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WO2009144999A1 - Agent de revêtement hydrophile, film de revêtement hydrophile et base hydrophile - Google Patents

Agent de revêtement hydrophile, film de revêtement hydrophile et base hydrophile Download PDF

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Publication number
WO2009144999A1
WO2009144999A1 PCT/JP2009/055931 JP2009055931W WO2009144999A1 WO 2009144999 A1 WO2009144999 A1 WO 2009144999A1 JP 2009055931 W JP2009055931 W JP 2009055931W WO 2009144999 A1 WO2009144999 A1 WO 2009144999A1
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Prior art keywords
component
mass
hydrophilic coating
hydrophilic
agent
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Ceased
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PCT/JP2009/055931
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English (en)
Japanese (ja)
Inventor
亮一 中井
雅雄 木口
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Harima Chemicals Inc
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Harima Chemicals Inc
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Priority to KR1020107013733A priority Critical patent/KR101234133B1/ko
Priority to JP2010514406A priority patent/JP5361883B2/ja
Priority to CN2009801015942A priority patent/CN101910334B/zh
Publication of WO2009144999A1 publication Critical patent/WO2009144999A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a hydrophilic coating for imparting antifogging properties to spectacle lenses, window materials, etc., a hydrophilic coating obtained from the hydrophilic coating, and a hydrophilic substrate on which the hydrophilic coating is formed. .
  • hydrophilic coating agents for imparting antifogging properties to spectacle lenses, window materials, and the like, which are made of glass or plastic material as a base material, are known.
  • Patent Document 1 listed below discloses a hydrophilic hard coat composition for forming a hydrophilic film that achieves both scratch resistance and antifogging properties. Specifically, a monomer having at least three (meth) acryloyl groups in one molecule, a hydrophilic monomer having a functional group selected from a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and an inorganic colloid sol A hydrophilic hard coat composition is disclosed.
  • Patent Document 2 discloses a coating agent for forming an anti-fogging film having excellent wear resistance, which can shorten the time of the leveling process. Specifically, it comprises a mixture of a water-absorbing polyol such as organic isocyanate and polyethylene glycol, an acrylic polyol having a hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate as a structural unit, an active hydrogen group-containing surfactant, and a solvent.
  • a coating agent is disclosed.
  • Patent Document 3 discloses an antifogging spectacle lens in which an antifogging coat layer made of an organic material and an inorganic material is formed on a plastic lens substrate for spectacles on which a hard coat layer is formed.
  • an anti-fogging coating layer a coating composition containing colloidal silica, polyvinyl alcohol, polyacrylic acid and a water-containing organic solvent is laminated as a first layer, and methyl silicate is formed on the first layer.
  • a layer formed by laminating a second layer containing aluminum acetylacetone and a water-containing organic solvent is disclosed.
  • a coating composition containing ethyl silicate, colloidal silica, and a water-containing organic solvent is laminated as a first layer, and a polyvinyl alcohol partial kenne is laminated on the first layer.
  • a layer formed by laminating a second layer containing a compound, methyl silicate, acetylacetone aluminum, epoxy silica and the like is disclosed.
  • Patent Document 4 discloses an antifogging coating for forming a coating film having an excellent antifogging performance life.
  • an anti-fogging paint containing colloidal silica sol and a hydrophilic polymer as essential components is described.
  • the hydrophilic polymer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, modified polyvinyl pyrrolidone, and hydrophilic acrylic polymer.
  • the anti-fogging paint may further contain a crosslinking agent such as a polyisocyanate compound.
  • Patent Document 5 discloses a technique for providing a coating agent excellent in adhesion between glass and a coating layer, and glass excellent in scratch resistance and scattering prevention performance using the same. And it is described that this coating agent contains a silane coupling agent, polycaprolactone, polydimethylsiloxane, and an isocyanate resin or a melamine resin.
  • the hydrophilic film formed from the coating agent disclosed in any of the above documents does not have all of hydrophilicity, high hardness, scratch resistance, solvent resistance, and alkali resistance.
  • An object of the present invention is to provide a hydrophilic film having high hardness and excellent scratch resistance, and further having excellent solvent resistance and alkali resistance.
  • One aspect of the present invention includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen and a weight average molecular weight (M w ) of 5,000 to 200,000, (C) a silane coupling agent, and (D) A hydrophilic coating agent containing a main component containing a polylactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent, comprising (A) component and (B) component
  • the mass ratio [(A) / (B)] is 5/95 to 95/5, and the mass ratio of the sum of the components (A) and (B) to the component (C) [(A + B) / ( C)] is 30/70 to 95/5, the mass ratio [(B) / (D)] of the component (B) to the component (D) is 90/10 to 10/90, and (F) A hydrophilic coating agent characterized in that the surfactant having active hydrogen is 0 to 30% by mass relative to the total
  • the content of the colloidal silica (A) is 5 to 60% by mass
  • the content of the acrylic polymer (B) is 10 to 60% by mass
  • the content of the silane coupling agent (C) is 5%.
  • Hydrophilic property wherein the content ratio of the (D) polylactone polyol is 5 to 75 mass% and the content ratio of the surfactant (F) having active hydrogen is 0 to 15 mass%.
  • another aspect of the present invention is a hydrophilic film obtained by applying any one of the above hydrophilic coating agents to a base material and curing it.
  • another aspect of the present invention is a hydrophilic substrate characterized by being coated with the above hydrophilic film.
  • the hydrophilic coating agent in the present embodiment includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen and a weight average molecular weight (M w ) of 5,000 to 200,000, (C) a silane coupling agent, A hydrophilic coating containing (D) a polylactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent, (A) component and (B) The mass ratio [(A) / (B)] to the component is 5/95 to 95/5, and the mass ratio of the sum of the components (A) and (B) to the component (C) [(A + B ) / (C)] is 30/70 to 95/5, and the mass ratio [(B) / (D)] of the component (B) to the component (D) is 90/10 to 10/90, (F) The surfactant having active hydrogen is 0 to 30% by mass based on the total amount of the component (B) and the component (F).
  • the colloidal silica sol (A) is a component that imparts hydrophilicity to the resulting coating by a silanol group (—Si—OH) on the surface, and further imparts high hardness and solvent resistance.
  • the colloidal silica sol (A) is a colloid or sol of a silica-based compound having a silanol group (—Si—OH) using water, methanol, ethanol, isopropyl alcohol, butanol, xylene, dimethylformamide or the like as a dispersion medium.
  • examples of the colloidal silica sol include those containing silica fine particles and long-chain molecules as dispersoids, which are produced using a basic catalyst using methyl silicate, ethyl silicate and oligomers thereof as raw materials.
  • the average particle size of the dispersoid is preferably 1 to 200 nm, more preferably 10 to 100 nm, from the viewpoint of excellent coating stability and transparency after curing.
  • the average particle diameter is a value calculated in terms of specific surface area.
  • the content (solid content) of the silica-based compound in the colloidal silica sol (A) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass from the viewpoint of excellent particle stability.
  • colloidal silica sol (A) examples include commercially available products such as MEK-ST and methanol silica sol Snowtex series (both manufactured by Nissan Chemical Co., Ltd.); Quartron (manufactured by Fuso Chemical Co., Ltd.); Cataloid S ( Catalyst Chemical Industry Co., Ltd.); Ludox (Grace Co., Ltd.); Silica Doll (Nihon Chemical Industry Co., Ltd.); Adelite (Asahi Denka Kogyo Co., Ltd.) and the like.
  • commercially available products such as MEK-ST and methanol silica sol Snowtex series (both manufactured by Nissan Chemical Co., Ltd.); Quartron (manufactured by Fuso Chemical Co., Ltd.); Cataloid S ( Catalyst Chemical Industry Co., Ltd.); Ludox (Grace Co., Ltd.); Silica Doll (Nihon Chemical Industry Co., Ltd.); Adelite (Asahi Denka Kogyo Co.,
  • the content of the colloidal silica sol (A) in the nonvolatile component of the main component of the hydrophilic coating agent of this embodiment is preferably 5 to 60% by mass, more preferably 5 to 55% by mass, and particularly preferably 10 to 30% by mass. .
  • the content ratio of the colloidal silica sol (A) is less than 5% by mass, the hydrophilicity and solvent resistance of the resulting film tend to be lowered, and the hardness tends to be lowered.
  • the content of the colloidal silica sol (A) exceeds 60% by mass, the hardness of the resulting coating becomes too high, so that cracks are likely to occur and the scratch resistance tends to decrease. is there.
  • the acrylic polymer (B) in the present embodiment is a component that forms a hydrophilic film while maintaining alkali resistance, solvent resistance and the like on the obtained film.
  • the acrylic polymer (B) in this embodiment is an acrylic polymer having active hydrogen and a weight average molecular weight of 5,000 to 200,000. Due to the active hydrogen contained in the acrylic polymer (B), the acrylic polymer (B) forms a crosslinked structure with the colloidal silica sol (A) via the silane coupling agent (C). Moreover, the active hydrogen of the acrylic polymer (B) also becomes a crosslinking point by the curing agent (E).
  • the acrylic polymer (B) having active hydrogen is obtained by polymerizing a monomer mixed solution containing a radical polymerizable monomer having a functional group having active hydrogen (hereinafter, also simply referred to as active hydrogen-containing monomer).
  • a monomer mixed solution containing a radical polymerizable monomer having a functional group having active hydrogen hereinafter, also simply referred to as active hydrogen-containing monomer.
  • Specific examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these, it is preferable to use solution polymerization in which a monomer mixed solution is dissolved in a solvent and polymerized in the presence of a polymerization initiator as necessary.
  • the functional group having active hydrogen include, for example, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, an amide group, a phosphate group, and a mercapto group.
  • a hydroxyl group is preferable from the viewpoint of excellent reactivity with the coupling agent and excellent stability of the coating agent.
  • the acrylic polymer (B) is not particularly limited as long as it is a polymer containing an active hydrogen-containing monomer unit as a constituent unit, and is a radical polymerization having no active hydrogen copolymerizable with the active hydrogen-containing monomer and the active hydrogen-containing monomer. It may be a copolymer with a reactive monomer (hereinafter also simply referred to as an active hydrogen-free monomer) or a homopolymer of an active hydrogen-containing monomer.
  • the content ratio of the active hydrogen-containing monomer unit in the acrylic polymer (B) is preferably 10% by mass or more, more preferably 20% by mass or more, and 100% by mass or less, and further preferably 80% by mass or less.
  • the content ratio of the active hydrogen-containing monomer unit is too low, the hydrophilicity of the resulting film tends to be insufficient.
  • the weight average molecular weight (M w ) of the acrylic polymer (B) is in the range of 5,000 to 200,000, preferably 10,000 to 100,000, and more preferably 10,000 to 30,000.
  • M w weight average molecular weight
  • the weight average molecular weight is less than 5,000, the water resistance and alkali resistance of the surface of the formed hydrophilic film are lowered.
  • the weight average molecular weight exceeds 200,000, the compatibility with the (A) colloidal silica sol is reduced, so that agglomeration occurs in the coating agent, making it difficult to apply or a good coating film is formed. It can no longer be obtained.
  • the hydroxyl value of the acrylic polymer (B) is preferably 10 to 70, more preferably 15 to 65. If the hydroxyl value is too low, the hydrophilicity tends to decrease. Moreover, when the said hydroxyl value is too high, there exists a tendency for the coating film obtained to become cloudy or the colloidal silica sol in a coating agent to aggregate.
  • the hydroxyl value is a value measured by potentiometric titration in accordance with JIS-K0070.
  • the mass ratio [(A) / (B)] of the colloidal silica sol (A) and the acrylic polymer (B) is 5/95 to 95/5 (0.05 to 19). 20/80 to 80/20 (0.25 to 4), more preferably 25/75 to 75/25 (0.3 to 3), particularly preferably 25/75 to 40/60. (0.3 to 0.6).
  • a / B is less than 5/95, the solvent resistance decreases.
  • a / B is higher than 95/5, a good coating film cannot be obtained due to cracks and the like, and the alkali resistance and scratch resistance are lowered.
  • the content ratio of the acrylic polymer (B) in the nonvolatile component of the main component of the hydrophilic coating agent of this embodiment is preferably in the range of 10 to 60% by mass, more preferably 20 to 55% by mass, and particularly preferably. Is 30 to 45% by mass.
  • the content ratio of the acrylic polymer (B) is less than 10% by mass, the hydrophilicity of the resulting film is lowered and the alkali resistance tends to be lowered.
  • the content ratio of the acrylic polymer (B) exceeds 60% by mass, the hardness of the resulting coating film tends to decrease, the solvent resistance decreases, and the scratch resistance tends to decrease.
  • radical polymerizable monomer having a hydroxyl group examples include a hydroxyl group-containing (meth) acrylic acid ester, vinyl ether, or (meth) acrylic acid ester glycol-based adduct.
  • radical polymerizable monomer having a hydroxyl group examples include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • Esters Hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether and cyclohexanedimethanol monovinyl ether; Hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether and cyclohexanedimethanol monoallyl ether; Polyalkylenes such as polyethylene glycol, polypropylene glycol, and tetramethylene glycol Polyol mono (meth) acrylate, which is an ester of polyethylene polyol and (meth) acrylic acid; a product manufactured by Daicel Chemical Industries, Ltd.
  • polyol mono (meth) acrylate examples include commercially available products such as BLEMMER AET series, APT series, AE series, AEP series, BLEMMER AP-400, AP-550, AP-800, BLEMMER PEP series, and PET series.
  • PPT series, PP series all manufactured by NOF Corporation
  • polyol mono (meth) acrylate is preferable because it does not gel during polymerization and does not rapidly increase in viscosity, and enables stable polymerization control.
  • a macromonomer in which a radical-reactive unsaturated double bond and a hydroxyl group are introduced into a polycaprolactone oligomer is particularly preferable from the viewpoint of improving scratch resistance.
  • radical polymerizable monomer containing a carboxyl group examples include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, ⁇ -Unsaturated carboxylic acids such as carboxy-polycaprolactone mono (meth) acrylate.
  • radical polymerizable monomer containing a sulfonic acid group examples include vinyl sulfonic acid, vinyl benzene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like.
  • radical polymerizable monomer containing an amide group examples include, for example, (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl acrylamide, diacetone acrylamide, N -Methylolacrylamide and the like.
  • radical polymerizable monomer containing an amino group examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and the like.
  • radical polymerizable monomer containing a phosphate group examples include (meth) acryloyloxyalkyl acid phosphates such as 2- (meth) acryloyloxyethyl acid phosphate.
  • radical polymerizable monomer having no functional group having active hydrogen examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meta ) Acrylate, benzyl (meth) acrylate, alkyl (meth) acrylate such as dicyclopentadienyl (meth) acrylate; glycidyl (meth) acrylate; trifluoroethyl (meth) acrylate; polysiloxane-containing (meth) acrylate; styrene, Aromatic vinyl compounds such as vinyltoluene and ⁇ -methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl compounds containing alkoxysilyl groups such as 3-methacryloxypropyltriethoxysilane and
  • Any of the above monomers may be used alone or in combination of two or more.
  • the polymerization initiator examples include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-hexyl peroxyneodecanate, and t-butyl peroxybivalate.
  • -Azo compounds such as azobis-iso-butyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile.
  • the polymerization initiators may be used alone or in combination of two or more.
  • the blending ratio of the polymerization initiator is preferably 0.01 to 8 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer.
  • Examples of the solvent for the solution polymerization include ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate, dimethylformamide, dimethyl sulfoxide, and N-methyl-2- Polar solvents such as pyrrolidone, alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbon-based organic solvents such as toluene, xylene, “Solvesso 100” (manufactured by Exxon Chemical), n-hexane, cyclohexane Aliphatic hydrocarbon / alicyclic hydrocarbon organic solvents such as methylcyclohexane, “Loose”, “Mineral Spirit EC” (both manufactured by Shell), cellosolve organic solvents such as methyl cellosolve, e
  • the acrylic polymer (B) is blended in a liquid state such as an acrylic resin solution, an acrylic emulsion, and an acrylic suspension.
  • the solid content concentration of the acrylic polymer (B) in the acrylic resin solution, acrylic emulsion, or acrylic suspension is 10 to 80% by mass, and more preferably 20 to 60% by mass when the acrylic polymer is produced. It is preferable from the viewpoint of workability.
  • the silane coupling agent (C) in the present embodiment is used to form a crosslinked structure between the colloidal silica sol (A) and the acrylic polymer (B) or the polylactone polyol (D). That is, the silane coupling agent (C) reacts with the active hydrogen of the acrylic polymer (B) or polylactone polyol (D) through the functional group at one end, while reacting with the alkoxysilyl group at the other end. A silanol group and a silanol bond on the surface of (A) are formed. Then, by forming a crosslinked structure between the colloidal silica sol (A) and the acrylic polymer (B) or the polylactone polyol (D), hydrophilicity and high alkali resistance are imparted to the obtained coating surface.
  • silane coupling agent (C) examples include, for example, glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd., Silaplane S-510 manufactured by Chisso Corporation, etc.), glycidoxy Epoxy group-containing silane coupling agents such as propyltriethoxysilane (KBE403 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6041 manufactured by Toray Dow Corning Co., Ltd.); aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) ) KBM903, Toray Dow Corning Co., Ltd.
  • glycidoxypropyltrimethoxysilane KBM403 manufactured by Shin-Etsu Chemical Co., Ltd., Silaplane S-510 manufactured by Chisso Corporation, etc.
  • glycidoxy Epoxy group-containing silane coupling agents such as propyltriethoxysilane
  • Group-containing silane coupling agent mercaptopropyltrimethoxysilane (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., Toray Dow) Mercapto group-containing silane coupling agents such as Z-Nepping Co., Ltd. (Z-6062, etc.); Ureidopropyltriethoxysilane (KBE585, Shin-Etsu Chemical Co., Ltd.), Z-6676 (Toray Dow Corning Co., Ltd.), etc.
  • isocyanate group-containing silane coupling agents such as isocyanatepropyltriethoxysilane (KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • silane coupling agents such as isocyanatepropyltriethoxysilane (KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, and isocyanatepropyltriethoxysilane are preferable from the viewpoint of excellent stability and reactivity of the coating agent.
  • a mass ratio of the total amount (A + B) of the colloidal silica sol (A) and the acrylic polymer (B) to the silane coupling agent (C) [(A + B) / (C )] Is 30/70 to 95/5 (0.42 to 19), preferably 50/50 to 90/10 (1 to 9), and more preferably 60/40 to 85/15 (1. 5 to 5.6), particularly preferably 70/30 to 80/20 (2.3 to 4).
  • the mass ratio [(A + B) / (C)] is less than 30/70, the film formability is lowered, so that the surface hardness, water resistance, and the like are lowered.
  • the content ratio of the silane coupling agent (C) in the nonvolatile component of the main component of the hydrophilic coating agent of this embodiment is preferably 5 to 30% by mass, more preferably 10 to 20% by mass.
  • the content of the silane coupling agent (C) is less than 5% by mass, a crosslinked structure is not sufficiently formed between the colloidal silica sol (A) and the acrylic polymer (B) or the polylactone polyol (D). Tend to be.
  • the polylactone polyol (D) in the present embodiment crosslinks with the colloidal silica sol (A) via the silane coupling agent (C), and also crosslinks with the curing agent (E). Gives elasticity. This imparts scratch resistance to the resulting coating.
  • the polylactone polyol (D) is obtained, for example, by ring-opening polymerization of a lactone monomer using a polyhydric alcohol as an initiator.
  • polyhydric alcohol examples include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 2-methyl 1,3-propane.
  • lactone monomers examples include ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ , ⁇ -dimethyl- ⁇ -caprolactone, 3, 3, 5 -Caprolactones such as trimethyl- ⁇ -caprolactone; polyvalerolactones such as ⁇ -valerolactone and ⁇ -methyl- ⁇ -valerolactone; propiolactones; butyrolactones; enanthlactones; dodecanolactone, etc. or derivatives thereof Etc.
  • polycaprolactone diol is represented by the following general formula (1).
  • Polycaprolactone triol is a trivalent hydrocarbon group R ′ in which three polyester chains having terminal hydroxyl groups as shown in the following formula (2) are bonded.
  • polylactone polyol (D) examples include commercially available products such as polycaprolactone triol (for example, Plaxel 303, 305, 308, 312 manufactured by Daicel Chemical Industries, Ltd.), polycaprolactone diol (manufactured by Daicel Chemical Industries, Plaxel). 205, 208, 210, 212).
  • polycaprolactone triol for example, Plaxel 303, 305, 308, 312 manufactured by Daicel Chemical Industries, Ltd.
  • polycaprolactone diol manufactured by Daicel Chemical Industries, Plaxel
  • 205, 208, 210, 212 examples of the polylactone polyol (D)
  • a polycaprolactone polyol having excellent rebound resilience due to a relatively large number of carbon atoms connecting the polyester bonds is particularly preferable.
  • the mass ratio [(B) / (D)] of the acrylic polymer (B) and the polylactone polyol (D) is 90/10 to 10/90 (0.11 to 9), preferably 80/20 to 40/60 (0.6 to 4).
  • the mass ratio [(B) / (D)] is less than 10/90, high scratch resistance can be obtained, but hydrophilicity decreases due to a decrease in the proportion of the acrylic polymer (B).
  • the mass ratio [(B) / (D)] exceeds 90/10, sufficient scratch resistance cannot be obtained.
  • the content ratio of the polylactone polyol (D) in the nonvolatile component of the main component of the hydrophilic coating agent of the present embodiment is in the range of 5 to 75% by mass, further 10 to 50% by mass, and particularly 15 to 30% by mass. It is preferable that When the content of the polylactone polyol (D) is less than 5% by mass, the scratch resistance tends to decrease. On the other hand, when the content of the polylactone polyol (D) exceeds 75% by mass, the hydrophilicity tends to decrease.
  • a small amount of a surfactant (F) having active hydrogen may be blended.
  • the hydrophilicity of the resulting coating surface is further improved.
  • the surfactant has active hydrogen, the hydrophilicity improving effect is maintained for a long time by reacting with the silane coupling agent (C) or the curing agent (E).
  • the blending ratio is too large, hardness and water resistance are lowered. Therefore, the content ratio is limited to the range described later.
  • the surfactant (F) is not particularly limited as long as it has active hydrogen. Specific examples include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant having a functional group having active hydrogen. Examples of the functional group having active hydrogen include a hydroxyl group, a carboxyl group, an amino group, and an amide group.
  • anionic surfactant containing active hydrogen examples include, for example, castor oil monosulfate, castor oil monophosphate, sorbitan fatty acid ester sulfate, sorbitan fatty acid ester phosphate, polyoxyalkylene glycerol ether monosulfate, polyoxyalkylene glycerol Ether monophosphate, perfluoroalkyl ester phosphate and the like can be mentioned.
  • cationic surfactant containing active hydrogen examples include dialkanolamine salts, polyoxyalkylene alkylamine ether salts, polyoxyalkylene alkylammonium salts, polyoxyalkylene dialkanolamine ether salts, and the like.
  • nonionic surfactant containing active hydrogen examples include polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester and the like.
  • amphoteric surfactants containing active hydrogen include N, N-di ( ⁇ -hydroxyalkyl) N-hydroxyethyl-N-carboxyalkylammonium betaine, N, N-di (polyoxyethylene) -N -Alkyl-N-sulfoalkylammonium betaines, perfluoroalkylbetaines and the like.
  • the content ratio is 30% by mass or less with respect to the total amount [(B) + (F)] of the acrylic polymer (B) and the surfactant (F), Preferably, it is 20% by mass or less, preferably 0% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the blending ratio of the surfactant (F) exceeds 30% by mass, the hardness, water resistance, alkali resistance, and solvent resistance of the resulting coating are lowered.
  • the content of the surfactant (F) in the nonvolatile component of the main component of the hydrophilic coating agent of this embodiment is preferably in the range of 0 to 15% by mass, more preferably 1 to 5% by mass.
  • the blending ratio of the surfactant (F) is too high, the hardness, water resistance, alkali resistance, and solvent resistance of the resulting film tend to be lowered.
  • the curing agent (E) in the present embodiment imparts high alkali resistance, water resistance, solvent resistance, etc. to the formed film by crosslinking the acrylic polymer (B) and the polylactone polyol (D). It is an ingredient to do.
  • the curing agent (E) is not particularly limited as long as it is a compound having at least two functional groups having reactivity with active hydrogen possessed by the acrylic polymer (B) and the polylactone polyol (D).
  • the curing agent (E) include at least two or more reactive functional groups, such as polyisocyanate, melamine resin curing agent, epoxy curing agent, carbodiimide curing agent, oxazoline curing agent, and the like. Is mentioned. Among these, polyisocyanates and melamine resin-based curing agents are particularly preferable because polyisocyanates are excellent in reactivity even at relatively low temperatures.
  • polyisocyanate examples include trifunctional polyisocyanates having a biuret, isocyanurate, and allophanate structure starting from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and the like.
  • examples of commercially available products are modified with hydrophilic groups such as D-165N (biuret structure), D-170N (isocyanurate structure), D-178N (allophanate structure), ethylene oxide, etc. manufactured by Mitsui Takeda Chemical Co., Ltd.
  • melamine resin-based curing agent examples include, for example, a Nikarac series manufactured by Sanwa Chemical Co., Ltd. as a commercial product.
  • epoxy curing agent examples include, for example, an epicoat series manufactured by Yuka Shell Epoxy Co., Ltd. and an Epolite series manufactured by Kyoeisha Chemical Co., Ltd. as commercially available products.
  • carbodiimide curing agent examples include, for example, a carbodilite series manufactured by Nisshinbo Co., Ltd. as a commercially available product.
  • oxazoline-based curing agent examples include, for example, EPOCROSS series manufactured by Nippon Shokubai Co., Ltd. as a commercial product.
  • the blending ratio of the curing agent (E) is appropriately selected depending on the types of the acrylic polymer (B) and polylactone polyol (D), the active hydrogen content, and the like. Specifically, for example, when the acrylic polymer (B) is a hydroxyl group-containing acrylic polymer and the curing agent (E) is a polyisocyanate, the isocyanate of the polyisocyanate with respect to 1 equivalent of the hydroxyl group of the hydroxyl group-containing acrylic polymer.
  • the blending ratio is preferably such that the group is 0.2 to 3 equivalents.
  • the isocyanate group of the polyisocyanate is 0. 1 with respect to 1 equivalent of the hydroxyl group of the polylactone triol.
  • the blending ratio is preferably 2 to 3 equivalents.
  • the total amount of the curing agent (E) the total amount required for curing the acrylic polymer (B) and the polylactone polyol (D) is blended.
  • the content of the curing agent (E) in the present embodiment is in the range of 10 to 200 parts by mass, further 20 to 100 parts by mass, particularly 30 to 60 parts by mass with respect to 100 parts by mass of the main agent. It is preferable.
  • the content ratio of the curing agent (E) is too low, the curing reaction does not proceed sufficiently, so that film formation tends to be difficult.
  • curing agent (E) is too high, there exists a tendency for hydrophilicity to fall.
  • the surface hydrophilic coating agent of this embodiment may further contain a cured metal catalyst (G).
  • a cured metal catalyst (G) By blending the cured metal catalyst (G), the hardness and alkali resistance of the coating obtained by promoting the condensation reaction between the colloidal silica sol (A) and the silane coupling agent (C) can be further improved.
  • the cured metal catalyst (G) include tin, titanium, zinc, iron, cobalt, aluminum metal salts, alkoxides, chelate compounds, and the like.
  • Specific examples include aluminum monoacetylacetonate, di-isopropoxytitanium bis (ethylacetoacetate), zirconium tetraethylacetoacetate and the like.
  • the content ratio of the cured metal catalyst (G) in the nonvolatile component of the main component of the hydrophilic coating agent of the present embodiment is 0.01 to 0.2% by mass, and further 0.05 to 0.1% by mass. It is preferable that it is the range of these.
  • the blending ratio of the cured metal catalyst (G) is too high, the hardness and alkali resistance of the resulting coating are improved, but the hydrophilicity tends to decrease.
  • an ultraviolet absorber, an antioxidant, a light stabilizer, a heat stabilizer, an antistatic agent, an antifoaming agent, etc. as necessary, as long as the effects of the present invention are not impaired.
  • these various additives may be further blended.
  • the surface hydrophilic coating agent of this embodiment does not contain polydimethylsiloxane.
  • Polydimethylsiloxane is known as a component that improves scratch resistance.
  • polydimethylsiloxane is hydrophobic. Therefore, hydrophilicity is lost when polydimethylsiloxane is contained in a large amount. Therefore, even if it does not contain polydimethylsiloxane or contains it, it is preferable to suppress it to a ratio of about 0.2% by mass or less and further about 0.1% by mass or less in the main agent.
  • the main component of the surface hydrophilic coating agent of the present embodiment is used as necessary, colloidal silica sol (A), acrylic polymer (B) solution, silane coupling agent (C), polylactone polyol (D), and It is prepared by mixing the surfactant (F) having active hydrogen, the cured metal catalyst (G), other additives and the like so as to have the above-described blending ratio.
  • curing agent (E) is mixed with a main ingredient just before application
  • a colloidal silica sol (A), a silane coupling agent (C), a polylactone polyol (D), a surfactant (F) blended as necessary, and a cured metal catalyst (G) are reserved.
  • the main agent is obtained by mixing while gradually adding the solution of the acrylic polymer (B).
  • a surface hydrophilic coating agent is prepared by adding a hardening
  • the acrylic polymer (B) is gradually dropped into the container over a period of about 30 to 60 minutes. Then, after the dropping is completed, the main agent is adjusted by further stirring at 40 ° C. for about 30 to 60 minutes. And just before apply
  • the base material is not particularly limited, and various resin base materials such as polycarbonate resin, polyacrylic resin, styrene resin, various metal base materials such as stainless steel, steel, and aluminum, and inorganic base materials such as glass are used without particular limitation. It is done. Further, the form of the substrate is not particularly limited, such as a plate, a film or a molded product.
  • Application method is not particularly limited, and various application methods such as dipping, roll coating, spin coating, and bar coating can be used without particular limitation.
  • the applied surface coating agent is thermally cured by heating at a temperature of about 60 to 180 ° C., preferably about 80 to 150 ° C. for 15 to 120 minutes, preferably about 30 to 60 minutes. Thereby, a hydrophilic film is formed. Moreover, as long as it is possible, hardening by normal temperature hardening or photocuring may be sufficient.
  • the thickness of the hydrophilic coating is not particularly limited, but is preferably about 2 to 90 ⁇ m, and more preferably about 5 to 50 ⁇ m.
  • Such a surface coating agent is preferably used for forming a hydrophilic coating on lenses such as glasses and goggles, window materials for buildings, vehicles, and instruments, electronic device parts, and the like.
  • a monomer component consisting of 50 parts of methyl methacrylate (MMA) and 50 parts of polyethylene glycol monomethacrylate (MA-50A, manufactured by Nippon Emulsifier Co., Ltd.) was added as a polymerization catalyst with azobis-2-methylbromonitrile (ABN-). E and 4.0 parts of Nippon Hydrazine Kogyo Co., Ltd.) were mixed by stirring to prepare a monomer mixture.
  • MMA methyl methacrylate
  • MA-50A polyethylene glycol monomethacrylate
  • ABSN- azobis-2-methylbromonitrile
  • the monomer mixture was added dropwise to the above mixed solvent at 60 ° C. over 3 hours, and the reaction was terminated after 3 hours.
  • a resin solution containing an acrylic polymer having a hydroxyl value of 25 and a weight average molecular weight (M w ) of 28000 was produced.
  • Synthesis Example 3 In the same manner as in Synthesis Example 1, except that a monomer component consisting of 50 parts of MMA, 30 parts of N, N-dimethylacrylamide (DMAA), and 20 parts of 2-hydroxyethyl acrylate (2-HEA) was used as the monomer component. A resin solution containing an acrylic polymer having a hydroxyl value of 31 and an amide group and a weight average molecular weight (M w ) of 14,000 was produced.
  • DMAA N, N-dimethylacrylamide
  • 2-HEA 2-hydroxyethyl acrylate
  • Synthesis Example 6 Similar to Synthesis Example 1, except that 100 parts of a monomer composed of MA-50A is used as a monomer component, 6 parts of ABN-E is used as a polymerization catalyst, and 2 parts of 2-mercaptomethanol is added. Thus, a resin solution containing an acrylic polymer having a weight average molecular weight (M w ) of 4000 was produced.
  • M w weight average molecular weight
  • Table 1 summarizes the types of polymerization compositions in Synthesis Examples 1 to 7, the weight average molecular weight (M w ) of the obtained acrylic polymer, the viscosity and nonvolatile content of the resin solution, and the hydroxyl value of the acrylic polymer.
  • Example 1 With the composition as shown in Table 2, a hydrophilic coating agent was prepared by the following method.
  • a hydrophilic coating agent was obtained by stirring and mixing 53 parts of WB40-100 solution as a curing agent with the obtained main agent.
  • Example 2 A hydrophilic coating agent was obtained in the same manner as in Example 1 except that it was prepared according to the composition shown in Table 2.
  • Adhesion An adhesion test was conducted in accordance with the “cross-cut method” test method of JIS K 5600-5-6. Specifically, 100 crosscuts (cut pieces) were formed by cutting the coating film applied to the test plate in the vertical and horizontal directions with a cutter knife and reaching the substrate. Then, a cellophane adhesive tape (for example, product number Nichiban Tape No. 1 manufactured by Nichiban Co., Ltd.) was pasted on the cross cut. And after peeling the cellophane adhesive tape affixed, the number of crosscuts which remained without peeling was counted.
  • a cellophane adhesive tape for example, product number Nichiban Tape No. 1 manufactured by Nichiban Co., Ltd.
  • test plate (water resistant) The test plate was immersed in water at 23 ° C. ⁇ 2 ° C. for 3 days. Then, the appearance of the test piece after immersion was observed, and the water resistance was judged according to the test method of 4.4 “Appearance of coating film” in JIS K 5600-1-1. Excellent: colorless and transparent. Normal: Translucent Inferior: Whitening or dissolution.
  • the test plate was immersed in a 5% aqueous sodium hydroxide solution at 23 ° C. ⁇ 2 ° C. for 3 days. Then, the appearance of the test piece after immersion was observed, and the alkali resistance was judged according to the test method of 4.4 “Appearance of coating film” of JIS K 5600-1-1. Excellent: colorless and transparent. Normal: Translucent Inferior: Whitening or dissolution.
  • the coated surface of the test plate was opposed to the surface of hot water at 50 ° C. with a spacing of 1 cm, and the time until the coating surface began to cloud was measured. Excellent: It took more than 2 minutes to start cloudy. Normal: The time until cloudy began was 1 minute or more and less than 2 minutes. Inferior: Time until cloudy start was less than 1 minute.
  • All the films obtained from the surface coating agents prepared in Examples 1 to 14 had a water contact angle of 50 ° or less, and were excellent in hydrophilicity. Further, the pencil hardness was H or more. Furthermore, it was excellent in scratch resistance. Further, the appearance was colorless and transparent, and no cracks were generated. Furthermore, the solvent resistance, alkali resistance, water resistance, antifogging property, antistatic property and antifouling property were also excellent.
  • the hydrophilic film obtained in Comparative Example 1 had low scratch resistance. This is because (D) polylactone polyol is not contained. Moreover, the hydrophilic film obtained in Comparative Example 2 also had low scratch resistance. This is because the content ratio of (D) polylactone polyol was too low. Moreover, the hydrophilic film obtained in Comparative Example 3 had low hydrophilicity. This is because the content ratio of the acrylic polymer (B) was too low. Further, the hydrophilic film obtained in Comparative Example 4 was cracked, and the alkali resistance, scratch resistance, etc. were low. This is because the content ratio of the acrylic polymer (B) is too low compared to the content ratio of the colloidal silica (A).
  • the hydrophilic film obtained in Comparative Example 5 had low solvent resistance. This is because the content of colloidal silica (A) was too low compared to the content of acrylic polymer (B). Moreover, the hydrophilic film obtained in Comparative Example 6 had low alkali resistance and relatively low hydrophilicity. This is because the content ratio of the silane coupling agent (C) is too low compared to the content ratio of the colloidal silica (A) and the acrylic polymer (B).
  • the hydrophilic film obtained in Comparative Example 7 had low hardness, low adhesion, low water resistance, alkali resistance, etc., and low hydrophilicity.
  • the hydrophilic film obtained in Comparative Example 8 had low hardness, low adhesion, low water resistance, alkali resistance, and the like. This is because the content ratio of the surfactant (F) having active hydrogen was too high. Moreover, the hydrophilic film obtained in Comparative Example 9 had low water resistance and alkali resistance. This is because the molecular weight of the acrylic polymer (B) was too low. Moreover, the hydrophilic coating film obtained in Comparative Example 10 was unable to form a practical coating film due to aggregation of the coating solution. This is because the molecular weight of the acrylic polymer (B) is too high, and the (A) colloidal silica sol becomes difficult to disperse.
  • the hydrophilic coating agent of one aspect of the present invention comprises (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen and a weight average molecular weight (M w ) of 5,000 to 200,000, (C) A silane coupling agent, (D) a polylactone polyol, and (E) a curing agent, and (F) a surfactant having active hydrogen as a sum of components (B) and (F).
  • the mass ratio [(A) / (B)] of the component (A) and the component (B) is 5/95 to 95/5 without containing more than 30% by mass with respect to the amount, (A) The mass ratio [(A + B) / (C)] of the sum of the component and the component (B) to the component (C) is 30/70 to 95/5, and the ratio of the component (B) to the component (D) The mass ratio [(B) / (D)] is 90/10 to 10/90.
  • a hydrophilic coating agent it is possible to form a hydrophilic film having high hardness, excellent scratch resistance, and excellent solvent resistance and alkali resistance.
  • the acrylic polymer (B) has a hydroxyl value of 10 to 70, it is preferable from the viewpoint of imparting more excellent hydrophilicity to the film.
  • the curing agent (E) contains at least one selected from the group consisting of a nurate polyurethane resin, a burette polyurethane resin, and an allophanate polyurethane resin. From the viewpoint of sex.
  • the hydrophilic coating agent further contains a cured metal catalyst (G), and the condensation reaction between the colloidal silica sol (A) and the silane coupling agent (C) is promoted. It is preferable from the viewpoint that the hardness and alkali resistance can be further improved.
  • the hydrophilic coating agent according to another aspect of the present invention includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen and a weight average molecular weight (M w ) of 5,000 to 200,000, and (C) A hydrophilic coating agent containing a silane coupling agent, (D) a polylactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent,
  • the content of the colloidal silica (A) in the non-volatile component is 5 to 60% by mass, preferably 10 to 30% by mass
  • the content of the acrylic polymer (B) is 10 to 60% by mass, preferably 30 to 45% by mass
  • the content of the silane coupling agent (C) is 5 to 30% by mass, preferably 10 to 20% by mass
  • the content of the (D) polylactone polyol is 5 to 75%.
  • the content of the surfactant having the (F) the active hydrogen is 0 to 15 mass%. According to such a hydrophilic coating agent, it is possible to form a hydrophilic film having high hardness, excellent scratch resistance, and excellent solvent resistance and alkali resistance.
  • the mass ratio [(A) / (B)] of the component (A) to the component (B) is 5/95 to 95/5, and the sum of the components (A) and (B) and (C)
  • the mass ratio [(A + B) / (C)] to the component is 30/70 to 95/5, and the mass ratio [(B) / (D)] of the component (B) to the component (D) is It is preferably 90/10 to 10/90.
  • hydrophilic coating according to another aspect of the present invention is obtained by applying any one of the above hydrophilic coating agents to a substrate and curing it.
  • a hydrophilic film has high hardness, excellent scratch resistance, and excellent solvent resistance and alkali resistance.
  • the hydrophilic substrate according to another aspect of the present invention is characterized in that it is coated with the hydrophilic coating.
  • a hydrophilic substrate has a high hardness, excellent scratch resistance, and a surface excellent in solvent resistance and alkali resistance.
  • the hydrophilic coating agent of the present invention is widely used for hydrophilic hard coat materials, antifogging coating agents, antistatic coating agents, antifouling coating agents such as oil stains and fingerprints, and the like.

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Abstract

L'invention porte sur un film de revêtement hydrophile ayant une dureté élevée et une excellente résistance à l'abrasion. Le film de revêtement hydrophile a également une excellente résistance aux solvants et une excellente résistance aux alcalis. L'invention porte également sur un agent de revêtement hydrophile contenant (A) un sol de silice colloïdale, (B) un polymère acrylique contenant un hydrogène actif et ayant une masse moléculaire moyenne en poids (Mw) de 5 000-200 000, (C) un agent de couplage de type silane, (D) un polyol de polylactone et (E) un agent de durcissement. L'agent de revêtement hydrophile contient moins de 30 % en masse de (F) un tensioactif contenant un hydrogène actif par rapport à la masse totale du composant (E) et du composant (F). Le rapport en masse entre le composant (A) et le composant (B), à savoir (A)/(B), est de 5/95 à 95/5 ; le rapport en masse entre le total du composant (A) et du composant (B) et le composant (C), à savoir (A + B)/(C), est de 30/70 à 95/5 ; et le rapport en masse entre le composant (B) et le composant (D), à savoir (C)/(D), est de 90/10 à 10/90.
PCT/JP2009/055931 2008-05-26 2009-03-25 Agent de revêtement hydrophile, film de revêtement hydrophile et base hydrophile Ceased WO2009144999A1 (fr)

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KR1020107013733A KR101234133B1 (ko) 2008-05-26 2009-03-25 친수성 피복제, 친수성 피막 및 친수성 기재
JP2010514406A JP5361883B2 (ja) 2008-05-26 2009-03-25 親水性被覆剤、親水性被膜、及び親水性基材
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Cited By (18)

* Cited by examiner, † Cited by third party
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WO2012035939A1 (fr) * 2010-09-14 2012-03-22 コニカミノルタオプト株式会社 Film de résine, procédé de production de film de résine, plaque de polarisation, et afficheur à cristaux liquides
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JP2013203957A (ja) * 2012-03-29 2013-10-07 Dainippon Toryo Co Ltd 水系塗料組成物、該水系塗料組成物の製造方法及びショッププライマー
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JP2014025050A (ja) * 2012-06-22 2014-02-06 Basf Japan Ltd 耐汚染性に優れた塗料組成物及びこれを塗装して得られる塗膜
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WO2022176510A1 (fr) * 2021-02-19 2022-08-25 藤倉化成株式会社 Revêtement anti-buée
JP2023144227A (ja) * 2022-03-28 2023-10-11 三菱ケミカル株式会社 ウレタン樹脂組成物、塗料組成物、積層体

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JP7358030B2 (ja) * 2018-01-31 2023-10-10 住友ゴム工業株式会社 親水性基材
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KR102470307B1 (ko) * 2022-01-17 2022-11-25 주식회사 일신웰스 친수성 코팅 조성물 및 이의 제조방법
KR102744599B1 (ko) * 2022-07-08 2024-12-19 임연아 김서림 방지 조성물 및 그 제조방법

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JPWO2011142130A1 (ja) * 2010-05-14 2013-07-22 株式会社Kri 修飾金属酸化物ゾル
JP5716748B2 (ja) * 2010-09-14 2015-05-13 コニカミノルタ株式会社 樹脂フィルム、樹脂フィルムの製造方法、偏光板、及び液晶表示装置
WO2012035939A1 (fr) * 2010-09-14 2012-03-22 コニカミノルタオプト株式会社 Film de résine, procédé de production de film de résine, plaque de polarisation, et afficheur à cristaux liquides
JP2013203957A (ja) * 2012-03-29 2013-10-07 Dainippon Toryo Co Ltd 水系塗料組成物、該水系塗料組成物の製造方法及びショッププライマー
EP2664659A1 (fr) * 2012-05-15 2013-11-20 Carl Zeiss Vision International GmbH Revêtement antibuée
US10338278B2 (en) 2012-05-15 2019-07-02 Carl Zeiss Vision International Gmbh Anti-fog coating
US9500860B2 (en) 2012-05-15 2016-11-22 Carl Zeiss Vision International Gmbh Anti-fog coating
JP2014025050A (ja) * 2012-06-22 2014-02-06 Basf Japan Ltd 耐汚染性に優れた塗料組成物及びこれを塗装して得られる塗膜
WO2014024686A1 (fr) * 2012-08-10 2014-02-13 ハリマ化成株式会社 Agent de revêtement durcissable de type en deux parties
JP2014037454A (ja) * 2012-08-10 2014-02-27 Harima Chemicals Inc 二液硬化型被覆剤
KR20150023683A (ko) 2012-08-10 2015-03-05 하리마 카세이 가부시키가이샤 2액 경화형 피복제
US9752046B2 (en) 2013-03-21 2017-09-05 Nihon Parkerizing Co., Ltd. Aqueous hydrophilic coating composition capable of forming coating film having excellent self-cleaning ability against stains adhered thereon, and surface-treated material having formed thereon coating film having excellent self-cleaning ability against stains adhered thereon
CN103468213B (zh) * 2013-08-28 2016-04-27 奇瑞汽车股份有限公司 一种防雾组成物及防雾汽车玻璃制备方法
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JP2017071724A (ja) * 2015-10-09 2017-04-13 セコ コーポレイション リミテッド 防曇剤
JP2018172566A (ja) * 2017-03-31 2018-11-08 旭化成株式会社 防曇塗膜およびコーティング組成物
JP7026446B2 (ja) 2017-03-31 2022-02-28 旭化成株式会社 防曇塗膜およびコーティング組成物
US11634609B2 (en) * 2017-06-02 2023-04-25 Ppg Industries Ohio, Inc. Polymers, coating compositions containing such polymers, and anti-fingerprint coatings formed therefrom
KR102346941B1 (ko) * 2017-06-02 2022-01-03 피피지 인더스트리즈 오하이오 인코포레이티드 중합체, 이 중합체를 함유하는 코팅 조성물, 및 이로부터 형성된 지문 방지 코팅
KR20200015593A (ko) * 2017-06-02 2020-02-12 피피지 인더스트리즈 오하이오 인코포레이티드 중합체, 이 중합체를 함유하는 코팅 조성물, 및 이로부터 형성된 지문 방지 코팅
JP2020522402A (ja) * 2017-06-02 2020-07-30 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． ポリマー、そのようなポリマーを含有するコーティング組成物、およびその組成物から形成された防指紋コーティング
JP2019065099A (ja) * 2017-09-29 2019-04-25 三菱ケミカル株式会社 ウレタン塗料組成物及び成形体
JP6996199B2 (ja) 2017-09-29 2022-01-17 三菱ケミカル株式会社 ウレタン塗料組成物及び成形体
CN109021729A (zh) * 2018-06-27 2018-12-18 江苏美的清洁电器股份有限公司 涂料、过滤件与吸尘器
KR20210028215A (ko) * 2018-08-02 2021-03-11 아크조노벨코팅스인터내셔널비.브이. 소프트-필, 방오 코팅을 위한 폴리실록산-변형된 폴리우레탄을 포함하는 코팅 조성물
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JPWO2021182331A1 (fr) * 2020-03-10 2021-09-16
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JP7619359B2 (ja) 2020-03-10 2025-01-22 日油株式会社 防曇剤組成物、該組成物から形成される防曇膜を有する防曇性物品
WO2022176510A1 (fr) * 2021-02-19 2022-08-25 藤倉化成株式会社 Revêtement anti-buée
JP2022127163A (ja) * 2021-02-19 2022-08-31 藤倉化成株式会社 防曇塗料
JP7780069B2 (ja) 2021-02-19 2025-12-04 藤倉化成株式会社 防曇塗料
CN114437626A (zh) * 2021-12-09 2022-05-06 科顺防水科技股份有限公司 聚氨酯防水涂料及其制备方法
JP2023144227A (ja) * 2022-03-28 2023-10-11 三菱ケミカル株式会社 ウレタン樹脂組成物、塗料組成物、積層体

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