Antifogging agent composition, antifogging product having an antifogging film formed from the composition

Abstract

The present invention is a kind of antifogging agent composition, it comprises copolymer (A), multifunctional blocked isocyanate compound (B) and surfactant (C), wherein, the copolymer (A) is a (methyl) acrylate copolymer obtained by a monomer mixture comprising monomer (A-1), monomer (A-2) and monomer (A-3), and the surfactant (C) comprises a specific amount of anionic surfactant (C-1), a specific amount of surfactant (C-2) with a quaternary ammonium salt structure and a specific amount of fluorine-based nonionic surfactant (C-3). The antifogging performance of the antifogging film formed by the antifogging agent composition is excellent, it is not easy to produce dripping marks, and the produced dripping marks fade over time under a high humidity environment.

Description

Technical Field

[0001] The present invention relates to an antifogging agent composition and an antifogging product having an antifogging film formed by the composition. Background Art

[0002] In headlights and other headlamps of automobiles, sometimes high-humidity air enters the lamp cavity, the lens becomes cold due to external air or rainfall, and moisture condenses on the inner surface to generate fog. As a result, there is a problem that the brightness of the headlight is reduced and the appearance of the lens surface is damaged, causing discomfort to the user. In order to prevent such lens fogging, a method is known to form an anti-fog film (dried coating or cured coating) by applying an anti-fog agent to the part where fog is generated (inside the lens).

[0003] For example, Patent Document 1 discloses an antifogging agent composition containing a specific copolymer, a multifunctional blocked isocyanate compound, an anionic surfactant, and a cationic surfactant. In addition, Patent Document 2 discloses an antifogging agent composition containing a specific copolymer, a multifunctional blocked isocyanate compound, an anionic surfactant, and a betaine-type surfactant. Furthermore, Patent Document 3 discloses an antifogging agent composition containing a specific copolymer, a multifunctional blocked isocyanate compound, a fluorine-based anionic surfactant, and a betaine-type surfactant.

[0004] Furthermore, Patent Document 4 discloses an anti-fogging agent containing a fluorinated betaine-type surfactant or a fluorinated anionic surfactant, and a fluorinated nonionic surfactant.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2016 / 047430

[0008] Patent Document 2: Japanese Patent Application Publication No. 2016-169287

[0009] Patent Document 3: Japanese Patent Application Publication No. 2016-169288

[0010] Patent Document 4: Japanese Patent Application Publication No. 2016-60878 Summary of the invention

[0011] Technical Problems to be Solved by the Invention

[0012] On the other hand, it is known that if water contacts the anti-fog film to form a water film and the generated water droplets are dried, the surfactant dissolved in the water will precipitate to form dripping marks, resulting in poor appearance of the headlight. The anti-fog agent disclosed in the above-mentioned patent documents 1 to 3 uses an anionic surfactant and a cationic surfactant at the same time, or uses an anionic surfactant and a betaine-type surfactant at the same time, so that the two different surfactants form an ion pair, thereby reducing the outflow of the surfactant caused by water, and has excellent anti-fog performance and the effect of inhibiting the above-mentioned dripping marks.

[0013] However, the anti-fogging films disclosed in Patent Documents 1 to 3 have a concern that even in a high humidity environment, deep drip marks generated under specific conditions such as heavy condensation may not easily disappear.

[0014] Furthermore, the anti-fogging agent disclosed in Patent Document 4 has the following technical problem: since it does not have a resin component for retaining a surfactant, once water droplets are generated, all the surfactant will flow out and the anti-fogging property will disappear.

[0015] In view of the above situation, the object of the present invention is to provide an anti-fogging agent composition having excellent anti-fogging performance, being less likely to produce drip marks, and the produced drip marks becoming lighter over time under a high humidity environment, and an anti-fogging product having an anti-fogging film formed by the composition.

[0016] Technical means to solve technical problems

[0017] That is, the present invention relates to an antifogging agent composition, which comprises a copolymer (A), a polyfunctional blocked isocyanate compound (B) and a surfactant (C), wherein the antifogging agent composition:

[0018] The copolymer (A) is a (meth)acrylate copolymer obtained from a monomer mixture, wherein the monomer mixture comprises: one or more monomers (A-1) selected from the group consisting of monomers represented by the following general formula (1) and monomers represented by the following general formula (2); a monomer (A-2) represented by the following general formula (3); and one or more monomers (A-3) selected from the group consisting of monomers represented by the following general formula (4) and monomers represented by the following general formula (5),

[0019] [Chemical formula 1]

[0020]

[0021] In the general formula (1), R 1 is a hydrogen atom or a methyl group, R 2is a linear or branched alkyl group having 1 to 4 carbon atoms, -C(CH3)2CH2COCH3, -C2H4N(CH3)2 or -C3H6N(CH3)2, R 3 is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms,

[0022] [Chemical formula 2]

[0023]

[0024] In the general formula (2), R 4 is a hydrogen atom or a methyl group,

[0025] [Chemical formula 3]

[0026]

[0027] In the general formula (3), R 5 is a hydrogen atom or a methyl group, R 6 is a straight-chain, branched or cyclic hydrocarbon group having 1 to 16 carbon atoms,

[0028] [Chemical formula 4]

[0029]

[0030] In the general formula (4), R 7 is a hydrogen atom or a methyl group, R 8 A linear or branched alkylene group having 2 to 4 carbon atoms or -C2H4(OCO(CH2)5) n -, n is 1 to 5,

[0031] [Chemical formula 5]

[0032]

[0033] In the general formula (5), R 9 is a hydrogen atom or a methyl group, R 10 is a straight-chain or branched alkylene group having 1 to 4 carbon atoms,

[0034] The surfactant (C) comprises an anionic surfactant (C-1), a surfactant having a quaternary ammonium salt structure (C-2) and a fluorine-based nonionic surfactant (C-3),

[0035] Relative to 100 parts by mass of the copolymer (A), the anionic surfactant (C-1) is 1 part by mass or more and 10 parts by mass or less, the surfactant (C-2) having a quaternary ammonium salt structure is 0.01 parts by mass or more and 3 parts by mass or less, and the fluorine-based nonionic surfactant (C-3) is 0.05 parts by mass or more and 5 parts by mass or less,

[0036] The mass ratio of the fluorinated nonionic surfactant (C-3) to the total amount of the anionic surfactant (C-1) and the surfactant having a quaternary ammonium salt structure (C-2) {(C-3) / [(C-1)+(C-2)]} is greater than or equal to 0.005 and less than or equal to 2.5.

[0037] In addition, the present invention relates to an anti-fogging product having an anti-fogging film formed from the anti-fogging agent composition on a substrate.

[0038] Effects of the Invention

[0039] The details of the mechanism of action of the antifogging agent composition, antifogging film and antifogging product of the present invention are still unclear, but are presumed as follows. However, the present invention is not limited to this mechanism of action.

[0040] The antifogging agent composition of the present invention contains a specific copolymer (A), a multifunctional blocked isocyanate compound (B), and the anionic surfactant (C-1), the surfactant (C-2) having a quaternary ammonium salt structure, and the fluorine-based nonionic surfactant (C-3) as a surfactant (C). The water solubility of the ion pair formed by using the anionic surfactant (C-1) and the surfactant (C-2) having a quaternary ammonium salt structure at the same time is lower than that of the anionic surfactant (C-1) or the surfactant (C-2) having a quaternary ammonium salt structure. Therefore, the antifogging film using only the anionic surfactant (C-1) and the surfactant (C-2) having a quaternary ammonium salt structure as surfactants will not absorb moisture even if exposed to a high humidity environment, and the dripping mark will not fade. On the other hand, by blending a certain amount of the fluorine-based nonionic surfactant (C-3) into these surfactants, the fluorine-based nonionic surfactant (C-3) improves the surface activity of the above-mentioned ion pair and improves the hygroscopicity of the dripping mark. As a result, in a high humidity environment, the dripping mark is gradually affected by moisture and fades over time. Therefore, the anti-fogging film obtained from the anti-fogging agent composition of the present invention has excellent anti-fogging performance, is less likely to produce drip marks, and the produced drip marks will fade over time in a high humidity environment. DETAILED DESCRIPTION

[0041] The anti-fogging agent composition of the present invention comprises a copolymer (A), a multifunctional blocked isocyanate compound (B) and a surfactant (C).

[0042] <Copolymer (A)>

[0043] The copolymer (A) of the present invention is a (meth)acrylate copolymer obtained from a monomer mixture containing at least the following monomers (A-1) to (A-3).

[0044] <Monomer (A-1)>

[0045] The monomer (A-1) is one or more selected from the group consisting of a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2).

[0046] [Chemical formula 6]

[0047]

[0048] In the general formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms, -C(CH3)2CH2COCH3, -C2H4N(CH3)2 or -C3H6N(CH3)2, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0049] [Chemical formula 7]

[0050]

[0051] In the general formula (2), R 4 A hydrogen atom or a methyl group.

[0052] In the general formula (1), the linear or branched alkyl group having 1 to 4 carbon atoms includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. 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 a hydrogen atom, preferably R 2 and R 3 are independently a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. 4 A hydrogen atom is preferred. At least one monomer (A-1) may be used, or two or more monomers may be used in combination.

[0053] <Monomer (A-2)>

[0054] The monomer (A-2) is a monomer represented by the following general formula (3).

[0055] [Chemical formula 8]

[0056]

[0057] In the general formula (3), R 5 is a hydrogen atom or a methyl group, R 6It is a linear, branched or cyclic hydrocarbon group having 1 to 16 carbon atoms.

[0058] In the general formula (3), as the linear, branched or cyclic hydrocarbon group having 1 to 16 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-nonyl, isobornyl, alkyl groups such as dodecyl, tetradecyl, hexadecyl, octadecyl, and docosyl; alkenyl groups such as oleyl; aryl groups such as phenyl, etc. From the perspective of improving the adhesion and water resistance of the anti-fogging film to the substrate and improving the anti-fogging property of the anti-fogging film, the carbon number is preferably 1 to 8. At least one monomer (A-2) may be used, or two or more monomers may be used in combination.

[0059] <Monomer (A-3)>

[0060] The monomer (A-3) is at least one selected from the group consisting of a monomer represented by the following general formula (4) and a monomer represented by the following general formula (5).

[0061] [Chemical formula 9]

[0062]

[0063] In the general formula (4), R 7 is a hydrogen atom or a methyl group, R 8 A linear or branched alkylene group having 2 to 4 carbon atoms or -C2H4(OCO(CH2)5) n -, n is 1 to 5.

[0064] [Chemical formula 10]

[0065]

[0066] In the general formula (5), R 9 is a hydrogen atom or a methyl group, R 10 It is a linear or branched alkylene group having 1 to 4 carbon atoms.

[0067] In the general formula (4), the linear or branched alkylene group having 2 to 4 carbon atoms includes, for example, ethylene, propylene, 2-methylmethylene, butylene, 2-methylpropylene, 3-methylpropylene, 2,2-dimethylmethylene, 2-ethylmethylene, and the like. From the perspective of improving the water resistance and antifogging durability of the antifogging film, R 8 It is 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 still more preferably an ethylene group or a propylene group.

[0068] In the general formula (5), the linear or branched alkylene group having 1 to 4 carbon atoms includes, for example, methylene, ethylene, propylene, 2-methylmethylene, butylene, 2-methylpropylene, 3-methylpropylene, 2,2-dimethylmethylene, 2-ethylmethylene, etc. From the perspective of improving the water resistance and anti-fog durability of the anti-fog film, R 10 It 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 still more preferably a methylene group or an ethylene group.

[0069] At least one monomer (A-3) may be used, or two or more monomers may be used in combination.

[0070] Hereinafter, the ratio of each monomer component in the monomer mixture forming the copolymer (A) of the present invention will be described.

[0071] In the total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), the monomer (A-1) is preferably 35 parts by mass or more and 90 parts by mass or less. In the total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), from the perspective of improving anti-fogging properties, the monomer (A-1) is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and from the perspective of water resistance and suppression of drip marks, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.

[0072] In the total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), the monomer (A-2) is preferably 5 parts by mass or more and 60 parts by mass or less. In the total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), from the perspective of improving water resistance and adhesion and suppressing drip marks, the monomer (A-2) is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and from the perspective of making the anti-fogging property last, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

[0073] In a total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), the monomer (A-3) is preferably 5 parts by mass or more and 30 parts by mass or less. In a total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), from the perspective of improving water resistance and suppressing drip marks, the monomer (A-3) is preferably 8 parts by mass or more, more preferably 10 parts by mass or more, and from the perspective of improving adhesion, it is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0074] In the monomer mixture, the total proportion of the monomers (A-1) to (A-3) is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0075] In addition, the following monomers can be used as other monomers in addition to the monomers (A-1) to (A-3) in the monomer mixture, for example, aromatic vinyl monomers such as styrene, vinyltoluene, and α-methylstyrene; vinyl monomers containing a quaternary ammonium salt structure such as (meth)acryloyloxyethyltrimethylammonium chloride and (meth)acryloylaminopropyltrimethylammonium chloride; alicyclic acrylic monomers such as (meth)phenoxyethyl acrylate, tetrahydrofurfuryl (meth)acrylate, and isobornyl (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; styrenesulfonic acid, vinylsulfonic acid, and methallylsulfonic acid; Vinyl monomers containing sulfonic acid groups, such as 2-(meth)acrylamide-2-methylpropanesulfonic acid, 3-sulfopropyl (meth)acrylate, and their ammonium salts, organic amine salts, and alkali metal salts; vinyl monomers containing phosphate groups, such as 2-(meth)acryloyloxyethyl acid phosphate, and their ammonium salts, organic amine salts, and alkali metal salts; 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol (meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate ester, N,N'-methylenebis[(meth)acrylamide] and other difunctional (meth)acrylates; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and other multifunctional vinyl monomers; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, vinyltrimethoxysilane and other vinyl monomers having an alkoxysilyl group; (meth)acrylate glycidyl, vinyl glycidyl ether, allyl glycidyl ether and other vinyl monomers having an epoxy group, etc.

[0076] <Method for preparing copolymer (A)>

[0077] The copolymer (A) of the present invention is obtained by copolymerizing the monomer mixture. As the structure of the copolymer, any structure in a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer can be used. From the perspective of being able to improve the effect of the antifogging agent composition headed by antifogging, and being able to easily prepare the antifogging agent composition, a random copolymer is preferred. As a polymerization method for obtaining a copolymer, various known polymerization methods such as free radical polymerization, cationic polymerization, living anionic polymerization, and living cationic polymerization can be used, and in particular, free radical polymerization is preferred from the ease of industrial productivity and various performances. As a free radical polymerization method, conventional bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, etc. can be used, but in terms of being able to be directly used as an antifogging agent composition after polymerization, solution polymerization is preferred.

[0078] As the polymerization solvent used in the solution polymerization method, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, diacetone alcohol, etc. can be used; alcohol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl lactate, ethyl lactate, etc.; aromatic solvents such as benzene, toluene, xylene, etc., amide solvents such as formamide, dimethylformamide, etc.; water, etc. The polymerization solvents can be used alone or in combination of two or more.

[0079] The free radical polymerization initiator can use commonly used organic peroxides, azo compounds, etc. As the organic peroxide, for example, benzoyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, tert-butyl peroxy-2-hexanoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, etc. As the azo compound, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, etc. can be listed. The free radical polymerization initiator can be used alone or in combination of two or more.

[0080] The amount of the free radical polymerization initiator added is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the monomer mixture. In order to easily control the exothermic heat of polymerization, it is preferred to perform polymerization while dripping the free radical polymerization initiator into the reaction vessel. The temperature for performing the polymerization reaction can be appropriately changed according to the type of free radical polymerization initiator used, but for industrial production, it is preferably 30 to 150° C., and more preferably 40 to 100° C.

[0081] From the perspective of imparting water resistance to the anti-fogging film, the weight average molecular weight (Mw) of the copolymer (A) is preferably 20,000 or more, more preferably 30,000 or more. From the perspective of improving the coating and handling properties of the anti-fogging agent composition, the weight average molecular weight (Mw) of the copolymer (A) is preferably 120,000 or less, more preferably 110,000 or less.

[0082] The weight average molecular weight (Mw) of the copolymer (A) can be determined by GPC method. The sample can be measured under the following conditions using a 0.2 mass % solution prepared by dissolving the sample in dimethylformamide and filtering the solution with a 0.5 μm membrane filter.

[0083] <Measurement of weight average molecular weight (Mw)>

[0084] Analytical device: HLC-8320GPC (manufactured by TOSOH CORPORATION)

[0085] Chromatographic columns: KD-802.5 (manufactured by SHOWA DENKO KK), KD-803 (manufactured by SHOWA DENKO KK), KD-80M (manufactured by SHOWA DENKO KK) connected in series

[0086] Column size: 8.0×300mm

[0087] Eluent: dimethylformamide

[0088] Flow rate: 1.0mL / min

[0089] Detector: Differential refractometer

[0090] Column temperature: 40°C

[0091] Standard sample: polystyrene

[0092] <Multifunctional blocked isocyanate compound (B)>

[0093] The polyfunctional blocked isocyanate compound (B) of the present invention is a compound obtained by blocking the isocyanate group of a compound having two or more isocyanate groups in one molecule with a blocking agent. As long as the polyfunctional blocked isocyanate compound (B) is cross-linked with at least the copolymer (A) to form a cured film, there is no particular limitation. At least one polyfunctional blocked isocyanate compound (B) may be used, or two or more may be used in combination.

[0094] 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 toluene 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 such as biuret bodies, isocyanurate bodies, adducts, and allophanate bodies of these diisocyanate group-containing compounds. Among the above, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, and derivatives thereof are preferred from the viewpoint of suppressing yellowing.

[0095] Examples of the terminal blocking agent include compounds such as diethyl malonate, 3,5-dimethylpyrazole, ε-caprolactam, phenol, methyl ethyl ketoxime, and alcohols. Among the above, diethyl malonate is preferred because of its good low-temperature curability.

[0096] As the polyfunctional blocked isocyanate compound (B), an isocyanurate or biuret form of hexamethylene diisocyanate blocked with diethyl malonate is preferably used from the viewpoints of low temperature curability and low yellowing property.

[0097] Regarding the usage ratio of the copolymer (A) and the multifunctional blocked isocyanate compound (B), the equivalent ratio (NCO / OH) of the isocyanate group of the multifunctional blocked isocyanate compound (B) to the hydroxyl group of the copolymer (A) is preferably 0.1 or more and 1.5 or less. From the perspective of improving the water resistance of the anti-fog film and improving water resistance and moisture resistance, it is preferably 0.2 or more, preferably 0.3 or more, and from the perspective of improving anti-fog properties and adhesion, it is preferably 1.2 or less.

[0098] In addition, from the perspective of promoting the cross-linking reaction, a catalyst may be used. Examples of the catalyst include metal organic compounds such as tin octoate, dibutyltin bis(2-ethylhexanoate), dioctyltin bis(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]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene.

[0099] <Surfactant (C)>

[0100] The surfactant (C) of the present invention comprises an anionic surfactant (C-1), a surfactant having a quaternary ammonium salt structure (C-2) and a fluorine-based nonionic surfactant (C-3).

[0101] As the anionic surfactant (C-1), all the anionic surfactants known in the past can be used, for example, fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates and alkylnaphthalene sulfonates such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate; naphthalenesulfonic acid dialkyl phosphate ester salts, naphthalenesulfonic acid formaldehyde condensation products, dialkyl sulfosuccinates, dialkyl phosphate ester salts, polyoxyethylene alkylphenyl ether sodium sulfate and other polyoxyethylene sulfates. In addition, as the anionic surfactant (C-1), for example, fluorine-based anionic surfactants such as perfluoroalkyl carboxylates, perfluoroalkenyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkenyl sulfonates, perfluoroalkyl phosphates, and perfluoroalkenyl phosphates can be listed. From the perspective of excellent anti-fog performance and anti-fog durability, and the difficulty in seeing water dripping marks, the anionic surfactant (C-1) is preferably a fluorine-based anionic surfactant. At least one of the anionic surfactants (C-1) can be used, and two or more can be used in combination.

[0102] As the surfactant (C-2) having a quaternary ammonium salt structure, compounds having at least one quaternary ammonium group in the molecule, such as a cationic surfactant or a betaine-type surfactant, can be cited, and all the surfactants having a quaternary ammonium salt structure known in the past can be used. At least one surfactant (C-2) having a quaternary ammonium salt structure can be used, or two or more can be used in combination.

[0103] Examples of the cationic surfactant include amine salts such as ethanolamines, dodecylamine acetate, triethanolamine monoformate, and stearylamide ethyl diethylamine acetate; alkyl trimethyl ammonium salts such as dodecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride; dialkyl dimethyl ammonium salts such as didodecyl dimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and octadecyl dimethyl benzyl ammonium chloride; and fluorine-based cationic surfactants such as perfluoroalkyl trimethyl ammonium salts and perfluoroalkenyl trimethyl ammonium salts.

[0104] Examples of the betaine-type surfactant include fatty acid-type betaine-type surfactants such as dimethyl alkyl dodecyl betaine and dimethyl alkyl octadecyl betaine; sulfonic acid-type betaine-type surfactants such as dimethyl alkyl sulfobetaine; alkyl glycine; and fluorine-based betaine-type surfactants such as perfluoroalkyl betaine and perfluoroalkenyl betaine.

[0105] As the fluorine-based nonionic surfactant (C-3), all previously known fluorine-based nonionic surfactants can be used, for example, perfluoroalkylamine oxides, perfluoroalkenylamine oxides, perfluoroalkylethylene oxide adducts, perfluoroalkenylethylene oxide adducts, oligomers with perfluoroalkyl and hydrophilic groups, oligomers with perfluoroalkenyl and hydrophilic groups, oligomers with perfluoroalkyl and lipophilic groups, oligomers with perfluoroalkenyl and lipophilic groups, oligomers with perfluoroalkyl and hydrophilic groups and lipophilic groups, oligomers with perfluoroalkenyl and hydrophilic groups and lipophilic groups, etc. From the perspective of improving anti-fog durability and making drip marks inconspicuous, and making drip marks disappear under high humidity environments, the fluorine-based nonionic surfactant (C-3) is preferably a fluorine-based nonionic surfactant having two or more perfluoroalkenyl groups in the molecule. At least one of the fluorine-based nonionic surfactants (C-3) can be used, and two or more can also be used in combination.

[0106] The amount of the anionic surfactant (C-1) is 1.0 parts by mass or more and 10.0 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the perspective of improving anti-fogging properties and heat resistance, the amount of the anionic surfactant (C-1) is more preferably 2.0 parts by mass or more, and more preferably 2.5 parts by mass or more relative to 100 parts by mass of the copolymer (A), and from the perspective of suppressing drip marks, it is more preferably 8.0 parts by mass or less, and more preferably 7.0 parts by mass or less.

[0107] The surfactant (C-2) having a quaternary ammonium salt structure is 0.01 to 3 parts by mass relative to 100 parts by mass of the copolymer (A). From the perspective of improving anti-fogging properties, the surfactant (C-2) having a quaternary ammonium salt structure is more preferably 0.02 parts by mass or more, more preferably 0.10 parts by mass or more, and from the perspective of suppressing drip marks, it is more preferably 2.5 parts by mass or less, more preferably 1.5 parts by mass or less.

[0108] The fluorine-based nonionic surfactant (C-3) is 0.05 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the perspective of improving the anti-fog durability and making the drip marks inconspicuous and making the drip marks disappear under a high humidity environment, the fluorine-based nonionic surfactant (C-3) is more preferably 0.10 parts by mass or more relative to 100 parts by mass of the copolymer (A), and from the perspective of heat resistance, adhesion, and drip marks, it is more preferably 3 parts by mass or less, and further preferably 1 part by mass or less.

[0109] From the perspective of anti-fog durability, the mass ratio of the surfactant (C-2) having a quaternary ammonium salt structure to the anionic surfactant (C-1) ((C-2) / (C-1)) is preferably greater than 0.01, more preferably greater than 0.03, and from the perspective of making it easier for water drip marks to disappear over time in a high humidity environment, it is preferably less than 0.8, more preferably less than 0.3.

[0110] The mass ratio of the fluorinated nonionic surfactant (C-3) to the total amount of the anionic surfactant (C-1) and the surfactant (C-2) having a quaternary ammonium salt structure {(C-3) / [(C-1)+(C-2)]} is 0.005 or more and 2.5 or less. From the perspective of making it easier for water dripping marks to disappear over time in a high humidity environment, the mass ratio of the fluorinated nonionic surfactant (C-3) to the total amount of the anionic surfactant (C-1) and the surfactant (C-2) having a quaternary ammonium salt structure {(C-3) / [(C-1)+(C-2)]} is preferably 0.02 or more.

[0111] If the fluorine-based nonionic surfactant (C-3) and the non-fluorine-based nonionic surfactant (C-3') are used simultaneously, the effect of making the water dripping marks fade in a high humidity environment is improved. The non-fluorine-based nonionic surfactant (C-3') can use all the previously known non-fluorine-based nonionic surfactants, for example, polyoxyethylene lauryl ethers, polyoxyethylene oleyl ethers and other polyoxyethylene higher alcohol ethers; polyoxyethylene alkyl aryl ethers such as octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether; polyoxyethylene acyl esters such as polyethylene glycol monostearate; polyoxyethylene sorbitan fatty acid esters such as polypropylene glycol ethylene oxide adduct, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate; phosphate esters such as alkyl phosphate esters and polyoxyethylene alkyl ether phosphate esters; sugar esters, cellulose ethers, etc. From the perspective of heat resistance and drip marks, the amount of the non-fluorinated nonionic surfactant (C-3') added is preferably less than that of the fluorinated nonionic surfactant (C-3). For example, relative to 100 parts by mass of the copolymer (A), the amount of the non-fluorinated nonionic surfactant (C-3') added is preferably 3.0 parts by mass or less, more preferably 1.0 parts by mass or less, and further preferably 0.5 parts by mass or less.

[0112] <Colloidal Silica (D)>

[0113] From the perspective of further improving the effect of fading the trace of dripping water under a high humidity environment, the antifogging agent composition of the present invention can include colloidal silica (D). The colloidal silica (D) is a particle of silica dispersed in a dispersion medium, and known colloidal silica can be used. From the perspective of the transparency of the cured film, the particle diameter of the colloidal silica (D) is preferably less than 100nm, more preferably less than 50nm, and more preferably less than 30nm, and from the perspective of adhesion, the particle diameter of the colloidal silica (D) is preferably more than 10nm. In addition, the particle diameter is represented by the cumulative average particle diameter measured by a dynamic light scattering method. The colloidal silica (D) can be used alone or in combination with two or more.

[0114] Examples of the dispersion medium include water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; polyol solvents such as ethylene glycol; polyol derivatives such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monopropyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diacetone alcohol; amide solvents such as dimethylacetamide; ester solvents such as ethyl acetate; aromatic hydrocarbon solvents such as toluene, and the like.

[0115] Examples of commercially available products of the colloidal silica (D) include water-dispersible colloidal silica sols (trade names: SNOWTEX 30, SNOWTEX O, SNOWTEX OS, SNOWTEX C, SNOWTEX N, etc.), methanol-dispersible colloidal silica (trade name: Methanol silica), and colloidal silica (trade name: PEG-ST), isopropyl alcohol 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), propylene glycol monomethyl ether dispersed colloidal silica (trade name: PGM-ST), dimethylacetamide dispersed colloidal silica (trade name: DMAC-ST), methyl ethyl ketone dispersed colloidal silica (trade name: MEK-ST-40), methyl isobutyl ketone dispersed colloidal silica (trade name: MIBK-ST), ethyl acetate dispersed colloidal silica (trade name: EAC-ST), propylene glycol monomethyl ether acetate dispersed colloidal silica (trade name: PMA-ST), toluene dispersed colloidal silica (trade name: TOL-ST) (all manufactured by Nissan Chemical Corporation). The colloidal silica (D) is preferably dispersed in water or a hydrophilic solvent in a manner that does not hinder antifogging properties.

[0116] When the colloidal silica (D) is used, the colloidal silica (D) is preferably 120 parts by mass or less relative to 100 parts by mass of the copolymer (A). From the perspective of suppressing drip marks, the colloidal silica (D) is more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more relative to 100 parts by mass of the copolymer (A), and from the perspective of anti-fogging properties, it is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less.

[0117] The anti-fogging agent composition of the present invention may further contain a dilution solvent.

[0118] The purpose of using the diluent solvent is to adjust the solid content and viscosity suitable for the coating of the antifogging agent composition. As the diluent solvent, the polymerization solvent of the copolymer (A) is preferably used. The solid content and viscosity suitable for coating vary according to the coating method, but when the coating method is a spray coating method, the copolymer (A) in the antifogging agent composition is preferably 3% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less.

[0119] As other components, the anti-fogging agent composition of the present invention can be blended with various conventional additives such as a leveling agent, a curing catalyst, an antioxidant, an ultraviolet absorber, and a light stabilizer as required. The amount of the other components added can be blended in the conventional amount of each additive, but is usually 10 parts by mass or less relative to 100 parts by mass of the copolymer (A).

[0120] <Anti-fog products>

[0121] The anti-fogging product of the present invention is obtained by coating the anti-fogging agent composition on a coating object by a common coating method, and curing the coating object by heating to form an anti-fogging film on the surface of the coating object.

[0122] Regardless of the type of the object to be coated, a known resin substrate can be used, for example, polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc.

[0123] When applied to the object to be coated, in order to improve the wettability of the antifogging agent composition to the object to be coated and prevent uneven surface coating, it is preferred to remove foreign matter attached to the surface of the object to be coated before coating. Dust removal using high-pressure gas or ionized gas, ultrasonic cleaning using a detergent aqueous solution or an alcohol solvent, wiping using an alcohol solvent, cleaning using ultraviolet rays and ozone, etc. can be listed. As a coating method, for example, dipping, pouring, roller coating, rod coating, spraying, etc. can be listed.

[0124] From the viewpoint of obtaining good antifogging properties and coating film appearance, the thickness of the antifogging film is preferably about 0.5 to 10 μm, more preferably about 1 to 5 μm.

[0125] The anti-fog product can be used in any application, for example, in automobile lamps, such as headlights, auxiliary headlights, clearance lights, license plate lights, taillights, parking lights, reverse lights, direction lights, auxiliary direction lights, hazard warning lights, etc.

[0126] Example

[0127] The present invention is further described in detail with reference to the following examples, but the present invention is not limited to these examples.

[0128] <Preparation of copolymer (A)>

[0129] <Preparation of copolymer (AI)>

[0130] 300 parts by mass of diacetone alcohol as a polymerization solvent was added to a reaction vessel equipped with a thermometer, a stirring device, a nitrogen inlet pipe and a condenser, and heated to 80°C while blowing nitrogen. Next, a solution prepared by mixing 45 parts by mass of N,N-dimethylacrylamide as a monomer (A-1), 35 parts by mass of n-butyl acrylate as a monomer (A-2), 20 parts by mass of 2-hydroxyethylacrylamide as a monomer (A-3), and 1.0 parts by mass of tert-hexyl peroxypivalate (manufactured by NOF CORPORATION., trade name "Perhexyl PV" (effective ingredient 70% by mass)) as a free radical polymerization initiator was dripped into the reaction vessel over 2 hours. After the dripping was completed, the mixture was kept at 80°C and stirred for another hour, and then cooled to prepare a solution of a copolymer (AI). The polymerization conversion rate of the feed monomers of the copolymer (AI) was measured by gas chromatography, and the result was 100%. The weight average molecular weight of the copolymer (AI) was measured by gel permeation chromatography and found to be 91,000. The solid content of the solution of the copolymer (AI) was 25.2% by mass. The hydroxyl value (theoretical value) of the copolymer (AI) was 97.5 mgKOH / g.

[0131] <Preparation of copolymer (A-II)>

[0132] 300 parts by mass of diacetone alcohol as a polymerization solvent was added to a reaction vessel equipped with a thermometer, a stirring device, a nitrogen inlet pipe and a condenser, and heated to 80°C while blowing nitrogen. Next, a solution of 50 parts by mass of N,N-dimethylacrylamide as a monomer (A-1), 35 parts by mass of cyclohexyl acrylate as a monomer (A-2), 15 parts by mass of 2-hydroxyethyl acrylate as a monomer (A-3), and 1.0 parts by mass of tert-hexyl peroxy pivalate (manufactured by NOF CORPORATION., trade name "Perhexyl PV" (effective ingredient 70% by mass)) as a free radical polymerization initiator was dripped into the reaction vessel over 2 hours. After the dripping was completed, the mixture was kept at 80°C and stirred for another hour, and then cooled to prepare a solution of a copolymer (A-II). The polymerization conversion rate of the feed monomers of the copolymer (A-II) was measured by gas chromatography, and the result was 100%. The weight average molecular weight of the copolymer (A-II) was measured by gel permeation chromatography and found to be 80,000. The solid content of the solution of the copolymer (A-II) was 24.9% by mass. The hydroxyl value (theoretical value) of the copolymer (A-II) was 72.5 mgKOH / g.

[0133] <Example 1>

[0134] <Preparation of antifogging agent composition>

[0135] 600 parts by mass of propylene glycol monomethyl ether were added to 400 parts by mass of a solution containing 100 parts by mass of the copolymer (AI) obtained above as the copolymer (A) to adjust the concentration of the diluted copolymer (AI) solution to 10.0% by mass. Next, 89.9 parts by mass of isocyanurate of hexamethylene diisocyanate blocked with diethyl malonate (manufactured by Asahi Kasei Corporation, trade name “Duranate MF-K60B”) as a polyfunctional blocked isocyanate compound (B), 5.0 parts by mass of sodium di(2-ethylhexyl)sulfosuccinate (manufactured by NOF CORPORATION, trade name “Rapisol A80”, 80% by mass of active ingredient) as an anionic surfactant (C-1), 0.50 parts by mass of tetra-n-butylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) as a surfactant having a quaternary ammonium salt structure (C-2), 0.40 parts by mass of perfluoroalkylene polyoxyethylene (manufactured by Neos Corporation, trade name “fergent 215M”), 0.05 parts by mass of polyether-modified polydimethylsiloxane (manufactured by BYK, trade name “BYK333”) as a leveling agent, to prepare an antifogging agent composition.

[0136] <Production of anti-fog products>

[0137] The antifogging agent composition obtained above was applied on a polycarbonate (PC) plate by spraying in an atmosphere of 25°C and 30% RH so that the film thickness of the cured coating film was about 2 to 4 μm, and heat-cured at 120°C for 30 minutes to produce an antifogging product (test piece) having an antifogging film.

[0138] Table 1 shows the results obtained by the following evaluation methods (1) to (6) using the test pieces obtained above.

[0139] <Evaluation of anti-fogging properties>

[0140] <(1) Steam test>

[0141] The test piece was placed 2 cm above the water surface of a warm water bath maintained at 80°C with the coating film facing downward, and the coating film was continuously irradiated with steam from the warm water bath. The presence or absence of fog after 10 seconds of irradiation was visually evaluated according to the following 4 levels. In addition, as long as the evaluation is C or above, there is no problem in practical use.

[0142] A: No fog was observed.

[0143] B: Momentary fogging was observed, but a water film was immediately formed and no fogging occurred.

[0144] C: Obvious fog was observed, but a water film was formed after 10 seconds and no fogging occurred.

[0145] D: After 10 seconds of steam irradiation, an uneven water film was observed on a part or the entire coating surface.

[0146] <(2) Durability test>

[0147] The test piece was placed 2 cm above the water surface of a warm water bath maintained at 80°C with the coating film facing downward. The coating film was irradiated with steam from the warm water bath for 10 seconds, and then the test piece was dried at room temperature for 5 to 10 minutes in an upright state. The coating film was evaluated after repeating this operation 30 times in the same manner as in <(1) Steam Test>. In addition, as long as the evaluation is C or above, there is no problem in practical application.

[0148] <(3) Steam test after heat resistance test>

[0149] The test piece was placed in a dryer set at 120°C for 10 days, and then placed at room temperature for 24 hours. Then, the test piece was evaluated in the same manner as in <(1) Steam Test>. In addition, as long as the evaluation is C or above, there is no problem in practical use.

[0150] <(4) Water dripping marks>

[0151] Place the test piece 2 cm above the water surface of a warm water bath maintained at 80°C with the coating facing downward. After irradiating the coating with steam from the warm water bath for 10 seconds, stand the test piece upright to produce water droplets. Make the test piece horizontal and leave it at room temperature to dry. Visually evaluate the presence or absence of water dripping marks after drying according to the following 4 levels. In addition, as long as the evaluation is C or above, there is no problem in practical application.

[0152] A: The dripping marks are not noticeable.

[0153] B: The dripping marks are basically not noticeable.

[0154] C: The drip marks are slightly noticeable.

[0155] D: The dripping mark is deep.

[0156] <(5) Changes of water drop marks over time in a high humidity environment>

[0157] The drip marks were generated in the same manner as in <(4) Drip marks>, and the drip marks were visually evaluated according to the following 4 levels after being left to stand for 10 days in a constant temperature and humidity chamber set at 20°C and 75% RH or 30°C and 75% RH. If the evaluation was C or higher, there was no problem in practical use.

[0158] A: The dripping marks disappear.

[0159] B: The dripping marks are much lighter than before the test.

[0160] C: The dripping mark is lighter than before the test.

[0161] D: The dripping mark has not changed compared with that before the test.

[0162] <(6) Adhesion>

[0163] The presence or absence of peeling of the coating film was evaluated visually according to JIS K 5400 8.5.1 in accordance with the following three levels. If the evaluation is B or higher, there is no problem in practical use.

[0164] A: No peeling was observed at all.

[0165] B: Peeling was observed in part.

[0166] C: All peeled off.

[0167] <Examples 2 to 23, Comparative Examples 1 to 7>

[0168] <Preparation of antifogging agent composition and production of antifogging products>

[0169] In each example and comparative example, except that the raw materials of Example 1 were changed to the raw materials and their ratios described in Tables 1 to 3, the antifogging agent compositions of Examples 2 to 23 and Comparative Examples 1 to 7 were prepared by the same operation as in Example 1. Furthermore, antifogging products (test pieces) having the antifogging films of Examples 2 to 23 and Comparative Examples 1 to 7 were prepared by the same operation as in Example 1.

[0170] The results obtained by using the test pieces obtained above and the evaluation methods (1) to (6) described above are shown in Tables 1 to 3.

[0171]

[0172]

[0173]

[0174] In Tables 1 to 3, the polyfunctional blocked isocyanate compound (B) is:

[0175] Duranate MF-K60B represents an isocyanurate of hexamethylene diisocyanate terminated with a malonic acid diester (manufactured by Asahi Kasei Corporation, active ingredient 60% by mass, NCO content 6.5% by mass);

[0176] Duranate WM44-L70G represents an isocyanurate of hexamethylene diisocyanate blocked with a malonic acid diester (manufactured by Asahi Kasei Corporation, active ingredient 70% by mass, NCO content 5.3% by mass).

[0177] In Tables 1 to 3, as surfactant (C):

[0178] Rapisol A80 represents sodium di(2-ethylhexyl)sulfosuccinate (manufactured by NOF CORPORATION, active ingredient 80% by mass);

[0179] Pelex TR represents sodium ditridecyl sulfosuccinate (manufactured by Kao Corporation, active ingredient 70% by mass);

[0180] Perfluoroolefin sulfonate (manufactured by Neos Corporation, active ingredient 100% by mass) is indicated by FTERGENT 100;

[0181] PolyFox PF-156A represents diammonium perfluoroalkyl polyoxyethylene disulfonate (manufactured by OMNOVA Solutions Inc., active ingredient 30% by mass);

[0182] TBAB represents tetra-n-butylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass);

[0183] DTAB represents dodecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., active ingredient 100% by mass);

[0184] NISSANANON BL-SF represents lauryl dimethylaminoacetic acid betaine (manufactured by NOF CORPORATION, active ingredient 33.5 to 37.5 mass %);

[0185] Softazoline LSB-R represents lauramide propyl hydroxysulfobetaine (manufactured by Kawaken Fine Chemicals Co., Ltd., active ingredient 29% by mass);

[0186] FTERGENT 215M represents perfluoroalkenyl polyoxyethylene (manufactured by Neos Corporation, 100% by mass of active ingredient, containing one perfluoroalkenyl group in the molecule);

[0187] FTERGENT 218GL represents perfluoroalkenyl polyoxyethylene (manufactured by Neos Corporation, 100% by mass of active ingredient, containing 3 perfluoroalkenyl groups in the molecule);

[0188] Tergent 222F represents perfluoroalkenyl polyoxyethylene (manufactured by Neos Corporation, 100% by mass of active ingredient, containing 2 perfluoroalkenyl groups in the molecule);

[0189] NONION ID209 represents polyoxyethylene isodecyl ether (manufactured by NOF CORPORATION, active ingredient 100% by mass);

[0190] BYK3560 represents polyether macromonomer-modified acrylate (manufactured by BYK, active ingredient 100% by mass).

[0191] In Tables 1 to 3, colloidal silica (D) is:

[0192] SNOWTEX O represents a water-dispersed colloidal silica sol (manufactured by Nissan Chemical Corporation, active ingredient 20% by mass, particle size 12 nm).

[0193] In Tables 1 to 3, as leveling agents:

[0194] BYK333 represents polyether-modified polydimethylsiloxane (manufactured by BYK, active ingredient 100% by mass).

Claims

1. An antifogging agent composition comprising a copolymer (A), a multifunctional blocked isocyanate compound (B), a surfactant (C) and colloidal silica (D), wherein the antifogging agent composition is characterized in that: The copolymer (A) is a (meth)acrylate copolymer obtained from a monomer mixture, wherein the monomer mixture comprises: one or more monomers (A-1) selected from the group consisting of monomers represented by the following general formula (1) and monomers represented by the following general formula (2); a monomer (A-2) represented by the following general formula (3); and one or more monomers (A-3) selected from the group consisting of monomers represented by the following general formula (4) and monomers represented by the following general formula (5), In the general formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms, -C(CH3)2CH2COCH3, -C2H4N(CH3)2 or -C3H6N(CH3)2, R 3 is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, In the general formula (2), R 4 is a hydrogen atom or a methyl group, In the general formula (3), R 5 is a hydrogen atom or a methyl group, R 6 is a straight-chain, branched or cyclic hydrocarbon group having 1 to 16 carbon atoms, In the general formula (4), R 7 is a hydrogen atom or a methyl group, R 8 A linear or branched alkylene group having 2 to 4 carbon atoms or -C2H4(OCO(CH2)5) n -, n is 1 to 5, In the general formula (5), R 9 is a hydrogen atom or a methyl group, R 10 is a straight-chain or branched alkylene group having 1 to 4 carbon atoms, The surfactant (C) comprises an anionic surfactant (C-1), a surfactant having a quaternary ammonium salt structure (C-2) and a fluorine-based nonionic surfactant (C-3), The fluorine-based nonionic surfactant (C-3) is a perfluoroalkenyl ethylene oxide adduct, Relative to 100 parts by mass of the copolymer (A), the anionic surfactant (C-1) is 1 part by mass or more and 10 parts by mass or less, the surfactant (C-2) having a quaternary ammonium salt structure is 0.01 parts by mass or more and 3 parts by mass or less, and the fluorine-based nonionic surfactant (C-3) is 0.05 parts by mass or more and 5 parts by mass or less, The mass ratio of the fluorinated nonionic surfactant (C-3) to the total amount of the anionic surfactant (C-1) and the surfactant having a quaternary ammonium salt structure (C-2) {(C-3) / [(C-1)+(C-2)]} is 0.005 or more and 2.5 or less, The colloidal silica (D) is contained in an amount of 5 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the copolymer (A).

2. The anti-fogging agent composition according to claim 1, characterized in that The mass ratio ((C-2) / (C-1)) of the surfactant (C-2) having a quaternary ammonium salt structure to the anionic surfactant (C-1) is 0.01 to 0.

8.

3. The anti-fogging agent composition according to claim 1 or 2, characterized in that The anionic surfactant (C-1) is a fluorine-based anionic surfactant.

4. The antifogging agent composition according to claim 1 or 2, characterized in that: In a total of 100 parts by mass of the monomer (A-1), the monomer (A-2) and the monomer (A-3), the monomer (A-1) is from 35 parts by mass to 90 parts by mass, the monomer (A-2) is from 5 parts by mass to 60 parts by mass, and the monomer (A-3) is from 5 parts by mass to 30 parts by mass.

5. The anti-fogging agent composition according to claim 1 or 2, characterized in that: Regarding the usage ratio of the copolymer (A) and the polyfunctional blocked isocyanate compound (B), the equivalent ratio (NCO / OH) of the isocyanate group of the polyfunctional blocked isocyanate compound (B) to the hydroxyl group of the copolymer (A) is 0.1 to 1.

5.

6. An anti-fog product, characterized in that: An antifogging film formed from the antifogging agent composition according to any one of claims 1 to 5 is provided on a substrate.

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