydimethylsiloxane and the fluoroalkylsilane are bonded to the substrate by heating at 50 to 250 ° C. Heating may be performed under normal pressure, increased pressure, reduced pressure, or an inert atmosphere. Microwave heating is also effective.
　最後に、余剰分が乾固物となって滑水層上に残留するので、この余剰分を有機溶剤で湿らした紙タオルや布および／または乾いた紙タオルや布で払拭することにより滑水層が形成された基材が得られる。 Finally, since the surplus is dried and remains on the sliding layer, the surplus is wiped with a paper towel or cloth dampened with an organic solvent and / or a dry paper towel or cloth. A substrate on which a layer has been formed is obtained.
　本発明における滑水性とは、実施例の評価方法で述べるような方法で評価されるもので、サンプル表面上に５０μｌの純水を滴下した後、該サンプルを徐々に傾けていき、水滴が動き始める時点の傾斜角度を測定することで評価するものである。尚、該傾斜角度を転落角（°）とし、転落角は協和界面科学製ＣＡ－Ａ型を用いて大気中（約２５℃）で測定した。 In the present invention, the water slidability is evaluated by a method as described in the evaluation method of the example. After dropping 50 μl of pure water on the sample surface, the sample is gradually tilted, and the water droplets move. It is evaluated by measuring the tilt angle at the start. The inclination angle was defined as a sliding angle (°), and the sliding angle was measured in the atmosphere (about 25 ° C.) using a CA-A type manufactured by Kyowa Interface Science.
　以下に本発明の実施例について説明する。尚、本発明はこれらの実施例に限定されるものではない。滑水層の評価方法を以下に示す。 Examples of the present invention will be described below. The present invention is not limited to these examples. The evaluation method of the sliding layer is shown below.
　〔滑水層の評価方法〕
　（１）接触角
　滑水層を有するサンプル表面に、純水約２μｌを置いたときの水滴とサンプル表面とのなす角を接触角計で測定した。尚、接触角計には協和界面科学製ＣＡ－Ｘ型を用い、大気中（約２５℃）で測定した。接触角の初期性能が、１００°以上のものを撥水性の指標に関して合格（表２中で○と表記）とした。 [Evaluation method of water slide layer]
(1) Contact angle The angle formed by the water droplet and the sample surface when about 2 μl of pure water was placed on the sample surface having the water slidable layer was measured with a contact angle meter. The contact angle meter was a CA-X model manufactured by Kyowa Interface Science and measured in the atmosphere (about 25 ° C.). When the initial performance of the contact angle was 100 ° or more, the water repellency index was acceptable (indicated as “◯” in Table 2).
　（２）転落角
　サンプルを水平に保持した状態で、サンプル表面上に５０μｌの純水を滴下した後、サンプルを徐々に傾けていき、水滴が動き始める時点の傾斜角度を転落角（°）とした。尚、転落角は協和界面科学製ＣＡ－Ａ型を用いて大気中（約２５℃）で測定した。転落角の初期性能が、２２°以下のものを滑水性の指標に関し合格（表２中で○と表記）とした。 (2) Falling angle After holding 50 μl of pure water on the sample surface while holding the sample horizontally, the sample is gradually tilted, and the tilt angle at the time when the water droplet starts to move is defined as the falling angle (°). did. 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 was 22 ° or less, it was determined to pass (shown as “◯” in Table 2) with respect to the sliding property index.
　（３）耐アルカリ性
　サンプルを０．１質量％のＮａＯＨ水溶液に室温で２ｈ接触させた。その後、サンプルを水洗して乾燥させた後、目視観察を行うとともに、前記「（１）接触角」に記載した手順で接触角を測定し、接触角が９０°以上のものを合格（表２中で○と表記）とした。 (3) Alkali resistance The sample was brought into contact with a 0.1 mass% NaOH aqueous solution at room temperature for 2 h. Thereafter, the sample was washed with water and dried, then visually observed, and the contact angle was measured according to the procedure described in “(1) Contact angle”. (Indicated by ○).
　（４）耐水性
　サンプル表面に工業用水を噴霧し、５０℃×３ｈ乾燥させ、その後サンプル表面を綿１００％の雑巾を用いて３００ｇ／ｃｍ2の荷重で５往復払拭した。払拭後、目視観察を行うとともに、前記「（１）接触角」に記載した手順で接触角を測定し、接触角が９０°以上のものを合格（表２中で○と表記）とした。 (4) Water resistance Industrial water was sprayed on the sample surface and dried at 50 ° C. for 3 hours, and then the sample surface was wiped 5 times with a load of 300 g / cm 2 using a 100% cotton cloth. After wiping, visual observation was performed, and the contact angle was measured according to the procedure described in “(1) Contact angle”. A contact angle of 90 ° or more was determined to be acceptable (indicated as “◯” in Table 2).
　（５）耐摩耗性
　ガラス用研摩剤ミレークＥ４０Ｔ（三井金属鉱業製）を水道水に分散させたセリア懸濁液（１０質量％）を染み込ませた綿布で、サンプルに約１.５ｋｇ／ｃｍ2の荷重をかけて、被膜の周縁部から被膜の中心部を経て反対側の被膜周縁部まで摺動することで研摩をした。この摺動作業にて、綿布が元の場所に戻ったときを１回研摩回数とし、研摩領域の全領域が親水化（セリア懸濁液を弾かなくなる状態）するまでの研摩回数を評価した。４０回以上を合格（表２中で○と表記）とした。 (5) Abrasion resistance A cotton cloth impregnated with a ceria suspension (10% by mass) in which abrasive for glass EmiraT E40T (Mitsui Mining & Mining) is dispersed in tap water, and about 1.5 kg / cm 2 on the sample. Was applied by sliding from the peripheral edge of the coating to the peripheral edge of the coating on the opposite side through the central portion of the coating. In this sliding operation, the time when the cotton cloth returned to the original position was defined as the number of times of polishing, and the number of times of polishing until the entire region of the polishing region became hydrophilic (a state in which the ceria suspension was not repelled) was evaluated. 40 times or more was regarded as acceptable (indicated as “◯” in Table 2).
　（実施例１）
　（１）処理剤の調製
　サンプルの作製条件を表１に示す。先ず、ジメチルシロキサンユニットの数が２５０の両末端トリアルコキシタイプ直鎖状ポリジメチルシロキサン〔（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2{Ｓｉ（ＣＨ3）2Ｏ}250Ｓｉ（ＣＨ3）2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕；０．４０ｇ、メチルエチルケトン；４８．８５ｇ、フルオロカーボンユニットの数が６のフルオロアルキルシラン〔ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕；０．６０ｇとイソプロピルアルコール；４８．８５ｇを混合し、約５分間攪拌した。次いで、０．５Ｎ硝酸水溶液；１．０ｇを添加し、室温で２時間攪拌して、直鎖状ポリジメチルシロキサンとフルオロアルキルシランを加水分解した。以上の方法により、処理剤の総量に対し、混入された直鎖状ポリジメチルシロキサンの質量濃度（「ポリジメチルシロキサン濃度」と記載する）が０．４質量％、処理剤の総量に対し、混入されたフルオロアルキルシランの質量濃度（「フルオロアルキルシラン濃度」と記載する）が０．６質量％の処理剤を得た。 Example 1
(1) Preparation of treatment agent Table 1 shows sample preparation conditions. First, both terminal trialkoxy type linear polydimethylsiloxane having 250 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 {Si (CH 3 ) 2 O} 250 Si (CH 3 ) 2 CH 2 CH 2 Si (OCH 3) 3]; 0.40 g, methyl ethyl ketone; 48.85G, fluoroalkyl silanes having fluorocarbon units 6 [CF 3 (CF 2) 5 CH 2 CH 2 Si (OCH 3) 3 ]; 0.60 g and isopropyl alcohol; 48.85 g were mixed and stirred for about 5 minutes. Next, 0.5 g of nitric acid aqueous solution (1.0 g) was added, and the mixture was stirred at room temperature for 2 hours to hydrolyze linear polydimethylsiloxane and fluoroalkylsilane. By the above method, the mass concentration of the linear polydimethylsiloxane mixed (described as “polydimethylsiloxane concentration”) is 0.4 mass% with respect to the total amount of the processing agent, and is mixed with respect to the total amount of the processing agent. Thus, a treating agent having a mass concentration of fluoroalkylsilane (referred to as “fluoroalkylsilane concentration”) of 0.6% by mass was obtained.
　（２）ガラス基板の洗浄
　３００ｍｍ×３００ｍｍ×２ｍｍ厚サイズのフロートガラスの表面を研摩液を用いて研摩し、水洗及び乾燥した。なお、ここで用いた研摩液は、ガラス用研摩剤ミレークＡ（Ｔ）（三井金属鉱業製）を水に混合した２ｗｔ％のセリア懸濁液を用いた。 (2) Cleaning of glass substrate The surface of 300 mm × 300 mm × 2 mm thick float glass 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 abrasives, Miraku A (T) (manufactured by Mitsui Kinzoku Mining Co., Ltd.) with water.
　（３）滑水層の形成
　上記（１）で調製した処理剤；１．０ｍｌをガラス基板上に滴下し、綿布（商品名；ベンコット）でガラス全面に十分引き伸ばした後、５分程度風乾した。その後、ガラスを電気炉に入れ１０分間熱処理した。このとき、ガラスの最高温度（熱処理温度）は１５０℃であった。最後に、目視で白くまだらに残留している余剰な撥水成分をイソプロピルアルコールで湿らした紙タオルで拭き上げて、目視観察で問題の無い透明なサンプルを得た。 (3) Formation of water-sliding layer The treatment agent prepared in (1) above: 1.0 ml was dropped on a glass substrate, and fully stretched over the entire surface of the glass with a cotton cloth (trade name; Bencott), and then air-dried for about 5 minutes. . Thereafter, the glass was placed in an electric furnace and heat-treated for 10 minutes. At this time, the maximum temperature (heat treatment temperature) of the glass was 150 ° C. Finally, the excess water-repellent component remaining visually mottled was wiped off with a paper towel moistened with isopropyl alcohol to obtain a transparent sample having no problem with visual observation.
　上記［滑水層の評価方法］に記載した要領で評価したところ、表２に示すとおり、初期転落角は２０°と良好な水滴転落性を示した。さらに、耐アルカリ性試験後の目視観察においてサンプルの透明性に変化が無く、接触角も９０°以上であった。また、耐水性試験後の目視観察においてサンプルの透明性に変化が無く、接触角も９０°以上であり、耐久性に優れていた。また、耐摩耗性の評価においては研摩領域の全領域を親水化させるのに５０往復を要し、耐摩耗性に優れていた。 As evaluated in the manner described in [Evaluation method of water sliding layer] above, as shown in Table 2, the initial falling angle was 20 °, indicating a good water droplet falling property. Furthermore, in the visual observation after the alkali resistance test, there was no change in the transparency of the sample, and the contact angle was 90 ° or more. Further, in the visual observation after the water resistance test, there was no change in the transparency of the sample, the contact angle was 90 ° or more, and the durability was excellent. Further, in the evaluation of wear resistance, 50 reciprocations were required to make the entire polishing region hydrophilic, and the wear resistance was excellent.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　（実施例２）
　フルオロアルキルシラン濃度を１．５質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２０°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 (Example 2)
Except that the fluoroalkylsilane concentration was 1.5% by mass, everything was the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 20 °, showing good water droplet falling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（実施例３）
　直鎖状ポリジメチルシロキサンとして、ジメチルシロキサンユニットの数が５０の両末端トリアルコキシタイプ直鎖状ポリジメチルシロキサン〔（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2{Ｓｉ（ＣＨ3）2Ｏ}50Ｓｉ（ＣＨ3）2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕を用いた以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２０°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 (Example 3)
As the linear polydimethylsiloxane, a trialkoxy type linear polydimethylsiloxane having 50 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 {Si (CH 3 ) 2 O} 50 Si ( Except for using CH 3 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 ], all were the same as in Example 1, and a transparent sample with no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 20 °, showing good water droplet falling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（実施例４）
　直鎖状ポリジメチルシロキサンとして、ジメチルシロキサンユニットの数が４００の両末端トリアルコキシタイプ直鎖状ポリジメチルシロキサン〔（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2{Ｓｉ（ＣＨ3）2Ｏ}400Ｓｉ（ＣＨ3）2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕を用いた以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２１°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 Example 4
As the linear polydimethylsiloxane, both terminal trialkoxy type linear polydimethylsiloxane having 400 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 {Si (CH 3 ) 2 O} 400 Si ( Except for using CH 3 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 ], all were the same as in Example 1, and a transparent sample with no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 21 ° and the water droplet falling property was good, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（実施例５）
　直鎖状ポリジメチルシロキサンの濃度を２．５質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２０°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 (Example 5)
Except that the concentration of the linear polydimethylsiloxane was 2.5% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 20 °, showing good water droplet falling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（実施例６）
　フルオロアルキルシラン濃度を２．０質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２２°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 (Example 6)
Except for the fluoroalkylsilane concentration of 2.0% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial tumbling angle was 22 °, showing good water droplet tumbling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（実施例７）
　処理剤をガラス基板の全面に十分引き伸ばした後、８０℃で熱処理した以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２１°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 (Example 7)
Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then heat-treated at 80 ° C., everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial falling angle was 21 ° and the water droplet falling property was good, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（実施例８）
　処理剤をガラス基板の全面に十分引き伸ばした後、２２０℃で熱処理した以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２２°と良好な水滴転落性を示し、さらに、耐アルカリ性、耐水性も良好であり、耐久性に優れていた。また、耐摩耗性に優れていた。 (Example 8)
Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then heat-treated at 220 ° C., everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial tumbling angle was 22 °, showing good water droplet tumbling properties, and the alkali resistance and water resistance were also good, and the durability was excellent. Moreover, it was excellent in abrasion resistance.
　（比較例１）
　処理剤をガラス基板の全面に十分引き伸ばした後、熱処理しなかった以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角と耐水性は良好であったが、耐アルカリ性及び耐摩耗性は不十分であった。 (Comparative Example 1)
Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then was not heat-treated, everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial sliding angle and water resistance were good as shown in Table 2, but the alkali resistance and wear resistance were insufficient.
　（比較例２）
　処理剤をガラス基板の全面に十分引き伸ばした後、３２０℃で熱処理した以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角と初期接触角が不十分であった。 (Comparative Example 2)
Except that the treatment agent was sufficiently stretched over the entire surface of the glass substrate and then heat-treated at 320 ° C., everything was the same as in Example 1, and a transparent sample having no problem by visual observation was obtained. As a result, as shown in Table 2, the initial falling angle and the initial contact angle were insufficient.
　（比較例３）
　直鎖状ポリジメチルシロキサンとして、ジメチルシロキサンユニットの数が２２の両末端トリアルコキシタイプ直鎖状ポリジメチルシロキサン〔（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2{Ｓｉ（ＣＨ3）2Ｏ}22Ｓｉ（ＣＨ3）2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕を用いた以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、耐摩耗性が不十分であった。 (Comparative Example 3)
As the linear polydimethylsiloxane, both terminal trialkoxy type linear polydimethylsiloxane having 22 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 {Si (CH 3 ) 2 O} 22 Si ( Except for using CH 3 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 ], all were the same as in Example 1, and a transparent sample with no problem in visual observation was obtained. As a result, as shown in Table 2, the physical properties were insufficient in wear resistance.
　（比較例４）
　直鎖状ポリジメチルシロキサンとして、ジメチルシロキサンユニットの数が１０００の両末端トリアルコキシタイプ直鎖状ポリジメチルシロキサン〔（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2{Ｓｉ（ＣＨ3）2Ｏ}1000Ｓｉ（ＣＨ3）2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕を用いた以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、耐摩耗性が不十分であった。 (Comparative Example 4)
As the linear polydimethylsiloxane, both terminal trialkoxy type linear polydimethylsiloxane having 1000 dimethylsiloxane units [(CH 3 O) 3 SiCH 2 CH 2 {Si (CH 3 ) 2 O} 1000 Si ( Except for using CH 3 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 ], all were the same as in Example 1, and a transparent sample with no problem in visual observation was obtained. As a result, as shown in Table 2, the physical properties were insufficient in wear resistance.
　（比較例５）
　フルオロアルキルシランとして、フルオロカーボンユニットの数が１のフルオロアルキルシラン〔ＣＦ3ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3〕を用いた以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、耐アルカリ性及び耐摩耗性が不十分であった。 (Comparative Example 5)
Except for using fluoroalkyl silane [CF 3 CH 2 CH 2 Si (OCH 3 ) 3 ] having one fluorocarbon unit as the fluoroalkyl silane, it is the same as Example 1 and is transparent with no problem in visual observation. Sample was obtained. As a result, as shown in Table 2, the physical properties were insufficient in alkali resistance and wear resistance.
　（比較例６）
　直鎖状ポリジメチルシロキサンの濃度を０．１質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２４°となり滑水性が不十分であった。 (Comparative Example 6)
Except that the concentration of the linear polydimethylsiloxane was 0.1% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial sliding angle was 24 ° and the sliding property was insufficient as shown in Table 2.
　（比較例７）
　直鎖状ポリジメチルシロキサンの濃度を３．５質量％とした以外は、すべて実施例１と同じとした。熱処理後に目視で白くまだらに残留している余剰な撥水成分をイソプロピルアルコールで湿らした紙タオルで拭き上げることを試みたが、完全に除去することができなかった。目視観察で余剰成分が白くまだらに残留しており、外観上問題があった。 (Comparative Example 7)
All were the same as Example 1 except that the concentration of the linear polydimethylsiloxane was 3.5% by mass. Attempts were made to wipe off the excess water-repellent component that remained visually mottled after heat treatment with a paper towel moistened with isopropyl alcohol, but could not be completely removed. As a result of visual observation, the surplus components remained white and mottled, and there was a problem in appearance.
　（比較例８）
　フルオロアルキルシランの濃度を０．２質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、耐アルカリ性及び耐摩耗性が不十分であった。 (Comparative Example 8)
Except that the concentration of fluoroalkylsilane was 0.2% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the physical properties were insufficient in alkali resistance and wear resistance.
　（比較例９）
　フルオロアルキルシランの濃度を３．０質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、初期転落角は２４°となり滑水性が不十分であった。 (Comparative Example 9)
Except that the concentration of fluoroalkylsilane was 3.0% by mass, all were the same as in Example 1, and a transparent sample having no problem in visual observation was obtained. As a result, as shown in Table 2, the initial sliding angle was 24 ° and the sliding property was insufficient as shown in Table 2.
　（比較例１０）
　直鎖状ポリジメチルシロキサンの濃度を０．３質量％とし、フルオロアルキルシランの濃度を０．３質量％とした以外は、すべて実施例１と同じとし、目視観察で問題の無い透明なサンプルを得た。結果、物性は表２に示すとおり、耐アルカリ性及び耐摩耗性が不十分であった。 (Comparative Example 10)
Except that the concentration of linear polydimethylsiloxane was 0.3% by mass and the concentration of fluoroalkylsilane was 0.3% by mass, all were the same as in Example 1, and a transparent sample with no problem in visual observation was used. Obtained. As a result, as shown in Table 2, the physical properties were insufficient in alkali resistance and wear resistance.
　（比較例１１）
　直鎖状ポリジメチルシロキサンの濃度を３．０質量％とし、フルオロアルキルシランの濃度を３．０質量％とした以外は、すべて実施例１と同じとした。熱処理後に目視で白くまだらに残留している余剰な撥水成分をイソプロピルアルコールで湿らした紙タオルで拭き上げることを試みたが、完全に除去することができなかった。目視観察で余剰成分が白くまだらに残留しており、外観上問題があった。 (Comparative Example 11)
All were the same as Example 1 except that the concentration of linear polydimethylsiloxane was 3.0% by mass and the concentration of fluoroalkylsilane was 3.0% by mass. Attempts were made to wipe off the excess water-repellent component that remained visually mottled after heat treatment with a paper towel moistened with isopropyl alcohol, but could not be completely removed. As a result of visual observation, the surplus components remained white and mottled, and there was a problem in appearance.

Claims (2)

  1. ジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及びフルオロカーボンユニット（ＣＦ2又はＣＦ3）の数が４～６であるフルオロアルキルシランのそれぞれを、基材表面に化学的に結合せしめて滑水層を形成する滑水性物品の製法であり、
    該製法は、処理剤を物品表面に塗布する工程と、処理剤が塗布された物品を５０～２５０℃で加熱する工程を有し、
    前記処理剤は、少なくとも一つの末端に加水分解可能な官能基を２個又は３個有し、且つジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及び一般式［１］で表されるフルオロアルキルシラン
    Figure JPOXMLDOC01-appb-C000001
     （ここで、Ｙ1は１価の加水分解可能な官能基である。さらに、［ｍ］は４～６の整数であり、フルオロカーボンユニット（ＣＦ2又はＣＦ3）の数を表す。さらに、［ｐ］は１～３の整数であり、加水分解可能な官能基の数を表す。）、有機溶媒、酸、及び水を有する処理剤であり、該処理剤の総量に対し、加水分解反応前における質量濃度で前記直鎖状ポリジメチルシロキサンが０．２～３．０質量％、前記フルオロアルキルシランが０．４～２．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとの総量が０．７～４．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランの質量比が７．５：１～１：１２．５である処理剤である。     Linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane having 4 to 6 fluorocarbon units (CF 2 or CF 3 ) Each of these is chemically bonded to the substrate surface to form a water slidable layer, and a method for producing a water slidable article,
    The production method includes a step of applying a treatment agent to the surface of an article, and a step of heating the article to which the treatment agent is applied at 50 to 250 ° C.,
    The treatment agent has two or three hydrolyzable functional groups at at least one end, and a linear chain having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—). -Like polydimethylsiloxane and fluoroalkylsilane represented by the general formula [1]
    Figure JPOXMLDOC01-appb-C000001
     (Where Y 1 is a monovalent hydrolyzable functional group. Furthermore, [m] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ). p] is an integer of 1 to 3 and represents the number of hydrolyzable functional groups)), a treatment agent having an organic solvent, an acid, and water, and the total amount of the treatment agent before the hydrolysis reaction. The linear polydimethylsiloxane is 0.2 to 3.0% by mass, the fluoroalkylsilane is 0.4 to 2.5% by mass, the linear polydimethylsiloxane and the fluoroalkylsilane Is a treating agent having a total amount of 0.7 to 4.5% by mass and a mass ratio of the linear polydimethylsiloxane to the fluoroalkylsilane of 7.5: 1 to 1: 12.5.
  2. ジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及びフルオロカーボンユニット（ＣＦ2又はＣＦ3）の数が４～６であるフルオロアルキルシランのそれぞれを、基材表面に化学的に結合せしめて形成された滑水層を有する滑水性物品であり、
    前記滑水層は、少なくとも一つの末端に加水分解可能な官能基を２個又は３個有し、且つジメチルシロキサンユニット（－Ｓｉ（ＣＨ3）2Ｏ－）の数が３０～４００である直鎖状ポリジメチルシロキサン、及び一般式［１］で表されるフルオロアルキルシラン
    Figure JPOXMLDOC01-appb-C000002
     （ここで、Ｙ1は１価の加水分解可能な官能基である。さらに、［ｍ］は４～６の整数であり、フルオロカーボンユニット（ＣＦ2又はＣＦ3）の数を表す。さらに、［ｐ］は１～３の整数であり、加水分解可能な官能基の数を表す。）、有機溶媒、酸、及び水を有する処理剤であり、該処理剤の総量に対し、加水分解反応前における質量濃度で前記直鎖状ポリジメチルシロキサンが０．２～３．０質量％、前記フルオロアルキルシランが０．４～２．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランとの総量が０．７～４．５質量％、前記直鎖状ポリジメチルシロキサンと前記フルオロアルキルシランの質量比が７．５：１～１：１２．５である処理剤を、物品表面に塗布し、５０～２５０℃での加熱を経て物品の表面と化学的に結合せしめ、前記ジメチルシロキサンユ
    ニットと前記フルオロカーボンユニットを基材表面に露出させて形成されたものである。     Linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane having 4 to 6 fluorocarbon units (CF 2 or CF 3 ) A water-slidable article having a water-sliding layer formed by chemically bonding each of the above to a substrate surface,
    The water-sliding layer has two or three hydrolyzable functional groups at at least one end, and the number of dimethylsiloxane units (—Si (CH 3 ) 2 O—) is 30 to 400. Linear polydimethylsiloxane and fluoroalkylsilane represented by general formula [1]
    Figure JPOXMLDOC01-appb-C000002
     (Where Y 1 is a monovalent hydrolyzable functional group. Furthermore, [m] is an integer of 4 to 6, and represents the number of fluorocarbon units (CF 2 or CF 3 ). p] is an integer of 1 to 3 and represents the number of hydrolyzable functional groups)), a treatment agent having an organic solvent, an acid, and water, and the total amount of the treatment agent before the hydrolysis reaction. The linear polydimethylsiloxane is 0.2 to 3.0% by mass, the fluoroalkylsilane is 0.4 to 2.5% by mass, the linear polydimethylsiloxane and the fluoroalkylsilane A treatment agent having a total amount of 0.7 to 4.5% by mass and a mass ratio of the linear polydimethylsiloxane to the fluoroalkylsilane of 7.5: 1 to 1: 12.5 is applied to the surface of the article. And after heating at 50-250 ° C The dimethylsiloxane unit and the fluorocarbon unit are exposed on the surface of the base material and chemically bonded to the surface of the substrate.
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