Classifications

• • 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
  • 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
  • C08G18/6237—Polymers of esters containing glycidyl groups of alpha-beta ethylenically unsaturated carboxylic acids; reaction products thereof
• • 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
  • C08G18/28—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
  • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
• • 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
  • C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
• • 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
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • 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
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
• • 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
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G2290/00—Compositions for creating anti-fogging
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

• Antifogging coating liquid and antifogging article are Antifogging coating liquid and antifogging article
• the present invention relates to an antifogging coating solution and an antifogging article. More particularly, the present invention relates to an anti-fogging article excellent in scratch resistance, initial anti-fogging property, anti-fogging maintenance property and adhesion, and an anti-fogging coating solution that provides the same.
• An object of the present invention is to provide an anti-fogging coating solution that gives an anti-fogging coating film having good scratch resistance, initial anti-fogging property, anti-fogging maintenance property and adhesion, and in particular, An object of the present invention is to provide the coating solution having performance as a one-component coating solution.
• Still another object of the present invention is to provide an antifogging article provided with the coating film of the coating solution of the present invention.
• ! ⁇ ⁇ ! ⁇ Is independently of each other a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X 1 is a hydroxyl group having a hydroxyl group and interrupted by an oxygen atom,
• Homopolymers consisting of repeating units represented by Z and Z or the above formula (1) and the following formulas (2) to (5)
• R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X 2 is an aliphatic group having an epoxy group.
• R 5 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• X 3 is an alkoxycarbonyl group, an alkyl ether group, an alkyl group, an alkenyl group, or an alkenyl group.
• 1 9 Oyobi 1 1 are each independently a hydrogen atom or aralkyl Kill group with carbon number from 1 to 5 and X 5 is or amide group or an amino group, an amide group or ⁇ amino group
• the repeating unit represented by each of the following formulas (1) is 70 mol% or more
• the antifogging coating solution of the present invention comprises a homopolymer composed of a repeating unit represented by the above formula (1) and / or a repeating unit represented by each of the above formula (1) and the above formulas (2) to (5).
• a homopolymer composed of a repeating unit represented by the above formula (1) and / or a repeating unit represented by each of the above formula (1) and the above formulas (2) to (5).
• a copolymer comprising 30 mol% or less of repeating units is contained as a resin component.
• R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X 1 has a hydroxyl group and is interrupted by an oxygen atom. It may be an aliphatic group.
• the repeating unit represented by the above formula (1) is represented by the following formula (1 ')
• R 1 CH CR 2
• Examples of such compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, and hydroxyalkyl methacrylate.
• R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X 2 is an aliphatic group having an epoxy group.
• the repeating unit represented by the above formula (2) is represented by the following formula (2 ')
• R 3 CH CR 4
• R 5 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• X 3 is an alkoxycarbonyl group, an alkyl ether group, an alkyl group, or an alkyl group.
• the repeating unit represented by the above formula (3) is represented by the following formula (3 ')
• Examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methyl vinyl ether, ethyl vinyl ether and the like.
• R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• X 4 is an aliphatic group having a strong lpoxyl group or a strong lpoxyl group. is there.
• R 7 CH CR 8
• Examples of powerful compounds include (meth) acrylic acid, itaconic acid, crotonic acid and the like.
• R 9 and R 1G are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• X 5 is an amide group or an amino group. Or an aliphatic group having an amide group or an amino group.
• the hydrogen atom bonded to the nitrogen atom contained in the amide group or the amino group may be substituted with an alkyl group, hydroxyalkyl group or alkoxyalkyl group having 1 to 5 carbon atoms.
• R 9 CH CR 10
• Examples of such compounds include aminomethyl (meth) acrylate, (meth) acrylamide, crotonamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N— Dihydroxymethyl (meth) acrylamide, N, N-dihydroxyethyl (meth) acrylamide, Hydroxymethylaminomethyl (meth) acrylate, 2-Hydrochichechilamino aminomethyl (meth) acrylate, 2- (2-Hydroxyethylamino ) Ethyl (meth) acrylate, N, N-di (2-hydroxymethyl) aminomethyl (meth) acrylate
• the repeating unit represented by the above formula (1) is represented by the above formula (1) as 1 mol, the repeating unit represented by the above formula (1) is 70 mol% or more and 100 mol% or less, More preferably, it is contained in an amount of 80 mol% or more and 95 mol% or less.
• the homopolymer or copolymer preferably has a polystyrene-reduced weight average molecular weight (Mw) of 100 to 50,000 as measured by gel permeation chromatography (GPC), and is preferably 1,000 to 30,000. It is more preferable that
• the coating liquid of the present invention further contains a crosslinking agent.
• crosslinking agents include blocked isocyanates, polyfunctional organosilicon compounds having two or more functional groups, compounds having two or more epoxy groups in the molecule, compounds having two or more oxetane rings in the molecule, and epoxy groups, Examples include compounds having two or more different groups selected from silanol groups and oxetane groups in the molecule, and other crosslinking agents.
• Blocking isocyanates include diisocyanate piuret structures such as hexamethylene diisocyanate and free isocyanate groups of compounds composed of isocyanurate structures, and block using methanol and ⁇ -force prolactam as blocking agents. And those having stabilized reactivity to heat are preferably used. These are commercially available products from Sumika Bayer Urethane Co., Ltd. Sumidur BL 3175, Death Module BL 3475, Death Module BL 3370, Death Module 3272, Death Module VPL S 2253, Death Module TP LS 2134; and Asahi Kasei Deyuranate 17 B-60 PX, Deyuranate TPA-B 80X, Deyuranate MF-K60 X, etc. manufactured by Kogyo Co., Ltd. are available.
• the same compounds as the bifunctional silane, trifunctional silane and tetrafunctional silane described later can be used as the organosilane compound used for the surface modification of the oxide fine particles.
• compounds having two or more epoxy groups in the molecule ethylene glycol darisidyl ether, glycerol polyglycidyl ether, bisphenol A, bisphenol, ethylene glycol, polyethylene glycol, propylene glycol, Polyglycidyl ether obtained from polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and sorbitol and epichlorohydrin, polybasic acids such as phthalic acid and hexahydrophthalic acid, and poly obtained from epichlorohydrin Glycidyl ether, aniline, toluidine, 4,4'-diaminodiphenylmethane, polyglycidylamine obtained from epiclorhydrin such as isocyan
• cross-linking agents examples include melamines such as hexamethylol melamine, methylol melamine, and alkyl ether himemethylol melamine.
• the crosslinking agent is preferably 15 parts by weight or less, more preferably 0.5 to 10 parts by weight with respect to a total of 100 parts by weight of the homopolymer or copolymer contained in the coating solution of the present invention, More preferably, it is 1.0 to 5.0 parts by weight.
• the coating solution of the present invention may further contain colloidal silica, a surfactant, a hard catalyst for promoting hardening, and a leveling agent for improving coating properties, if necessary.
• Colloidal silica can be obtained as a commercial product.
• examples include IPA-ST (particle size: 10 to 20 nm, solid content: 30%, isopropanol solvent), methanol silica sol manufactured by Nissan Chemical Industries, Ltd. (Particle size: 10-2 Onm, solid content: 30%, methanol solvent), NPC-ST-30 (particle size: 10-2 Onm, solid content: 30%, ethylene glycol mono-n-propyl ether solvent), EG—ST (particle size: 10-2) 0 nm, solid content: 30% ⁇ , ethylene glycol solvent), ST—OUP (chain silica, particle size: 10 to 20 nm, solid content: 15%, aqueous solvent), IPA—ST—UP (chain shear force) , $ Standing diameter: 10 to 20 nm, solid content: 15%, isopropanol solvent) and the like.
• particle size 1 is a colloidal shear force or with colloidal silica.
• Metal oxide fine particles in the range of ⁇ 100 nm can also be used.
• metals include, for example, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
• Z r, I ⁇ , and ⁇ i are used.
• Specific examples of the metal oxides for example, A 1 2 0 3, Sn_ ⁇ 2, Sb 2 0 5, Ta 2 ⁇ 5, Ce_ ⁇ 2, L a 2 O s, F e 2 ⁇ 3, ZnO, W_ ⁇ 3 , Zr 0 2 , I n 2 0 3 , T i 0 2 can be used. These oxides can be used after surface modification with an organosilane compound in order to enhance dispersibility in a solvent.
• Such surface modification with an organosilane compound can be carried out by bringing the organosilane compound into contact with the organosilane compound in a dispersion medium at a ratio of 20% by weight or less with respect to the oxide fine particles.
• the hydrolysis of the organosilane compound may be performed after the contact or may be performed after the contact.
• organosilane compounds examples include:
• R 3 Si X (wherein R is an alkyl group, a phenyl group or a vinyl group, or an (meth) organic group having an acryloxy group, a mercapto group, an amino group or an epoxy group, and X is a hydrolyzable group.
• a monofunctional silane represented by the formula: R 2 S iX 2 (the definition of R, X is the same as above); a bifunctional silane represented by the formula: RS iX 3 (the definition of R, X is the same as above)
• trifunctional silanes represented by the formula S i X 4 (wherein the definition of X is the same as above).
• the organic group is preferably an alkyl group having 1 to 4 carbon atoms.
• the hydrolyzable group is preferably a halogen atom or an alkoxy group having 1 to 4 carbon atoms.
• organosilane compounds include, for example, trimethylmethoxysilane.
• Triethylmethoxysilane Triethylmethoxysilane
• Sisilane triphenyl methoxy silane, diphenyl methyl methoxy silane, phenyl dimethyl methoxy silane, phenyl dimethyl ethoxy silane, vinyl dimethyl methoxy silane, vinyl dimethyl ethoxy silane, acryloxypropyl dimethyl methoxy silane, Kibubu Pyrudimethylmethoxysilane, Armercaptopropyldimethylmethoxysilane, Armercaptobropyr
• N- j3 aminopropyl dimethylmethaminopropyldimethylmethoxysilane, aminopropyl glycidoxypropyldimethoxyethoxysilane, ⁇ ⁇ (3, 4 one epoxy cyclo Monofunctional silanes such as xyl) ethyldimethylmethoxysilane; dimethyldimethoxysilane, jetyldimethoxysilane, dimethyljetoxysilane, jetyljetoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenyl Methyl jetoxy silane, vinyl methyl dimethoxy silane, Bier methyl jetoxy silane, alkylacryloxypropyl methyl dimercaptopropyl methyldimethoxysilane, final mercaptopropylmethyldiethoxysilane, N_iS (aminoethyl) ⁇ -a
• Examples thereof include trifunctional silanes such as toxisilane, ⁇ - (3,4-epoxy hexyl) ethyltrimethoxysilane, and tetrafunctional silanes such as tetraethylorthosilicate and tetramethylorthosilicate.
• trifunctional silanes such as toxisilane, ⁇ - (3,4-epoxy hexyl) ethyltrimethoxysilane
• tetrafunctional silanes such as tetraethylorthosilicate and tetramethylorthosilicate.
• dispersion medium examples include saturated aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, ⁇ -butanol, and 2-butyl alcohol; methyl caffeosolve, ethyl acetate solve, propyl cellosolve, and butyl cectosolve.
• propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl acetate
• esters such as methyl acetate, ethyl acetate, butyl acetate
• ethyl ether methyl isobutyl ether Ethers such as acetone, ketones such as methyl isobutyl ketone
• aromatic hydrocarbons such as xylene and toluene
• surfactants include HL, which is an indicator of the balance between hydrophilicity and hydrophobicity.
• Those having a threshold value of 10 or more are preferably used.
• surfactant having an HLB value of 10 or more for example, polyoxyethylene alkyl ether type, polyoxyethylene alkylamine type and polyoxyethylene alkylamide type surfactants are preferable.
• the curing catalyst for accelerating the curing is preferably added in order to efficiently accelerate the reaction in which each component undergoes a crosslinking condensation reaction and cures.
• alkali metal salt of carboxylic acid such as sodium acetate, ammonium salt, metal salt of acetylacetone, ammonium salt, metal salt of cetylacetate acetate, metal salt coordinated with cetylacetone and ethylacetate, Ethylenediamine metal salt hydrates, primary to tertiary amines, polyalkylamines, sulfonates, magnesium perchlorate, ammonium perchlorate, zinc naphthenate, tin octylate and other organic metal salts, tetrachloride Lewis acids such as tin, titanium tetrachloride and zinc chloride are listed. Further, these compounds may be used in combination with organic mercabtan, mercaptoalkylsilane, or the like.
• the curing catalyst may be added in
• the repelling agent is preferably added to improve the coating property of the coating solution and improve the appearance of the coating film.
• leveling agents include nonionic fluorine-based surfactants and nonionic silicone-based surfactants. These are commercially available products such as MegaFuck F-472 SF, MegaFack F-443, MegaFack F-1405, manufactured by Dainippon Ink & Chemicals, Inc., Nunidyne NS-1605, manufactured by Daikin Industries, Ltd.
• the antifogging coating solution of the present invention is, for example, 0 to 150 parts by weight of oxide fine particles such as colloidal force, and more preferably 10 to 125 parts per 100 parts by weight of the resin component. Parts by weight, 0 to 80 parts by weight of surfactant, more preferably 10 to 70 parts by weight.
• the coating solution usually contains a solvent.
• the preferred solid content concentration of the coating solution varies depending on the coating method. For example, 5 to 20% by weight is preferable when applied by the dipping method or spray method, and 15 to 35% by weight when applied by the spin coating method. %, Preferably 20 to 50% by weight when applied by the mouth coat method or gravure coat method, and 20 to 80 when applied by the screen printing method. It is preferable that it is weight%.
• Examples of the solvent include the same solvents as those described as the dispersion solvent used for the surface modification of the oxide fine particles.
• the anti-fogging coating solution of the present invention is applied directly to a base material, or to a base material that has been subjected to application of a functional film such as a primer or hard coat, or an electrical treatment such as corona treatment or plasma treatment. It is used by removing the solvent to form a coating film.
• a transparent base material is preferably used as the base material.
• examples of such a substrate include various substrates made of glass, polycarbonate resin, acrylic resin and, for example, an eyeglass lens substrate subjected to antireflection treatment.
• an optical lens such as an eyeglass lens is often provided with a multilayer antireflection film, for example, a multilayer antireflection film whose outermost layer is composed of Si 0 2 layers.
• antifogging properties can be imparted while maintaining the antireflection performance.
• the solvent is then removed from the coated film.
• the temperature in the solvent removal step is preferably 15 to 300 ° C., more preferably 40 to 200 ° C. as the ambient temperature.
• the time for the solvent removal step is preferably 1 second to 24 hours, more preferably 10 seconds to 5 hours.
• the thickness of the coating film after removal of the solvent by the coating liquid of the present invention depends on the type and application of the substrate. Although it is more different, the antifogging performance is better as the film thickness is larger, and even when the film thickness is larger, the transparency can be maintained. Usually, it is 10 / xm or less, and preferably 10 nm to 10 m.
• the coating film formed on the surface of the article by the coating solution of the present invention is in a crosslinked state and is a homopolymer comprising a repeating unit represented by the above formula (1) and / or the above formula (1) and the above formula (1). 2) to (5) containing as a resin component a copolymer comprising at least one repeating unit selected from the group consisting of repeating units represented by each of the above-mentioned X 1 , X 2 , X 3 , X 4 X 1 is preferably present in an amount of at least 65 mol%, more preferably 65 to 95 mol%, based on the total number of moles of X and X 5 .
• the coating film formed from the coating solution of the present invention is crosslinked to form a coating film having excellent scratch resistance.
• the residual amount of hydroxyl groups in the repeating unit represented by the above formula (1) is It affects the antifogging performance, and it is preferable that 65 mol% or more of hydroxyl groups remain as defined above.
• it is preferable to carry out a crosslinking reaction so that the amount of the hydroxyl group is reduced by 0 to 25 mol%, and in particular, the crosslinking is carried out so as to reduce by about 5%. It is preferable to carry out the reaction.
• Such a cross-linking reaction is carried out by subjecting the coating film to an atmospheric temperature of preferably 40 to 300 ° C., more preferably 60 to 200 ° C., preferably 1 second to 24 hours. More preferably, it can be carried out by heating for 10 seconds to 5 hours.
• the anti-fogging coating solution of the present invention has a hydroxyl group based on the resin component in the coating film structure, and has excellent initial anti-fogging properties and anti-fogging maintenance properties even when thinned. Give a membrane.
• those containing a surfactant having a high HLB value give a further excellent initial antifogging property and antifogging maintenance property because the amount of the surfactant eluted is small.
• those containing fine oxide particles such as colloidal silica exhibit excellent scratch resistance
• those containing an organosilicon compound as a crosslinking agent are inorganic substrates (base materials). Both show stable adhesion and contain blocked isocyanate In that case, there is one-component stability over a long period of time.
• the resin component for expressing the antifogging property was prepared as follows.
• the molecular weights of the resin components are all polystyrene-equivalent weight average molecular weights measured by GPC.
• the resulting copolymer was a copolymer of 2-hydroxyethyl methacrylate and dimethylaminoethyl methacrylate having a molecular weight of about 10,000.
• the polymer obtained was a homopolymer of 2-hydroxyethyl methacrylate having a molecular weight of about 10,000.
• the resulting copolymer was a copolymer of 2-hydroxyethyl methacrylate and acrylamide having a molecular weight of about 10 and 00.
• the mixture was heated and stirred at 0 ° C for 4 hours for copolymerization.
• the obtained copolymer was a copolymer of 2-hydroxyethyl methacrylate and glycidyl methacrylate having a molecular weight of about 10,00.
• the resulting copolymer was a copolymer of 2-hydroxyethyl methacrylate and acrylic acid having a molecular weight of about 10 and 00.
• the obtained copolymer was a copolymer of 2-hydroxymethyl methacrylate and methyl methacrylate having a molecular weight of about 100,000.
• Antifogging resin 1 (solid content: 24% by weight): 80 parts by weight Methyltrimethoxysilane: 1 part by weight
• Polyoxyethylene alkyl ether type surfactant 2 parts by weight
• Nonionic type fluorine leveling agent 0.1 part by weight
• Antifogging resin 2 (solid content: 24% by weight): 80 parts by weight
• Methyltrimethoxysilane 1 part by weight
• PA—ST— UP solid content: 15% by weight
• Polyoxyethylene alkylamide type surfactant 2 parts by weight
• Nonionic silicone leveling agent 0.1 part by weight
• Antifogging resin 3 (solid content: 24% by weight): 80 parts by weight
• PA— ST— UP solid content: 15% by weight
• Polyoxyethylene alkyl ether type surfactant 4 parts by weight
• Nonionic silicone leveling agent 0.1 part by weight
• Antifogging resin 3 (solid content: 24% by weight): 80 parts by weight
• NPC- ST-30 solid content: 30% by weight: 32 parts by weight
• Polyoxyethylene alkylamide type surfactant 4 parts by weight
• Nonionic silicone leveling agent 0.1 part by weight
• Antifogging resin 3 (solid content: 24% by weight): 80 parts by weight
• Methyltrimethoxysilane 2 parts by weight
• Nonionic silicone leveling agent 0.1 parts by weight
• Antifogging resin 4 (solid content: 24% by weight): 80 parts by weight
• Nonionic silicone leveling agent 0.1 parts by weight
• Antifogging resin 5 (solid content: 24% by weight): 80 parts by weight
• Polyoxyethylene alkyl ether type surfactant 2 parts by weight
• Nonionic silicone leveling agent 0.1 part by weight
• Anti-fog resin 6 (solid content: 24% by weight): 80 parts by weight
• Polyoxyethylene alkyl ether type surfactant 2 parts by weight
• Nonionic type fluorine leveling agent 0.1 part by weight
• Antifogging resin 2 (solid content: 24% by weight): 80 parts by weight
• Hexamethylolmelamine 0.5 parts by weight
• Polyoxyethylene alkyl ether type surfactant 2 parts by weight
• Noeon type silicone leveling agent 0.1 part by weight
• Antifogging resin 2 (solid content: 24% by weight): 80 parts by weight
• NPC-ST-30 solid content: 30% by weight: 80 parts by weight
• Polyoxyethylene alkyl ether type surfactant 12 parts by weight
• Nonionic silicone leveling agent 0.1 part by weight
• Polyoxyethylene alkylamide type surfactant 2 parts by weight
• Nonionic silicone leveling agent 0.1 parts by weight
• Antifogging resin 2 (solid content: 24% by weight): 80 parts by weight
• Methyltrimethoxysilane 1 part by weight
• Polyethylene glycol diglycidyl ether 1 part by weight
• Polyoxyethylene alkyl ether type surfactant 2 parts by weight
• Nonionic silicone leveling agent 0.1 parts by weight
• Antifogging resin 2 (solid content: 24% by weight): 80 parts by weight
• Methyltrimethoxysilane 2 parts by weight
• Polyoxyethylene alkylamide type surfactant 2 parts by weight
• Nonionic silicone leveling agent 0.1 parts by weight
• Anti-fog resin 7 (solid content: 24% by weight): 80 parts by weight Sumijoule BL3175 (solid content: 75% by weight): 1 part by weight
• Polyoxetylene alkylamide surfactant 2 parts by weight
• Nonionic silicone leveling agent 0.1 parts by weight Each coating solution was prepared by uniformly stirring and mixing each component according to the above formulation table.
• the above coating solutions are applied to one side of the substrate, and an article having a crosslinked film is placed in hot water at 50 ° C in a room at a temperature of 20 ° C and humidity of 50% RH, and the treated surface becomes cloudy or cloudy.
• the performance was judged by
• Antifogging evaluation is the same as the initial antifogging performance evaluation method.
• the haze value of the coated article was measured with a haze meter.
• Each coating solution prepared in the range of 15 to 35% by weight of the solid content as shown in the above-mentioned preparation table was applied to one side of the base material shown in Table 1 by spin coating, and at 60 ° C.
• the solvent was removed by heating for 10 minutes, and then the crosslinking reaction was carried out by heating in air at 120 ° C. for 30 minutes.
• Various evaluations were performed on the obtained articles having a crosslinked film in accordance with the above evaluation methods. The results are shown in Table 1. Further, Table 1 shows the amount of residual hydroxyl groups after the crosslinking reaction as a ratio (mol%) to the total number of moles of the groups XX 2 , X 3 , X 4 and X 5 .
• This value was calculated from the residual ratio of hydroxyl groups before and after the crosslinking reaction and the copolymerization ratio of each monomer in the polymer.
• the residual ratio of the hydroxyl group was determined by infrared absorption analysis (FT-IR method) as follows. First, each coating solution was applied onto a silicon wafer, heated at 60 ° C. for 10 minutes to remove the solvent, and a sample before crosslinking was obtained. Using this sample, the JIR-550 series infrared spectrophotometer JIR-5550 manufactured by JEOL Ltd. was used.
• the sample before crosslinking is In the same manner, the absorption intensity of the absorption band was measured for the sample obtained by performing a crosslinking reaction by heating for 30 minutes, and applying the measurement result to the calibration curve to determine the residual ratio of hydroxyl groups. Asked.
• the coating solutions 2, 3, 3 ', 5, and 9 used in Comparative Examples 1 to 4 are based on the compositions of the coating solutions 2, 3, 5, and 9, respectively. It is a coating liquid corresponding to the composition from which the silicon compound has been removed.
• the glass plate that is the base material used is clear glass (thickness 2mm) manufactured by Nippon Sheet Glass Co., Ltd.
• the poly-strength Ponate resin plate is made by Polychus ECK-100 manufactured by Tsutsunaka Plastic Industry Co., Ltd.
• the acrylic resin plate is Acrylite E plate (thickness 2 mm) manufactured by Mitsubishi Rayon Co., Ltd.
• a HOY A HYLUX multi-process lens manufactured by HOY A Co., Ltd. was used as a base material.
• Violent film swells 2 3-4 4 Comparative example 2 fc Ru Film swells 2 3-4 4

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• 2005
  • 2005-02-21 JP JP2005044777A patent/JP2006225614A/ja active Pending
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