Anti-fogging agent composition and Anti-fogging article having Anti-fogging film formed from said composition

Abstract

This anti-fogging agent composition contains a copolymer (A), a polyfunctional block isocyanate compound (B), a surfactant (C), and a solvent (D), wherein the solvent (D) contains a dihydric alcohol (D-1) and a glycol ether (D-2) with the content of (D-1) being 5-35 parts by mass and the content of (D-2) being 3-15 parts by mass with respect to 100 parts by mass of the anti-fogging agent composition, and the mass ratio [(D-1) / (D-2) ] of (D-1) to (D-2) being 0.5-8.0. This anti-fogging agent composition provides an anti-fogging film formed by heat curing that excels in appearance, adhesion, anti-fogging performance, and water streaking marks, and can suppress dripping or brush marks during coating, and can suppress solvent cracking when performing heat curing at a high temperature.

Description

Antifogging agent composition and antifogging article having antifogging film formed from said composition

[0001] The present invention relates to an antifogging agent composition and an antifogging article having an antifogging film formed from the composition.

[0002] In vehicle lighting fixtures such as automobile headlamps, high-humidity air can enter the lamp chamber, causing the lens to cool due to external air or rain, resulting in condensation of water on the inner surface, causing fogging. As a result, the brightness of the vehicle light is reduced and the aesthetic appearance of the lens surface is impaired, causing discomfort to users. To prevent such lens fogging, a known method is to apply an anti-fogging agent to the area where fogging occurs (the inner surface of the lens) to form an anti-fogging film (a dried coating film or a hardened coating film).

[0003] Patent Document 1 discloses an antifogging agent composition containing a specific hydrophilic resin, a surfactant, and a solvent.

[0004] The antifogging agent composition disclosed in Patent Document 1 can suppress solvent cracking and provide a good cured coating film appearance during coating and drying, and further has good coatability, resulting in a coating film with smooth surface upon coating.

[0005] JP 2016-027134 A

[0006] In recent years, automobile headlamps have increasingly adopted lens substrates with relatively high internal residual stress due to their larger size and complexity. When an anti-fog composition is applied to such lens substrates and then heat-cured, solvent cracks are likely to occur on the lens surface. Since there are limitations to the ingenuity of production processes such as painting and heat-curing, there is a growing need for anti-fog compositions to suppress solvent cracks.

[0007] The present inventors have discovered that glycol ether solvents, which are commonly used in conventional anti-fog compositions, impart good coatability and coating appearance to the anti-fog composition, but that they also corrode the base resin at high temperatures during heat curing. Some production lines are designed to rapidly increase the lens temperature in order to improve productivity by shortening the heat curing time, but it has been found that such processes can cause solvent cracking, which can impair the aesthetic appearance of the lens surface.

[0008] The anti-fogging agent composition disclosed in Patent Document 1 can suppress solvent cracking in the room temperature range during application, but if the lens is rapidly heated and dried during heat curing, solvent cracking occurs, which may impair the aesthetic appearance of the lens surface.

[0009] In view of the above circumstances, the present invention aims to provide an anti-fog agent composition that forms an anti-fog film by heat curing with good appearance, adhesion, anti-fog properties, and no drip marks, and that can suppress dripping and blushing during application and solvent cracking when heat curing is performed at high temperatures, and an anti-fog article having an anti-fog film formed from said composition. Note that when application and heat curing are performed in a high-humidity environment (e.g., a relative humidity of 80% or more), the heat of vaporization caused by the solvent volatilizing on the coating surface causes a rapid drop in the coating surface temperature, causing moisture in the air to condense on the coating surface, resulting in aggregation and precipitation of resin components and the generation of unevenness on the coating surface, causing the coating to appear white, a phenomenon known as blushing.

[0010] That is, the present invention provides an antifogging agent composition containing a copolymer (A), a polyfunctional blocked isocyanate compound (B), a surfactant (C), and a solvent (D), wherein the copolymer (A) is a (meth)acrylate copolymer obtained from a monomer mixture containing a monomer (A-1) represented by the following general formula (1): (In general formula (1), R １ is a hydrogen atom or a methyl group, and R ２ is a linear or branched alkyl group having 1 to 4 carbon atoms, -C(CH ３ ) ２ CH ２ COCH ３ , -C ２ H４ N (CH ３ ) ２ , or -C ３ H ６ N (CH ３ ) ２ and R ３ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. The solvent (D) contains a dihydric alcohol (D-1) and a glycol ether (D-2), and the dihydric alcohol (D-1) is a compound represented by the following general formula (7), and HO—R １５ -OH...(7) (In general formula (7), R １５ is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms. The glycol ether (D-2) is a compound represented by the following general formula (8), １６ -O-R １７ -OH...(8) (In general formula (8), R １６ represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms; R １７ is a linear or branched alkylene group having 1 to 4 carbon atoms.) The antifogging agent composition according to the present invention relates to an antifogging agent composition, in which the dihydric alcohol (D-1) is 5 parts by mass or more and 35 parts by mass or less, and the glycol ether (D-2) is 3 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the antifogging agent composition, and the mass ratio of the dihydric alcohol (D-1) to the glycol ether (D-2) [(D-1) / (D-2)] is 0.5 or more and 8.0 or less.

[0011] The present invention also relates to an anti-fogging article having an anti-fogging film formed from the anti-fogging agent composition on a substrate.

[0012] The present invention can provide an anti-fog agent composition that forms an anti-fog film by heat curing that has good appearance, adhesion, anti-fog properties, and water drip marks, and that can suppress dripping and blushing during application and solvent cracking when heat curing is performed at high temperatures, and an anti-fog article having an anti-fog film formed from the composition.

[0013] The antifogging agent composition of the present invention contains a copolymer (A), a polyfunctional blocked isocyanate compound (B), a surfactant (C), and a solvent (D).

[0014] <Copolymer (A)> The copolymer (A) of the present invention is a (meth)acrylate copolymer obtained from a monomer mixture containing the following monomer (A-1).

[0015] <Monomer (A-1)> The monomer (A-1) is a monomer represented by the following general formula (1). (In general formula (1), R １ is a hydrogen atom or a methyl group, and R ２ is a linear or branched alkyl group having 1 to 4 carbon atoms, -C(CH ３ ) ２ CH ２ COCH ３ , -C ２ H ４ N (CH ３ ) ２ , or -C ３ H ６ N (CH ３ ) ２ and R ３ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0016] In the general formula (1), examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group. In the general formula (1), from the viewpoint of improving the antifogging performance of the antifogging film and the adhesion to the substrate, R １ is preferably a hydrogen atom, and R ２ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group; R ３ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0017] As the monomer (A-1), preferably, N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide can be used.

[0018] The monomer (A-1) may be used alone or in combination of two or more.

[0019] The monomer mixture preferably contains, as other monomers in addition to the monomer (A-1), one or more monomers (A-3) selected from the group consisting of a monomer (A-2) represented by the following general formula (2), a monomer represented by the following general formula (3), and a monomer represented by the following general formula (4), and one or more monomers (A-4) selected from the group consisting of a monomer represented by the following general formula (5), and a monomer represented by the following general formula (6): (In general formula (2), R ４ is a hydrogen atom or a methyl group, and R ５ is a straight-chain, branched-chain, or cyclic hydrocarbon group having 1 to 18 carbon atoms. (In general formula (3), R ６ is a hydrogen atom or a methyl group, and R ７ is a linear alkylene group having 1 to 4 carbon atoms, and R ８ is a substituent having a heterocyclic skeleton. (In general formula (4), R ９ is a hydrogen atom or a methyl group, and R １０ is a substituent having a heterocyclic skeleton. (In general formula (5), R １１ is a hydrogen atom or a methyl group, and R １２ is a linear or branched alkylene group having 2 to 4 carbon atoms, or -C ２ H ４ (OCO(CH ２ ) ５ ) ｎ - and n is 1 to 5. (In general formula (6), R １３ is a hydrogen atom or a methyl group, and R １４ is a straight or branched alkylene group having 1 to 4 carbon atoms.

[0020] <Monomer (A-2)> The monomer (A-2) is a monomer represented by the following general formula (2). (In general formula (2), R ４ is a hydrogen atom or a methyl group, and R ５is a straight-chain, branched-chain, or cyclic hydrocarbon group having 1 to 18 carbon atoms.

[0021] In the general formula (2), examples of the linear, branched, or cyclic hydrocarbon group having 1 to 18 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-amyl, i-amyl, t-amyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-nonyl, isobornyl, lauryl, myristyl, cetyl, and stearyl; alkenyl groups such as oleyl; and aryl groups such as phenyl. From the viewpoints of improving the adhesion and water resistance between the anti-fogging film and the substrate and improving the anti-fogging performance of the anti-fogging film, the branched or cyclic hydrocarbon group having 3 to 16 carbon atoms is preferred, and the branched or cyclic hydrocarbon group having 4 to 12 carbon atoms is more preferred.

[0022] The monomer (A-2) may be used alone or in combination of two or more.

[0023] <Monomer (A-3)> The monomer (A-3) is at least one selected from the group consisting of monomers represented by the following general formula (3) and monomers represented by the following general formula (4). (In general formula (3), R ６ is a hydrogen atom or a methyl group, and R ７ is a linear alkylene group having 1 to 4 carbon atoms, and R ８ is a substituent having a heterocyclic skeleton. (In general formula (4), R ９ is a hydrogen atom or a methyl group, and R １０ is a substituent having a heterocyclic skeleton.

[0024] In the general formula (3), examples of the linear alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group, and examples of the substituent having a heterocyclic skeleton include an epoxy group, a 3,4-epoxycyclohexyl group, an oxetanyl group, a furyl group, a tetrahydrofuryl group, an oxotetrahydrofuryl group, a 2-oxo-1,3-dioxolanyl group, a mevalonate lactone group, and a cyclic trimethylol group. Examples include oxygen-containing heterocyclic substituents such as a propaneformal group; oxygen- and nitrogen-containing heterocyclic substituents such as a morpholino group; and nitrogen-containing heterocyclic substituents such as an N-succinimidyl group, a 1,2,2,6,6-pentamethyl-4-piperidyl group, a 2,2,6,6-tetramethyl-4-piperidyl group, and a 2,2,6,6-tetramethylpiperidine-1-oxyl group, and the heterocyclic ring is preferably a 3-, 4-, 5-, or 6-membered ring. From the viewpoint of suppressing whitening due to dripping marks, the substituent having a heterocyclic skeleton is preferably an oxygen-containing heterocyclic substituent.

[0025] In the general formula (4), examples of the substituent having a heterocyclic skeleton include oxygen-containing heterocyclic substituents such as epoxy groups, 3,4-epoxycyclohexyl groups, oxetanyl groups, furyl groups, tetrahydrofuryl groups, oxotetrahydrofuryl groups, 2-oxo-1,3-dioxolanyl groups, mevalonate lactone groups, and cyclic trimethylolpropane formal groups; oxygen- and nitrogen-containing heterocyclic substituents such as morpholino groups; and nitrogen-containing heterocyclic substituents such as N-succinimidyl groups, 1,2,2,6,6-pentamethyl-4-piperidyl groups, 2,2,6,6-tetramethyl-4-piperidyl groups, and 2,2,6,6-tetramethylpiperidine-1-oxyl groups, and the heterocyclic ring is preferably a 3-, 4-, 5-, or 6-membered ring. From the viewpoint of suppressing watermark whitening, the substituent having a heterocyclic skeleton is preferably an oxygen-containing heterocyclic substituent.

[0026] As the monomer (A-3), preferably, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, oxotetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, morpholinoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, and pentamethylpiperidyl (meth)acrylate can be used, and more preferably, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, oxotetrahydrofurfuryl (meth)acrylate, and cyclic trimethylolpropane formal (meth)acrylate can be used.

[0027] The monomer (A-3) may be used alone or in combination of two or more.

[0028] <Monomer (A-4)> The monomer (A-4) is at least one selected from the group consisting of a monomer represented by the following general formula (5) and a monomer represented by the following general formula (6). (In general formula (5), R １１ is a hydrogen atom or a methyl group, and R １２ is a linear or branched alkylene group having 2 to 4 carbon atoms, or -C ２ H ４ (OCO(CH ２ ) ５ ) ｎ - and n is 1 to 5. (In general formula (6), R １３ is a hydrogen atom or a methyl group, and R １４ is a straight or branched alkylene group having 1 to 4 carbon atoms.

[0029] In the general formula (5), examples of the linear or branched alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, a 2-methylmethylene group, a butylene group, a 2-methylpropylene group, a 3-methylpropylene group, a 2,2-dimethylmethylene group, and a 2-ethylmethylene group. １２is preferably a linear alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group, a propylene group, or a 2-methylmethylene group, and even more preferably an ethylene group or a propylene group.

[0030] In the general formula (6), examples of the linear or branched alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, a 2-methylmethylene group, a butylene group, a 2-methylpropylene group, a 3-methylpropylene group, a 2,2-dimethylmethylene group, and a 2-ethylmethylene group. １４ is preferably a linear alkylene group having 2 to 4 carbon atoms, more preferably a methylene group, an ethylene group, or a propylene group, and even more preferably a methylene group or an ethylene group.

[0031] As the monomer (A-4), preferably, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or 2-hydroxyethyl (meth)acrylamide can be used, and more preferably, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or 2-hydroxyethyl (meth)acrylamide can be used.

[0032] The monomer (A-4) may be used alone or in combination of two or more.

[0033] The hydroxyl value of copolymer (A) can be calculated from the hydroxyl value (theoretical value) of the monomer (A-4) by the following formula: [Hydroxyl value of monomer (A-4) (mg KOH / g)] = 56,100 / [Molecular weight of monomer (A-4) (g / mol)] [Hydroxyl value of copolymer (A)] = [Hydroxyl value of monomer (A-4) (mg KOH / g)] × [Mass of monomer (A-4) (g)] / [Mass of copolymer (A) (g)] From the viewpoints of improving water resistance and reducing water drip marks, the hydroxyl value is preferably 5 mg KOH / g or more, more preferably 20 mg KOH / g or more, and even more preferably 40 mg KOH / g or more, and from the viewpoint of improving adhesion, it is preferably 160 mg KOH / g or less, more preferably 120 mg KOH / g or less, and even more preferably 90 mg KOH / g or less.

[0034] The proportions of the individual monomer components in the monomer mixture forming the copolymer (A) of the present invention will be described below.

[0035] The content of the monomer (A-1) is preferably 10 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the monomer mixture. From the viewpoint of improving anti-fogging performance, the content of the monomer (A-1) is preferably 15 parts by mass or more and more preferably 20 parts by mass or more in 100 parts by mass of the monomer mixture, and from the viewpoint of improving adhesion and water resistance and reducing water drip marks, the content of the monomer (A-1) is preferably 45 parts by mass or less and more preferably 40 parts by mass or less in 100 parts by mass of the monomer mixture.

[0036] When the monomer (A-2) is used, the amount of the monomer (A-2) is preferably 3 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the monomer mixture. From the viewpoints of improving water resistance and adhesion and suppressing whitening due to dripping water, the amount of the monomer (A-2) is preferably 5 parts by mass or more and more preferably 8 parts by mass or more per 100 parts by mass of the monomer mixture, and from the viewpoint of improving anti-fogging performance, the amount of the monomer (A-2) is preferably 25 parts by mass or less and more preferably 20 parts by mass or less.

[0037] When the monomer (A-3) is used, the amount of the monomer (A-3) is preferably 20 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the monomer mixture. From the viewpoints of improving adhesion and suppressing whitening due to dripping water, the amount of the monomer (A-3) is preferably 30 parts by mass or more and more preferably 35 parts by mass or more per 100 parts by mass of the monomer mixture, and from the viewpoints of improving anti-fogging properties and thinning dripping water, the amount of the monomer (A-3) is preferably 60 parts by mass or less and more preferably 55 parts by mass or less per 100 parts by mass of the monomer mixture.

[0038] When the monomer (A-4) is used, the amount of the monomer (A-4) is preferably 5 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the monomer mixture. The amount of the monomer (A-3) is preferably 8 parts by mass or more and more preferably 10 parts by mass or more per 100 parts by mass of the monomer mixture from the viewpoints of improving water resistance and thinning water drip marks, and is preferably 25 parts by mass or less and more preferably 20 parts by mass or less from the viewpoint of improving adhesion.

[0039] When the monomers (A-2) to (A-4) are used, the total proportion of the monomers (A-1) to (A-4) in the monomer mixture is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0040] The monomer mixture may contain, as other monomers in addition to the monomers (A-1) to (A-4), aromatic vinyl monomers such as styrene, vinyl toluene, and α-methyl styrene; vinyl monomers containing a quaternary ammonium salt structure such as (meth)acryloyloxyethyl trimethyl ammonium chloride and (meth)acryloylaminopropyl trimethyl ammonium chloride; aromatic acrylic monomers such as phenoxyethyl (meth)acrylate; carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, and maleic acid, and their ammonium salts, organic amine salts, and alkali metal salts; sulfonic acid group-containing vinyl monomers such as styrene sulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, and 3-sulfopropyl (meth)acrylate, and their ammonium salts, organic amine salts, and alkali metal salts; Examples of vinyl monomers that can be used include phosphate group-containing vinyl monomers such as 2-(meth)acryloyloxyethyl acid phosphate, and their ammonium salts, organic amine salts, and alkali metal salts; bifunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol (meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, and N,N'-methylenebis[(meth)acrylamide]; polyfunctional vinyl monomers such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; and vinyl monomers having an alkoxysilyl group such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, and vinyltrimethoxysilane.

[0041] <Method for Producing Copolymer (A)> The copolymer (A) of the present invention can be obtained by copolymerizing the above-mentioned monomer mixture. The copolymer structure may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. However, a random copolymer is preferred from the viewpoints of improving the effects of the antifogging agent composition, including antifogging properties, and of easily preparing the antifogging agent composition. Various known polymerization methods, such as radical polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, and living cationic polymerization, are used as the polymerization method for obtaining the copolymer. However, radical polymerization is preferred from the viewpoints of ease of industrial productivity and a wide range of performance aspects. Examples of radical polymerization methods include conventional bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization. However, solution polymerization is preferred because the polymerized product can be used as an antifogging agent composition directly.

[0042] Examples of polymerization solvents used in the solution polymerization method include alcohol-based solvents such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, s-butanol, t-butanol, and diacetone alcohol; alcohol ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-butanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran and dioxane; ester-based solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, and ethyl lactate; aromatic solvents such as benzene, toluene, and xylene; amide-based solvents such as formamide and dimethylformamide; and water. The polymerization solvents may be used alone or in combination of two or more.

[0043] The radical polymerization initiator may be a commonly used organic peroxide, azo compound, or the like. Examples of the organic peroxide include benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-hexanoate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-butylperoxypivalate, and t-hexylperoxypivalate. Examples of the azo compound include 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. The radical polymerization initiator may be used alone or in combination of two or more.

[0044] The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass per 100 parts by mass of the monomer mixture. It is preferable to carry out the polymerization while adding the radical polymerization initiator dropwise to the reaction vessel, as this makes it easier to control the heat generated by polymerization. The temperature at which the polymerization reaction is carried out varies depending on the type of radical polymerization initiator used, but is preferably 30 to 150°C, more preferably 50 to 100°C, for industrial production.

[0045] The weight average molecular weight (Mw) of the copolymer (A) is preferably 50,000 or more, more preferably 100,000 or more, from the viewpoint of imparting water resistance to the anti-fogging film, and is preferably 400,000 or less, more preferably 300,000 or less, from the viewpoint of improving the coatability and handleability of the anti-fogging agent composition.

[0046] The weight average molecular weight (Mw) of the copolymer (A) can be determined by GPC. A sample is prepared by dissolving the sample in tetrahydrofuran to prepare a 0.2% by mass solution, and then filtering the solution through a 0.5 μm membrane filter. Measurement can be performed under the following conditions. <Measurement of Weight Average Molecular Weight (Mw)> Analytical device: HLC-8320GPC (manufactured by Tosoh Corporation) Column: KD-802.5 (manufactured by Showa Denko K.K.), KD-803 (manufactured by Showa Denko K.K.), and KD-80M (manufactured by Showa Denko K.K.) connected in series Column size: 8.0 × 300 mm Eluent: tetrahydrofuran Flow rate: 1.0 mL / min Detector: differential refractometer Column temperature: 40°C Standard sample: polystyrene

[0047] <Polyfunctional Blocked Isocyanate Compound (B)> The polyfunctional blocked isocyanate compound (B) of the present invention is a compound having two or more isocyanate groups per molecule, in which the isocyanate groups are blocked with a blocking agent. The polyfunctional blocked isocyanate compound (B) is not particularly limited as long as it undergoes a crosslinking reaction with at least the copolymer (A) to form a cured film. At least one type of polyfunctional blocked isocyanate compound (B) may be used, or two or more types may be used in combination.

[0048] In the polyfunctional blocked isocyanate compound (B), examples of the compound having two or more isocyanate groups in one molecule include diisocyanate group-containing compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylidene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, trimethylhexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, and 1,5-naphthalene diisocyanate; and derivatives of these diisocyanate group-containing compounds, such as biuret compounds, isocyanurate compounds, adduct compounds, and allophanate compounds. Among these, from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, and derivatives thereof are preferred.

[0049] Examples of the blocking agent include compounds such as dialkyl malonate, 3,5-dimethylpyrazole, ε-caprolactam, phenol, methyl ethyl ketoxime, alcohol, etc. Among these, dialkyl malonate is preferred from the viewpoint of good low-temperature curing properties.

[0050] As the polyfunctional blocked isocyanate compound (B), it is preferable to use an isocyanurate or biuret of hexamethylene diisocyanate blocked with a dialkyl malonate, from the viewpoints of low-temperature curing properties and low yellowing.

[0051] The amount of the polyfunctional blocked isocyanate compound (B) is preferably 3 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the viewpoints of improving the water resistance and moisture resistance of the anti-fogging film and thinning water drip marks, the amount is preferably 5 parts by mass or more and more preferably 8 parts by mass or more. From the viewpoints of improving the anti-fogging performance and adhesion of the anti-fogging film and suppressing whitening of water drip marks, the amount is preferably 20 parts by mass or less and more preferably 15 parts by mass or less.

[0052] Regarding the use ratio of the copolymer (A) to the polyfunctional blocked isocyanate compound (B), the equivalent ratio (NCO / OH) of the isocyanate groups of the polyfunctional blocked isocyanate compound (B) to the hydroxyl groups of the copolymer (A) is preferably 0.05 or more and 0.60 or less, and from the viewpoints of improving the water resistance and moisture resistance of the anti-fogging film and reducing the thickness of water drip marks, the equivalent ratio is more preferably 0.10 or more and even more preferably 0.20 or more, and from the viewpoints of improving the anti-fogging performance and adhesion of the anti-fogging film, the equivalent ratio is more preferably 0.50 or less and even more preferably 0.40 or less.

[0053] Furthermore, from the viewpoint of accelerating the crosslinking reaction, a catalyst may be used. Examples of the catalyst include metal organic compounds such as tin octoate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, and dibutyltin fatty acid salts; and tertiary amines such as tetramethylbutanediamine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene-7, and 1,5-diazabicyclo[4.3.0]nonene-5.

[0054] <Surfactant (C)> The surfactant (C) of the present invention may be at least one selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, and two or more types may be used in combination.

[0055] Examples of the anionic surfactant include fatty acid salts such as fatty acid alkali metal salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzenesulfonates and alkylnaphthalenesulfonates such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate; naphthalenesulfonic acid formalin condensate, dialkylsulfosuccinate, dialkylphosphate salt, polyoxyethylene sulfate salts such as sodium polyoxyethylene alkylphenyl ether sulfate; fluorine-containing anionic surfactants such as perfluoroalkyl group-containing carboxylates, perfluoroalkyl group-containing sulfonates, perfluoroalkenyl group-containing sulfonates, and perfluoroalkyl group-containing phosphate esters.From the viewpoint of improving the antifogging performance of the antifogging film, perfluoroalkenyl group-containing sulfonates and dialkylsulfosuccinates are preferred.

[0056] Examples of the cationic surfactant include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoformate, and stearamidoethyl diethylamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, tetrabutylammonium bromide, and lauryltrimethylammonium bromide. From the viewpoint of improving the antifogging performance of the antifogging film, quaternary ammonium salts are preferred.

[0057] Examples of the amphoteric surfactant include fatty acid-type amphoteric surfactants such as dimethyl alkyl lauryl betaine, dimethyl alkyl stearyl betaine, lauryl dimethyl aminoacetic acid betaine, and lauric acid amidopropyl dimethyl aminoacetic acid betaine; sulfonic acid-type amphoteric surfactants such as dimethyl alkyl sulfobetaine; amine oxide-type amphoteric surfactants such as alkyl (or alkenyl) dimethyl amine oxide, alkyl (or alkenyl) di(hydroxyethyl) amine oxide, polyoxyethylene alkyl (or alkenyl) ether dimethyl amine oxide, and polyoxyethylene alkyl (or alkenyl) ether di(hydroxyethyl) amine oxide; and amino acid-type amphoteric surfactants such as alkyl glycine. From the viewpoint of improving the anti-fogging performance of the anti-fogging film, fatty acid-type amphoteric surfactants are preferred.

[0058] Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene isodecyl ether, polyoxyethylene lauryl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol; polyoxyethylene acyl esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; polyoxyethylene sorbitan fatty acid esters such as polypropylene glycol ethylene oxide adduct, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate; phosphate esters such as alkyl phosphate esters and polyoxyethylene alkyl ether phosphate esters; sugar esters, cellulose ethers, and polyether macromers. From the viewpoint of improving the antifogging performance of the antifogging film, polyoxyethylene alkyl ethers and polyether macromers are preferred.

[0059] From the viewpoint that good anti-fogging performance can be obtained with a relatively small amount of surfactant (C), it is preferable to use a combination of an anionic surfactant and a cationic surfactant, or a combination of an anionic surfactant and an amphoteric surfactant, and it is even more preferable to use a nonionic surfactant in combination.

[0060] The surfactant (C) is preferably present in an amount of 0.5 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the viewpoint of improving the anti-fogging performance of the anti-fogging film, the surfactant (C) is more preferably present in an amount of 1 part by mass or more and even more preferably 1.5 parts by mass or more relative to 100 parts by mass of the copolymer (A). From the viewpoint of improving the transparency of the anti-fogging film and suppressing whitening due to dripping water, the surfactant (C) is more preferably present in an amount of 4 parts by mass or less and even more preferably 3 parts by mass or less. When an anionic surfactant and a cationic surfactant are used in combination, the mass ratio of the cationic surfactant to the anionic surfactant is preferably 0.01 to 0.50. When an anionic surfactant and an amphoteric surfactant are used in combination, the mass ratio of the amphoteric surfactant to the anionic surfactant is preferably 0.02 to 2.00. When an anionic surfactant and a cationic surfactant are used in combination and a nonionic surfactant is also used in combination, the mass ratio of the nonionic surfactant to the total of the anionic surfactant and the cationic surfactant is preferably 0.02 to 2.00, and when an anionic surfactant and an amphoteric surfactant are used in combination and a nonionic surfactant is also used in combination, the mass ratio of the nonionic surfactant to the total of the anionic surfactant and the amphoteric surfactant is preferably 0.02 to 2.00.

[0061] <Solvent (D)> The solvent (D) of the present invention contains at least a dihydric alcohol (D-1) and a glycol ether (D-2).

[0062] <Dihydric Alcohol (D-1)> The dihydric alcohol (D-1) is a compound represented by the following general formula (7): HO—R １５ -OH...(7) (In general formula (7), R １５ is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms.

[0063] Examples of the dihydric alcohol (D-1) include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, and 1,4-hexanediol. hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 2-methyl-2,4-pentanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4-heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, 2,3-heptanediol, 2,4-heptanediol, 2,5-heptanediol, 2,6-heptanediol, 3,4-heptanediol, 3,5-heptanediol, 4,5-heptanediol, and 2-ethyl-1,3-hexanediol.

[0064] From the viewpoint of suppressing dripping during coating, the dihydric alcohol (D-1) preferably has a boiling point of 240°C or less or has 8 or less carbon atoms, more preferably has a boiling point of 220°C or less or has 7 or less carbon atoms, and even more preferably has a boiling point of 210°C or less or has 6 or less carbon atoms. At least one dihydric alcohol (D) may be used, or two or more dihydric alcohols may be used in combination.

[0065] The dihydric alcohol (D-1) is contained in an amount of 5 parts by mass or more and 35 parts by mass or less relative to 100 parts by mass of the antifogging agent composition. From the viewpoint of suppressing solvent cracking, the dihydric alcohol (D-1) is contained in an amount of preferably 10 parts by mass or more and more preferably 15 parts by mass or more relative to 100 parts by mass of the antifogging agent composition, and from the viewpoint of suppressing poor drying and deterioration in adhesion during heat curing, the amount is preferably 30 parts by mass or less and more preferably 25 parts by mass or less.

[0066] <Glycol Ether (D-2)> The glycol ether (D-2) is a compound represented by the following general formula (8): １６ -O-R １７ -OH...(8) (In general formula (8), R １６ represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms; R １７ is a straight or branched alkylene group having 1 to 4 carbon atoms.

[0067] Examples of the glycol ether (D-2) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-n-octyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-butanol.

[0068] The glycol ether (D-2) has a boiling point of 180° C. or less, or R １６ and R １７ The total number of carbon atoms in the general formula (8) is preferably 8 or less, and the temperature is 160° C. or less, or １６ and R １７ It is more preferable that the total number of carbon atoms in １６ and R １７ It is more preferable that the total number of carbon atoms is 4 or less. At least one glycol ether (D-2) may be used, and two or more glycol ethers may be used in combination.

[0069] The glycol ether (D-2) is contained in an amount of 3 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the antifogging agent composition. From the viewpoint of dissolving the copolymer (A) and the surfactant (C), the glycol ether (D-2) is contained in an amount of preferably 5 parts by mass or more and more preferably 8 parts by mass or more relative to 100 parts by mass of the antifogging agent composition, and from the viewpoint of suppressing solvent cracking, the amount is preferably 12 parts by mass or less and more preferably 10 parts by mass or less.

[0070] The mass ratio of the dihydric alcohol (D-1) to the glycol ether (D-2) [(D-1) / (D-2)] is 0.5 or more and 8.0 or less, and from the viewpoint of suppressing dripping during coating, it is preferably 1.0 or more and more preferably 2.0 or more, and from the viewpoint of suppressing solvent cracking, it is preferably 6.0 or less and more preferably 4.0 or less.

[0071] <Colloidal Silica> The antifogging agent composition of the present invention can contain colloidal silica from the viewpoint of improving adhesion. The colloidal silica is fine particles of silica dispersed in a dispersion medium, and known colloidal silica can be used. From the viewpoint of the transparency of the antifogging film, the colloidal silica preferably has a particle diameter of 100 nm or less, more preferably 50 nm or less, and from the viewpoint of adhesion, the particle diameter is preferably 5 nm or more. The particle diameter is represented by the cumulant average particle diameter measured by dynamic light scattering. The colloidal silica may be used alone or in combination of two or more types.

[0072] Examples of the dispersion medium include water; alcohol-based solvents such as methanol, ethanol, isopropanol, 1-propanol, isobutanol, and 1-butanol; polyhydric alcohol-based solvents such as ethylene glycol; polyhydric alcohol derivatives such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monopropyl ether; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diacetone alcohol; amide-based solvents such as dimethylacetamide; ester-based solvents such as ethyl acetate; and aromatic hydrocarbon-based solvents such as toluene.

[0073] Examples of commercially available colloidal silica include water-dispersed colloidal silica sol (trade names: Snowtex O, Snowtex OS, Snowtex O-40, Snowtex OXS, etc.), methanol-dispersed colloidal silica (trade name: Methanol Silica Sol), isopropanol-dispersed colloidal silica (trade name: IPA-ST), ethylene glycol-dispersed colloidal silica (trade name: EG-ST), ethylene glycol mono-n-propyl ether-dispersed colloidal silica (trade name: NPC-ST-30), and propylene glycol monomethyl ether. Examples of suitable colloidal silica include colloidal silica dispersed in water (trade name: PGM-ST), colloidal silica dispersed in dimethylacetamide (trade name: DMAC-ST), colloidal silica dispersed in methyl ethyl ketone (trade name: MEK-ST-40), colloidal silica dispersed in methyl isobutyl ketone (trade name: MIBK-ST), colloidal silica dispersed in ethyl acetate (trade name: EAC-ST), colloidal silica dispersed in propylene glycol monomethyl ether acetate (trade name: PMA-ST), and colloidal silica dispersed in toluene (trade name: TOL-ST) (all manufactured by Nissan Chemical Industries, Ltd.). From the viewpoint of improving anti-fogging performance, the colloidal silica is preferably dispersed in water or a hydrophilic solvent.

[0074] When the colloidal silica is used, it is preferably 0.1 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the viewpoint of improving adhesion, the colloidal silica is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more relative to 100 parts by mass of the copolymer (A). From the viewpoint of improving transparency and anti-fogging performance, the colloidal silica is more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.

[0075] <Amino Acid Compound> The antifogging agent composition of the present invention can contain an amino acid compound from the viewpoint of reducing water drip marks. The amino acid compound of the present invention is an organic compound having one or more amino groups and one or more carboxy groups in the same molecule, and any conventionally known amino acid compound can be used, including natural aliphatic amino acids, natural aromatic amino acids, unnatural aliphatic amino acids, and unnatural aromatic amino acids. From the viewpoint of suppressing whitening due to drip marks, the amino acid compound may be an aminobenzoic acid compound, which is a non-natural aromatic amino acid, such as 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-3-hydroxybenzoic acid, 3-amino-4-hydroxybenzoic acid, anthranilic acid, 4-aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, 5-aminosalicylic acid, 5-aminoisophthalic acid, 2-aminoterephthalic acid, 3,5-diaminobenzoic acid, 4-aminophthalic acid, and 3,4-diaminobenzoic acid. Hydroxy group-containing aminobenzoic acid compounds are more preferred, such as 2-amino-3-hydroxybenzoic acid, 3-amino-4-hydroxybenzoic acid, anthranilic acid, 4-aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, and 5-aminosalicylic acid. At least one of the amino acid compounds may be used, and two or more of them may be used in combination.

[0076] When the amino acid compound is used, it is preferably 0.01 parts by mass or more and 5.00 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the viewpoint of suppressing whitening due to dripping water, the amount of the amino acid compound is more preferably 0.05 parts by mass or more and even more preferably 0.10 parts by mass or more relative to 100 parts by mass of the copolymer (A). From the viewpoint of improving anti-fogging performance and improving adhesion, the amount of the amino acid compound is more preferably 4.00 parts by mass or less and even more preferably 3.00 parts by mass or less.

[0077] The antifogging agent composition of the present invention may further contain a diluent solvent.

[0078] The dilution solvent is used for the purpose of adjusting the solid content and viscosity of the antifogging agent composition to be suitable for coating. As the dilution solvent, it is preferable to use a monohydric alcohol solvent which is thought to have little effect on solvent cracking of resin substrates, and examples thereof include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, and t-butanol. The solid content and viscosity of the dilution solvent suitable for coating vary, but the amount of the dilution solvent is usually preferably about 10 to 50 parts by mass, and more preferably about 20 to 40 parts by mass, per 100 parts by mass of the antifogging agent composition.

[0079] The antifogging agent composition of the present invention may contain, as other components, various conventional additives such as a leveling agent, a curing catalyst, an antioxidant, an ultraviolet absorber, a light stabilizer, etc. The amount of the other components added may be the conventional amount for each additive, but is usually 5 parts by mass or less per 100 parts by mass of the copolymer (A).

[0080] <Anti-Fog Article> The anti-fogging article of the present invention is obtained by applying the anti-fogging agent composition to an object to be coated by a coating method used for ordinary paints, and then heat-curing the composition to form an anti-fogging film on the surface of the object to be coated.

[0081] Any known resin substrate can be used as the substrate to be coated, regardless of its type, and examples thereof include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin.

[0082] When applying the antifogging agent composition to the substrate, it is preferable to remove any foreign matter adhering to the surface of the substrate before application in order to increase the wettability of the antifogging agent composition to the substrate and prevent repellency. Examples of methods include dust removal using high-pressure air or ionized air, ultrasonic cleaning with a detergent aqueous solution or an alcohol solvent, wiping using an alcohol solvent, and cleaning with ultraviolet light and ozone. Examples of application methods include immersion, flow coating, roll coating, bar coating, and spray coating.

[0083] The thickness of the anti-fogging film is preferably about 0.5 to 10 μm, more preferably about 1 to 5 μm, from the viewpoint of obtaining good anti-fogging properties and good coating appearance.

[0084] The antifogging article is not limited in its application, but can be used, for example, in vehicle lighting fixtures for automobiles, such as headlights, auxiliary headlights, width lights, license plate lights, tail lights, parking lights, back-up lights, turn signals, auxiliary turn signals, and emergency flashers.

[0085] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0086] <Production of Copolymer (A)> A reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube was charged with 250 parts by mass of n-butyl acetate as a polymerization solvent, and heated to 60°C while blowing in nitrogen gas. Next, a solution containing 30 parts by mass of N,N-dimethylacrylamide (manufactured by KJ Chemicals, trade name "DMAA") as monomer (A-1), 10 parts by mass of cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as monomer (A-2), 45 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as monomer (A-3), 15 parts by mass of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as monomer (A-4), 50 parts by mass of 1-butanol, and 0.5 parts by mass of t-butyl neodecanoate (manufactured by NOF Corporation, trade name "Perbutyl ND", active ingredient 70% by mass) as a radical polymerization initiator was added dropwise to the reaction vessel over 2 hours. After completion of the dropwise addition, the mixture was stirred for an additional 2 hours while maintaining the temperature at 60°C. The mixture was then heated to 70°C and stirred for 2 hours, and then cooled to produce a solution of copolymer (A). The polymerization conversion of the charged monomers of copolymer (A) was measured by gas chromatography and found to be 99% or more. Furthermore, the weight average molecular weight of copolymer (A) was measured by gel permeation chromatography and found to be 250,000. The solid content of the solution of copolymer (A) was 25% by mass. The hydroxyl value (theoretical value) of copolymer (A) was 72 mg KOH / g.

[0087] Example 1 Production of Antifogging Agent Composition To 400 parts by mass of a solution containing 100 parts by mass of the copolymer (A) obtained above, 200 parts by mass of 2,3-butanediol as the dihydric alcohol (D-1), 100 parts by mass of propylene glycol monomethyl ether as the glycol ether (D-2), and 300 parts by mass of 1-butanol as a dilution solvent were added, and the concentration of the diluted solution of copolymer (A) was adjusted to 10% by mass. Next, 14 parts by mass of an isocyanurate of hexamethylene diisocyanate blocked with dialkyl malonate (manufactured by Asahi Kasei Corporation, trade name "Duranate MF-K60B", active ingredient 60% by mass) as the polyfunctional blocked isocyanate compound (B), 2.0 parts by mass of sodium di(2-ethylhexyl)sulfosuccinate (manufactured by NOF Corporation, trade name "Rapisol A80", active ingredient 80% by mass) as the surfactant (C), 0.1 part by mass of dodecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass), and 1.0 part by mass of polyoxyethylene isodecyl ether (manufactured by NOF Corporation, trade name "Nonion ID-209", active ingredient 100% by mass), and 0.02 part by mass of polyether-modified polydimethylsiloxane (manufactured by BYK-Chemie KK, trade name "BYK-333") as a leveling agent were mixed together to produce an antifogging agent composition.

[0088] <(1) Evaluation of Solvent Crack> Assuming a case where the temperature is suddenly increased during heat curing, a substrate (polycarbonate resin plate) is left to stand for 2 hours in a dryer set to a heating temperature of 120°C or 130°C, and one drop (approximately 20 mg) of the antifogging composition obtained above is attached to the substrate (polycarbonate resin plate) when the temperature reaches 120°C or 130°C. The substrate (polycarbonate resin plate) with the antifogging composition attached is returned to the dryer and heat-cured for 20 minutes, after which the appearance of the droplet portion is observed with a laser microscope and evaluated according to the following four-point scale. Note that an evaluation of C or higher indicates no practical problem. A: No abnormality is observed in the appearance of the antifogging composition-adhered portion at a heating temperature of 130°C. B: Abnormality is observed in the appearance of the antifogging composition-adhered portion at a heating temperature of 130°C, but no abnormality is observed in the appearance of the antifogging composition-adhered portion at a heating temperature of 120°C. C: Slight abnormalities were observed in the appearance of the antifogging composition-adhered portion at a heating temperature of 120° C. D: Abnormalities were observed in the appearance of the antifogging composition-adhered portion at a heating temperature of 120° C.

[0089] <(2) Evaluation of Coatable Film Thickness> The anti-fog agent composition obtained above was spray-coated onto a 15 cm x 15 cm substrate (polycarbonate resin plate), and the substrate (polycarbonate resin plate) was placed upright in a dryer set to 120°C and heat-cured for 20 minutes. The test piece was removed from the dryer, and the thickness of the anti-fog film on the coated product, after visually confirming that no dripping had occurred, was measured and evaluated on the following three-point scale. Note that a rating of B or higher means that there is no problem in practical use. A: The maximum film thickness is 5 μm or more. B: The maximum film thickness is less than 5 μm and 4 μm or more. C: The maximum film thickness is less than 4 μm.

[0090] <(3) Evaluation of blushing> The antifogging agent composition obtained above was spray coated onto a substrate (polycarbonate resin plate) in an atmospheric environment of 30°C and 90% RH so that the thickness of the coating film after curing would be about 2 to 4 μm, and the plate was left in the same environment for 10 minutes. Next, heat curing was carried out at 120°C for 20 minutes to obtain a test piece. The coating film produced by the above method was visually observed and rated on the following three-point scale. Note that a rating of B or higher indicates no practical problem. A: No abnormalities such as whitening were observed. B: Whitening was observed in some areas. C: Whitening was observed throughout the plate.

[0091] <Preparation of Anti-Fog Article> The anti-fogging agent composition obtained above was spray coated onto a substrate (polycarbonate resin plate) in an atmospheric environment of 25°C and 30% RH so that the thickness of the coating film after curing would be about 2 to 4 µm, and the coating was then heat-cured at 120°C for 20 minutes to prepare an anti-fogging article (test piece) having an anti-fogging film.

[0092] The test pieces obtained above were used in the evaluation methods (4) to (7) below, and the results are shown in Table 1.

[0093] <(4) Initial Adhesion> In accordance with JIS K 5400 8.5.1, the presence or absence of peeling of the coating film was visually evaluated according to the following three levels. A rating of B or higher indicates no practical problem. A: No peeling was observed. B: Very partial peeling was observed. C: Complete peeling occurred.

[0094] <(5) Adhesion after moisture resistance test> The test pieces were left to stand at 50°C and 95% RH for 240 hours or 1000 hours, and then left to stand at room temperature for 1 hour. Thereafter, the presence or absence of peeling of the coating film was visually evaluated according to JIS K 5400 8.5.1 using the following three-level rating system. A rating of C or higher indicates no practical problems. A: No peeling was observed after 1000 hours of moisture resistance test. B: Peeling was observed after 1000 hours of moisture resistance test, but no peeling was observed after 240 hours. C: Very partial peeling was observed after 240 hours of moisture resistance test. D: Partial or complete peeling occurred after 240 hours of moisture resistance test.

[0095] <(6) Steam Anti-Fogging Properties> A test piece was placed with the coating surface facing downwards at a height of 2 cm above the water surface of a warm water bath maintained at 80°C, and the coating was continuously irradiated with steam from the warm water bath. The presence or absence of fogging after 10 seconds of irradiation was visually evaluated using the following four-point scale. A rating of B or higher indicates no practical problems. A: No fogging was observed. B: Fogging was observed, but the fogging disappeared within 10 seconds of steam irradiation. C: After 10 seconds of steam irradiation, an uneven water film was observed in part or all of the surface.

[0096] <(7) Water Drip Marks> A test piece was placed with the coating surface facing downwards at a height of 2 cm above the water surface of a warm water bath maintained at 80°C, and the coating was continuously irradiated with steam from the warm water bath for 30 seconds. After that, the test piece was held upright and the water drips were dried at room temperature for 10 to 15 minutes. This process was repeated 10 times, and the resulting water drip marks were visually evaluated according to the following three-point scale. Note that a rating of B or higher indicates no practical problem. A: Water drip marks are barely noticeable. B: Water drip marks are slightly noticeable or slightly white. C: Water drip marks are noticeable or white.

[0097] <Examples 2 to 44, Comparative Examples 1 to 9> <Production of antifogging agent compositions and preparation of antifogging articles> In each of the Examples and Comparative Examples, the antifogging agent compositions of Examples 2 to 44 and Comparative Examples 1 to 9 were produced in the same manner as in Example 1, except that the raw materials of Example 1 were changed to the raw materials and their proportions shown in Tables 1 to 4. Furthermore, antifogging articles (test pieces) having an antifogging film of Examples 2 to 44 and Comparative Examples 1 to 9 were produced in the same manner as in Example 1.

[0098] The results obtained for the antifogging agent compositions and antifogging films obtained above using the evaluation methods (1) to (7) above are shown in Tables 1 to 4.

[0099]

[0100]

[0101]

[0102]

[0103] In Tables 1 to 4, as monomers (A-1) to (A-4), DMAA is N,N-dimethylacrylamide (manufactured by KJ Chemicals, trade name "DMAA"); DEAA is N,N-diethylacrylamide (manufactured by KJ Chemicals, trade name "DEAA"); CHA is cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.); EHA is 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.); IBOA is isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.); THFA is tetrahydrofurfuryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.); CTFA is cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #200, CTFA"); GMA is glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.); HEA represents 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl value 483 mg KOH / g); HBA represents 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl value 389 mg KOH / g); and HEAA represents 2-hydroxyethyl acrylamide (manufactured by KJ Chemicals, trade name "HEAA", hydroxyl value 487 mg KOH / g).

[0104] In Tables 1 to 4, examples of the polyfunctional blocked isocyanate compound (B) include: Duranate MF-K60B, an isocyanurate of hexamethylene diisocyanate blocked with dialkyl malonate (manufactured by Asahi Kasei Corporation, active ingredient 60% by mass, NCO amount 6.5% by mass); and Duranate WM44-L70G, an isocyanurate of hexamethylene diisocyanate blocked with dialkyl malonate (manufactured by Asahi Kasei Corporation, active ingredient 70% by mass, NCO amount 5.3% by mass).

[0105] In Tables 1 to 4, surfactants (C) include: Rapisol: sodium di(2-ethylhexyl)sulfosuccinate (manufactured by NOF Corporation, trade name "Rapisol A-80", active ingredient 80% by mass); Pelex TR: sodium ditridecylsulfosuccinate (manufactured by Kao Corporation, trade name "Pelex TR", active ingredient 70% by mass); F100: perfluoroalkenyl sulfonate (manufactured by Neos Corporation, active ingredient 100% by mass); DTAB: dodecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass); TBAB: tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass); BL-SF: lauryldimethylaminoacetic acid betaine (manufactured by NOF Corporation, trade name "Nissan Anon BL-SF", active ingredient 35.5% by mass); BDL-SF is lauramidopropyl dimethylaminoacetic acid betaine (manufactured by NOF Corporation, trade name "Nissan Anon BDL-SF", active ingredient 30% by mass); DM10 is decyl dimethylamine oxide (manufactured by Lion Specialty Chemicals, trade name "Cadenax DM10D-W", active ingredient 40% by mass); DM14 is myristyl dimethylamine oxide (manufactured by Lion Specialty Chemicals, trade name "Cadenax DM14D-N", active ingredient 25% by mass); ID-209 is polyoxyethylene isodecyl ether (manufactured by NOF Corporation, trade name "Nonion ID-209", active ingredient 100% by mass); Softanol 120 is polyoxyethylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., "Softanol 120", active ingredient 100% by mass); BYK-3560 represents a polyether macromer-modified acrylate (manufactured by BYK-Chemie, active ingredient 100% by mass).

[0106] In Tables 1 to 4, as dihydric alcohols (D-1), 23BD represents 2,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 182°C); HG represents 2-methyl-2,4-pentanediol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 197°C); 13PD represents 1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 214°C); 14BD represents 1,4-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 228°C); and 3M15PD represents 3-methyl-1,5-pentanediol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 250°C).

[0107] In Tables 1 to 4, as glycol ethers (D-2), PGM represents propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 120°C); EGtBE represents ethylene glycol mono-t-butyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 152°C); MMB represents 3-methoxy-3-methyl-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 174°C); and EGHE represents ethylene glycol monohexyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass, boiling point 208°C).

[0108] In Tables 1 to 4, as colloidal silica, Snowtex O represents a water-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., active ingredient 20% by mass, particle size 12 nm); and Snowtex N represents a water-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd., active ingredient 20% by mass, particle size 12 nm).

[0109] In Tables 1 to 4, the amino acid compounds are: 4ABA represents 4-aminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass); and 4ASA represents 4-aminosalicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass).

[0110] In Tables 1 to 4, as the leveling agent, BYK-333 represents polyether-modified polydimethylsiloxane (manufactured by BYK-Chemie, active ingredient 100% by mass).

[0111] In Tables 1 to 4, as a dilution solvent, NBA represents 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass).

Claims

1. An anti-fogging agent composition comprising a copolymer (A), a polyfunctional blocked isocyanate compound (B), a surfactant (C), and a solvent (D), wherein the copolymer (A) is a (meth)acrylate copolymer obtained from a monomer mixture containing a monomer (A-1) represented by the following general formula (1): (In general formula (1), R １ is a hydrogen atom or a methyl group, and R ２ is a linear or branched alkyl group having 1 to 4 carbon atoms, -C(CH ３ ) ２ CH ２ COCH ３ , -C ２ H ４ N (CH ３ ) ２ , or -C ３ H ６ N (CH ３ ) ２ and R ３ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. ） 　 The solvent (D) contains a dihydric alcohol (D-1) and a glycol ether (D-2), and the dihydric alcohol (D-1) is a compound represented by the following general formula (7): HO—R １５ -OH...(7) (In general formula (7), R １５ is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms. The glycol ether (D-2) is a compound represented by the following general formula (8), １６ -O-R １７ -OH...(8) (In general formula (8), R １６ represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms; R １７ is a linear or branched alkylene group having 1 to 4 carbon atoms.) An antifogging agent composition, characterized in that, relative to 100 parts by mass of the antifogging agent composition, the dihydric alcohol (D-1) is 5 parts by mass or more and 35 parts by mass or less, and the glycol ether (D-2) is 3 parts by mass or more and 15 parts by mass or less, and the mass ratio of the dihydric alcohol (D-1) to the glycol ether (D-2) [(D-1) / (D-2)] is 0.5 or more and 8.0 or less.

2. The anti-fogging agent composition according to claim 1, wherein the monomer mixture contains a monomer (A-2) represented by the following general formula (2), one or more monomers (A-3) selected from the group consisting of a monomer represented by the following general formula (3) and a monomer represented by the following general formula (4), and one or more monomers (A-4) selected from the group consisting of a monomer represented by the following general formula (5) and a monomer represented by the following general formula (6): (In general formula (2), R ４ is a hydrogen atom or a methyl group, and R ５ is a straight-chain, branched-chain, or cyclic hydrocarbon group having 1 to 18 carbon atoms. (In general formula (3), R ６ is a hydrogen atom or a methyl group, and R ７ is a linear alkylene group having 1 to 4 carbon atoms, and R ８ is a substituent having a heterocyclic skeleton. (In general formula (4), R ９ is a hydrogen atom or a methyl group, and R １０ is a substituent having a heterocyclic skeleton. (In general formula (5), R １１ is a hydrogen atom or a methyl group, and R １２ is a linear or branched alkylene group having 2 to 4 carbon atoms, or -C ２ H ４ (OCO(CH ２ ) ５ ) ｎ - and n is 1 to 5. (In general formula (6), R １３ is a hydrogen atom or a methyl group, and R １４ is a straight or branched alkylene group having 1 to 4 carbon atoms.

3. An anti-fogging article having an anti-fogging film formed from the anti-fogging agent composition according to claim 1 or 2 on a substrate.

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