Antifogging agent composition, and antifogging article

Abstract

This antifogging agent composition contains a copolymer (A), colloidal silica (B), and a glycidyl group-containing compound (C), and is characterized in that: the copolymer (A) is a (meth)acrylate copolymer obtained from a monomer mixture at least containing a monomer (a-1) represented by general formula (1); and the glycidyl group-containing compound (C) is a glycidyl group-containing compound represented by general formula (2). The antifogging agent composition can form an antifogging coating film that has excellent coating film transparency, initial antifogging properties, and initial adhesion, is unlikely to cause water dripping marks, and does not reduce adhesion even when a coating film cured at a low temperature is exposed to high temperature and high humidity for a long period of time.

Description

Antifogging agent composition and antifogging article

[0001] The present invention relates to an anti-fogging agent composition and an anti-fogging article.

[0002] In vehicle lighting equipment such as automobile headlamps, high-humidity air can enter the lamp chamber, and the lens can be cooled by outside air or rainfall, causing condensation on the inner surface and resulting in fogging. As a result, the brightness of the vehicle light decreases, and the aesthetic appearance of the lens surface is impaired, which can cause discomfort to the user. To prevent such lens fogging, a method is known in which an anti-fogging agent is applied to the area where fogging occurs to form an anti-fogging coating.

[0003] In anti-fogging coatings, when a water film forms on the surface of the coating due to water-soluble components such as surfactants, a phenomenon called "water dripping" may occur where the water in the water film flows down locally. Since water-soluble components from the anti-fogging coating dissolve into the water film, when water dripping occurs and the water evaporates, the dissolved water-soluble components precipitate on the surface of the anti-fogging coating, leaving behind water drip marks, which is a problem as it detracts from the appearance of the vehicle's lighting fixtures.

[0004] To address the above issues, for example, Patent Document 1 discloses an antifogging agent composition that uses specific inorganic particles and a specific acrylic resin to prevent water streaks and exhibit excellent transparency, antifogging properties, and moisture resistance of the coating film. Furthermore, for example, Patent Document 2 discloses an antifogging agent composition that uses specific inorganic particles, a specific acrylic resin, and a specific solvent to prevent water streaks and exhibit excellent transparency, water resistance, adhesion, antifogging properties, and suppression of solvent cracks of the coating film.

[0005] Japanese Patent Publication No. 2022-127163, International Publication No. 2023 / 054457

[0006] On the other hand, from the perspective of reducing environmental impact, there is a growing demand for anti-fogging agents for automotive lamps that can be cured at low temperatures to reduce energy consumption during the manufacturing of automotive lamps. In this regard, the anti-fogging agent compositions disclosed in Patent Documents 1 and 2 have the problem that when the coating is cured at low temperatures, the curing of the coating is insufficient, and when the cured coating is exposed to a high-temperature, high-humidity environment for a long time, unreacted organic components leach out, increasing the proportion of inorganic components in the coating, which reduces adhesion to the substrate.

[0007] In view of the above circumstances, the present invention aims to provide an anti-fogging agent composition that can form an anti-fogging coating film that has excellent transparency, initial anti-fogging properties, and initial adhesion, is less prone to water streaks, and maintains its adhesion even when the coating film cured at low temperatures is exposed to high temperatures and high humidity for a long period of time.

[0008] In other words, the present invention is an anti-fogging agent composition comprising [1] a copolymer (A), colloidal silica (B), and a glycidyl group-containing compound (C), wherein the copolymer (A) comprises at least one of the general formulas (1): (In general formula (1), R １ R is a hydrogen atom or a methyl group, ２ and R ３ The (meth)acrylate copolymer is obtained from a monomer mixture containing a monomer (a-1) represented by the following formula: (a-1) is a hydrogen atom or a linear or branched alkyl group of carbon 1 to 4, and the glycidyl group-containing compound (C) is general formula (2): The present invention relates to an anti-fogging agent composition containing a glycidyl group represented by the general formula (2), where X is a functional group represented by general formula (3) with n = 0 to 8, and Y is a hydrogen atom, a linear or branched alkyl group of carbon chains 1 to 8, a phenyl group, or a functional group represented by general formula (3) with n = 0 to 8.

[0009] Furthermore, the present invention relates to the anti-fogging agent composition described in [1], wherein the copolymer (A) may be a (meth)acrylate copolymer (A1) obtained from a monomer mixture comprising a monomer (a-1) represented by the general formula (1) and a crosslinkable monomer (a-2) containing an N-methylol group, an N-alkoxymethyl group, or an epoxy group.

[0010] Furthermore, the present invention relates to the anti-fogging composition described in [1], wherein the copolymer (A) is a (meth)acrylate copolymer (A2) obtained from a monomer mixture comprising a monomer (a-1) represented by the general formula (1) and a monomer (a-5) containing a hydroxyl group, and may further contain a blocked polyisocyanate curing agent (D).

[0011] Furthermore, the present invention relates to [4] a monomer (a-5) containing the hydroxyl group, which has the general formula (7): (In general formula (7), R ９ R is a hydrogen atom or a methyl group, １０ is a linear or branched alkylene group having 1 to 8 carbon atoms.) Monomer represented by general formula (8): (In general formula (8), R １１ The present invention relates to the anti-fogging agent composition described in [3], which may be a monomer represented by a hydrogen atom or a methyl group, and n is an integer from 1 to 10.

[0012] Furthermore, the present invention also includes [5] the monomer mixture having the general formula (4): (In general formula (4), R ４ The anti-fogging composition according to any one of [1] to [4], which may also contain a monomer (a-3) having an aromatic group represented by ) where is a hydrogen atom or a methyl group, V is a linear or branched alkylene group having 0 to 4 carbon atoms, or a (poly)alkylene oxide chain having 1 to 4 repeating units, and W is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a hydroxyl group.

[0013] Furthermore, the present invention relates to an anti-fogging article having an anti-fogging coating film formed on a substrate from an anti-fogging agent composition described in any of [1] to [5].

[0014] The anti-fogging agent composition of the present invention has excellent transparency, initial anti-fogging properties, and initial adhesion of the coating film, is less prone to water streaks, and can form an anti-fogging coating film in which adhesion does not deteriorate even when the coating film cured at low temperatures is exposed to high temperatures and high humidity for a long period of time.

[0015] The anti-fogging agent composition of the present invention contains a copolymer (A), colloidal silica (B), and a glycidyl group-containing compound (C).

[0016] <Copolymer (A)> The copolymer (A) of the present invention is a (meth) acrylate copolymer obtained from a monomer mixture containing at least the following monomer (a-1).

[0017] <Monomer (a-1)> The monomer (a-1) has the general formula (1): (In general formula (1), R １ is a hydrogen atom or a methyl group, and R ２ and R ３ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms in the carbon chain.) It is represented by.

[0018] In the general formula (1), R ２ and R ３ are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms from the viewpoint of enhancing the anti-fogging performance of the anti-fogging coating film, and more preferably a hydrogen atom or an alkyl group having 1 carbon atom. The monomer (a-1) may be used alone or in combination of two or more.

[0019] Further, the copolymer (A) of the present invention forms a crosslinked structure and is preferably a thermosetting copolymer capable of crosslinking the copolymer from the viewpoint of enhancing the water resistance of the anti-fogging coating film and making it difficult to generate water dripping marks. As the thermosetting copolymer, in addition to the monomer (a-1) as a constitutional unit, a thermosetting monomer may be included. Such a thermosetting copolymer may be, for example, a (meth) acrylate copolymer (A1) obtained from a monomer mixture containing the monomer (a-1) represented by the general formula (1) and a crosslinkable monomer (a-2) containing an N-methylol group, an N-alkoxymethyl group, or an epoxy group, or a (meth) acrylate copolymer (A2) obtained from a monomer mixture containing the monomer (a-1) represented by the general formula (1) and a monomer (a-5) containing a hydroxyl group.

[0020] <Monomer (a-2)> The monomer (a-2) is a crosslinkable monomer containing an N-methylol group, an N-alkoxymethyl group, or an epoxy group. The monomer (a-2) may be used alone or in combination of two or more types.

[0021] Examples of the monomer (a-2) include N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, glycidyl(meth)acrylate, 4-hydroxybutylacrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl(meth)acrylate. From the viewpoint of making it difficult for water streaks to form on the anti-fogging composition, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and glycidyl(meth)acrylate are preferred as the monomer (a-2).

[0022] <Monomer (a-3)> In the copolymer (A1), the monomer mixture preferably contains the following monomer (a-3) from the viewpoint of improving the adhesion of the anti-fogging coating film.

[0023] The monomer (a-3) is given by general formula (4): (In general formula (4), R ４ V is a hydrogen atom or a methyl group, V is a linear or branched alkylene group having 0 to 4 carbon atoms, or a (poly)alkylene oxide chain having 1 to 4 repeating units, and W is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. The above "0 carbon atoms" means that V is absent and the oxygen atom is directly bonded to the aromatic ring. The monomer (a-3) may be used alone or in combination of two or more types.

[0024] In the general formula (4) above, V is preferably a linear or branched alkylene group having 0 to 2 carbon atoms, or a (poly)alkylene oxide chain having 1 to 2 repeating units, from the viewpoint of improving the adhesion of the anti-fogging coating film. Furthermore, W is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 2 carbon atoms, a halogen atom, a nitro group, a cyano group, or a hydroxyl group, from the viewpoint of improving the anti-fogging properties of the anti-fogging coating film.

[0025] Examples of the monomer (a-3) include phenyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate. From the viewpoint of improving the adhesion of the anti-fogging coating film, benzyl (meth)acrylate and 2-phenoxyethyl (meth)acrylate are preferred as the monomer (a-3).

[0026] In the copolymer (A1), the monomer mixture preferably contains the following monomer (a-4) from the viewpoint of improving the water resistance of the anti-fogging coating and making it less likely for water streaks to occur.

[0027] <Monomer (a-4)> The monomer (a-4) is given by general formula (5): (In general formula (5), R ５ R is a hydrogen atom or a methyl group, ６ is a linear or branched alkylene group having 1 to 8 carbon atoms. ) Monomer represented by general formula (6): (In general formula (6), R ７ R is a hydrogen atom or a methyl group, ８ (where is a hydrogen atom or a linear or branched alkylene group having 1 to 8 carbon atoms.) One or more monomers selected from the group consisting of these monomers.

[0028] Examples of the monomer (a-4) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and the like. From the viewpoint of excellent anti-fogging properties and water resistance of the anti-fogging coating film and difficulty in generating water dripping marks, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, t-butyl (meth)acrylate, and the like are preferable as the monomer (a-4). The monomer (a-4) may be used alone or in combination of two or more kinds.

[0029] In the copolymer (A1), the content of the monomer (a-1) is preferably 20 to 70% by mass in the monomer mixture. In the copolymer (A1), from the viewpoint of enhancing the anti-fogging properties of the copolymer and the transparency of the anti-fogging coating film, the content of the monomer (a-1) is more preferably 25% by mass or more, and even more preferably 35% by mass or more in the monomer mixture. And in the copolymer (A1), from the viewpoint of suppressing the water solubility of the copolymer (A) and enhancing the water resistance, the content of the monomer (a-1) is more preferably 55% by mass or less, and even more preferably 45% by mass or less in the monomer mixture. That is, in the copolymer (A1), the content of the monomer (a-1) is more preferably 25% by mass or more and 55% by mass or less, and even more preferably 35% by mass or more and 45% by mass or less in the monomer mixture.

[0030] In the copolymer (A1), the content of the monomer (a-2) is preferably 10 to 55% by mass in the monomer mixture. In the copolymer (A1), from the viewpoint of forming the crosslinked structure of the copolymer (A) and making it difficult to generate water drip marks, the content of the monomer (a-2) is more preferably 20% by mass or more, and even more preferably 30% by mass or more in the monomer mixture. And in the copolymer (A1), from the viewpoint of enhancing the transparency of the anti-fog coating film and the adhesion to the substrate, the content of the monomer (a-2) is more preferably 50% by mass or less, and even more preferably 45% by mass or less in the monomer mixture. That is, in the copolymer (A1), the content of the monomer (a-2) is more preferably 20% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 45% by mass or less in the monomer mixture.

[0031] In the copolymer (A1), when the monomer (a-3) is used, the content of the monomer (a-3) is preferably 5 to 40% by mass in the monomer mixture. In the copolymer (A1), from the viewpoint of improving the water resistance of the anti-fog coating film, the content of the monomer (a-3) is more preferably 11% by mass or more, and even more preferably 16% by mass or more in the monomer mixture. And the content of the monomer (a-3) is more preferably 30% by mass or less, and even more preferably 25% by mass or less in the monomer mixture from the viewpoint of maintaining the anti-fog property of the anti-fog coating film in the copolymer (A1). That is, in the copolymer (A1), the content of the monomer (a-3) is more preferably 11% by mass or more and 30% by mass or less, and even more preferably 16% by mass or more and 25% by mass or less in the monomer mixture.

[0032] In the copolymer (A1), when monomer (a-4) is used, the content of monomer (a-4) is preferably 1 to 25% by mass in the monomer mixture. In the copolymer (A1), from the viewpoint of improving the water resistance of the anti-fogging coating and making it difficult for water streaks to occur, the content of monomer (a-4) is more preferably 5% by mass or more, and even more preferably 10% by mass or more, in the monomer mixture. Furthermore, in the copolymer (A1), from the viewpoint of maintaining the adhesion of the anti-fogging coating, the content of monomer (a-4) is more preferably 20% by mass or less, and even more preferably 15% by mass or less, in the monomer mixture. That is, in the copolymer (A1), the content of monomer (a-4) is more preferably 5% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 15% by mass or less, in the monomer mixture.

[0033] <Monomer (a-5)> The monomer (a-5) is a monomer containing a hydroxyl group. The monomer (a-5) may be used alone or in combination of two or more types.

[0034] The monomer (a-5) may be any monomer containing a hydroxyl group, and is preferably a monomer represented by the following general formula (7) and / or general formula (8), for example, from the viewpoint of making it difficult for water stains to occur by facilitating the crosslinking reaction with the isocyanate curing agent. (In general formula (7), R ９ R is a hydrogen atom or a methyl group, １０ (This refers to a linear or branched alkylene group having 1 to 8 carbon atoms.) (In general formula (8), R １１ (where n is a hydrogen atom or a methyl group, and n is an integer between 1 and 10.)

[0035] Examples of the monomer (a-5) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate; and Praxel FA1DDM, FA2D, FA2K, FA4DT, FA5D, FM1, FM1D, FM2D, FM3, FM3K, FM4, FM5, and FM5L (all manufactured by Daicel Corporation, unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone). From the viewpoint of making it difficult for water streaks to form on the anti-fogging agent composition, 2-hydroxyethyl (meth)acrylate, FA1DDM, FA2D, FA2K, FM1, and FM2D are preferred as the monomer (a-5).

[0036] <Monomer (a-3)> In the copolymer (A2), the monomer mixture preferably contains the above monomer (a-3) from the viewpoint of improving the adhesion of the anti-fogging coating film.

[0037] <Monomer (a-6)> In the copolymer (A2), the monomer mixture may contain the following monomer (a-6) from the viewpoint of increasing the hydrophobicity of the anti-fogging coating and improving adhesion.

[0038] The monomer (a-6) is given by general formula (9): (In general formula (9), R １２ R is a hydrogen atom or a methyl group, １３ (wherein is a hydrogen atom or a linear, branched, or cyclic alkylene group having 1 to 16 carbon atoms.) The monomer (a-6) may be used alone or in combination of two or more types.

[0039] Examples of the monomer (a-6) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and cetyl (meth)acrylate. From the viewpoint of improving adhesion by increasing hydrophobicity while maintaining the anti-fogging properties of the anti-fogging coating film, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate are preferred as the monomer (a-6).

[0040] In the copolymer (A2), the content of monomer (a-1) is preferably 20 to 70% by mass in the monomer mixture. In the copolymer (A2), the content of monomer (a-1) is more preferably 25% by mass or more, and even more preferably 35% by mass or more, in the monomer mixture, from the viewpoint of improving the antifogging properties of the copolymer and the transparency of the antifogging coating film. Furthermore, in the copolymer (A2), the content of monomer (a-1) is more preferably 55% by mass or less, and even more preferably 45% by mass or less, in the monomer mixture, from the viewpoint of suppressing the water solubility of copolymer (A) and improving water resistance. In other words, in the copolymer (A2), the content of monomer (a-1) is more preferably 25% by mass or more and 55% by mass or less, and even more preferably 35% by mass or more and 45% by mass or less, in the monomer mixture.

[0041] In the copolymer (A2), the content of monomer (a-5) is preferably 10 to 55% by mass in the monomer mixture. In the copolymer (A2), the content of monomer (a-5) is more preferably 20% by mass or more, and even more preferably 30% by mass or more, in the monomer mixture, from the viewpoint of forming a cross-linked structure of copolymer (A) and making it difficult for water streaks to occur. Furthermore, in the copolymer (A2), the content of monomer (a-5) is more preferably 50% by mass or less, and even more preferably 45% by mass or less, in the monomer mixture, from the viewpoint of improving the transparency of the anti-fogging coating film and adhesion to the substrate. In other words, in the copolymer (A2), the content of monomer (a-5) is more preferably 20% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 45% by mass or less, in the monomer mixture.

[0042] Furthermore, in the copolymer (A2), monomer (a-5) and monomer (a-2) may be used in combination as thermosetting monomers. In this case, the total content of monomer (a-5) and monomer (a-2) in the monomer mixture is preferably 10 to 70% by mass. In the copolymer (A2), the total content of monomer (a-5) and monomer (a-2) in the monomer mixture is more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of forming a cross-linked structure of copolymer (A) and making it difficult for water stains to occur. Furthermore, in the copolymer (A2), the total content of monomer (a-5) and monomer (a-2) in the monomer mixture is more preferably 55% by mass or less, and even more preferably 45% by mass or less, from the viewpoint of improving the transparency of the anti-fogging coating film and adhesion to the substrate. In other words, in the copolymer (A2), the total content of monomer (a-5) and monomer (a-2) is more preferably 20% by mass or more and 55% by mass or less in the monomer mixture, and even more preferably 30% by mass or more and 45% by mass or less.

[0043] In the copolymer (A2), when monomer (a-3) is used, the content of monomer (a-3) is preferably 5 to 40% by mass in the monomer mixture. In the copolymer (A2), from the viewpoint of improving the water resistance of the anti-fogging coating film, the content of monomer (a-3) is more preferably 11% by mass or more, and even more preferably 16% by mass or more, in the monomer mixture. Furthermore, in the copolymer (A2), from the viewpoint of maintaining the anti-fogging properties of the anti-fogging coating film, the content of monomer (a-3) is more preferably 30% by mass or less, and even more preferably 25% by mass or less, in the monomer mixture. That is, in the copolymer (A2), the content of monomer (a-3) is more preferably 11% by mass or more and 30% by mass or less, and even more preferably 16% by mass or more and 25% by mass or less, in the monomer mixture.

[0044] In the copolymer (A2), when monomer (a-6) is used, the content of monomer (a-6) is preferably 1 to 40% by mass in the monomer mixture. In the copolymer (A2), from the viewpoint of increasing hydrophobicity and improving adhesion, the content of monomer (a-6) is more preferably 10% by mass or more, and even more preferably 15% by mass or more, in the monomer mixture. Furthermore, in the copolymer (A2), from the viewpoint of maintaining the anti-fogging properties of the anti-fogging coating film, the content of monomer (a-6) is more preferably 30% by mass or less, and even more preferably 20% by mass or less, in the monomer mixture. That is, in the copolymer (A2), the content of monomer (a-6) is more preferably 10% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 20% by mass or less, in the monomer mixture.

[0045] <Method for Producing Copolymer (A)> The copolymer (A) of the present invention is obtained by copolymerizing the monomer mixture. The copolymer structure may be any of the following: random copolymer, alternating copolymer, block copolymer, or graft copolymer. However, a random copolymer is preferred from the viewpoint of improving the effects of the antifogging agent composition, including antifogging properties, and from the viewpoint of easily preparing the antifogging agent composition. Various known polymerization methods such as radical polymerization, cationic polymerization, anionic living polymerization, and cationic living polymerization can be used as polymerization methods to obtain the copolymer. However, radical polymerization is particularly preferred from the standpoint of ease of industrial productivity and multifaceted performance. As radical polymerization methods, ordinary bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, etc. can be used. However, solution polymerization is preferred because it can be used directly as an antifogging agent composition after polymerization.

[0046] Examples of polymerization solvents used in the solution polymerization method include alcohol-based solvents such as water, methanol, ethanol, propanol, i-propanol, 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-methoxybutanol, and 3-methoxy-3-methylbutanol; 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, xylene, phenol, benzyl alcohol, and phenoxyethanol; and amide-based solvents such as formamide and dimethylformamide. Among these, alcohol-based solvents and alcohol ether-based solvents are preferred. The polymerization solvents may be used individually or in combination of two or more types.

[0047] The radical polymerization initiator can be a commonly used organic peroxide, azo compound, etc. Examples of the organic peroxide include benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxy-2-hexanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, and t-hexyl neodecanate. 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 types.

[0048] The amount of 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 add the radical polymerization initiator dropwise into the reaction vessel while polymerization is being carried out, as this makes it easier to control the heat generated during polymerization. The temperature at which the polymerization reaction is carried out is appropriately changed depending on the type of radical polymerization initiator used, but for industrial production, it is preferably 30 to 150°C, more preferably 40 to 100°C.

[0049] The number average molecular weight (Mn) of the copolymer (A) is preferably 10,000 or more, and more preferably 15,000 or more, from the viewpoint of imparting water resistance to the anti-fogging coating. The number average molecular weight (Mn) of the copolymer (A) is preferably 300,000 or less, and more preferably 200,000 or less, from the viewpoint of improving the paintability and handling properties of the anti-fogging agent composition.

[0050] The number-average molecular weight (Mn) of the copolymer (A) can be determined by the GPC method. <Measurement conditions for number-average molecular weight (Mn)> Analyst: HLC-8320GPC (manufactured by Tosoh Corporation) Guard column: TSKGUARDCOLUMN SUPER AW-H (manufactured by Tosoh Corporation) Column 1: TSK-GEL-SUPER AWM-H (manufactured by Tosoh Corporation) Column 2: TSK-GEL-SUPER AWM-H (manufactured by Tosoh Corporation) Detector: Suggestive refractometer Column temperature: 40°C Developing solvent: Dimethyl sulfoxide Reference material: Polystyrene Flow rate: 0.175 mL / min Sample concentration: 0.2% by mass Injection volume: 150 μL

[0051] <Colloidal Silica (B)> The colloidal silica (B) of the present invention primarily has the effect of improving anti-fogging properties due to hydrophilic groups on the silica surface and inside, and after film formation, it reduces the water solubility of the anti-fogging coating film by the cohesive force between silica particles, thereby making it less likely for water streaks to occur and also has the function of improving water resistance.

[0052] The colloidal silica (B) is SiO ２ The colloidal silica (B) is preferably silica particles represented by the chemical composition formula shown, which are dispersed in a medium to form a colloid. Examples of the medium include methanol, ethanol, 2-propanol, 1-butanol, xylene, dimethylformamide, and water. Among these, methanol, ethanol, 2-propanol, and water are preferred, and 2-propanol and water are more preferred. Furthermore, the surface of the silica particles of the colloidal silica (B) may be modified with a surface treatment agent such as a silane compound. At least one type of colloidal silica (B) may be used, and two or more types may be used in combination.

[0053] The colloidal silica (B) preferably has an average particle diameter of 5 to 100 nm, and more preferably 5 to 30 nm. The average particle diameter is the average primary particle diameter and is indicated by the median diameter (D50) of the volume-based particle size distribution measured by dynamic light scattering. If the average particle diameter is less than 5 nm, the adhesion of the resulting anti-fogging coating to the substrate tends to decrease, and if it exceeds 100 nm, the transparency of the resulting anti-fogging coating tends to decrease. The shape of the colloidal silica (B) can be particulate, chain-like, pearl necklace-like, etc. Among these, the particulate shape is preferred because it can improve the transparency of the anti-fogging coating.

[0054] Examples of commercially available colloidal silica (B) include the following product names: "Snowtex-XS", "Snowtex-S", "Snowtex-30", "Snowtex-50-T", "Snowtex-30L", "Snowtex-YL", "Snowtex-ZL", "Snowtex MP-1040", "Snowtex-UP", "Snowtex-PS-S", "Snowtex-PS-M", "Snowtex-OXS", "Snowtex-OS", "Snowtex-O", "Snowtex-O-40", "Snowtex-OL", "Snowtex-OYL", "Snowtex-OUP", "Snowtex-PS-SO", "Snowtex-PS-MO", and "Snowtex-NX". Examples include "S", "Snowtex-NS", "Snowtex-N", "Snowtex-N-40", "Snowtex-CXS", "Snowtex-C", "Snowtex-CM", "Snowtex-AK", "Snowtex-AK-L", "Snowtex-AK-Y", "Methanol Silica Sol", "MA-ST-M", "MA-ST-M", "MA-ST-L", "IPA-ST", "IPA-ST-L", "IPA-ST-ZL", "IPA-ST-UP", "EG-ST", "NPC-ST-30", "PGM-ST", "DMAC-ST" (all manufactured by Nissan Chemical Corporation), "PL-1", "PL-3", "PL-1-IPA", "PL-1-D" (all manufactured by Fuso Chemical Industries, Ltd.).Among these, "Snowtex-OS", "Snowtex-O", "Snowtex-O-40", "Snowtex-OL", "Snowtex-OYL", "Snowtex-N", "Snowtex-N-40", "Methanol Silica Sol", "MA-ST-M", "MA-ST-L", "IPA-ST", "IPA-ST-L", and "IP "A-ST-ZL", "PL-1", "PL-3", and "PL-1-D" are preferred, and "Snowtex-OS", "Snowtex-O", "Snowtex-O-40", "Snowtex-N", "Snowtex-N-40", "Methanol Silica Sol", "MA-ST-M", "IPA-ST", "PL-1", and "PL-1-D" are more preferred, having an average particle size of 8 to 30 nm, a particulate shape, and using water or a monohydric alcohol having 1 to 4 carbon atoms as the dispersion medium.

[0055] The colloidal silica (B) is preferably 100 parts by mass or more and 900 parts by mass or less per 100 parts by mass of the copolymer (A). From the viewpoint of improving the water resistance of the anti-fogging coating film, the colloidal silica (B) is more preferably 151 parts by mass or more, and even more preferably 230 parts by mass or more, per 100 parts by mass of the copolymer (A), and from the viewpoint of improving adhesion and transparency, it is more preferably 560 parts by mass or less, and even more preferably 400 parts by mass or less.

[0056] In the solid content of the anti-fogging agent composition, the total proportion of the copolymer (A) and the colloidal silica (B) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0057] <Glycidyl group-containing compound (C)> The glycidyl group-containing compound (C) of the present invention is of general formula (2): (In general formula (2), X is a functional group represented by general formula (3) with n = 0 to 8, and Y is a hydrogen atom, a linear or branched alkyl group of carbon chains 1 to 8, a phenyl group, or a functional group represented by general formula (3) with n = 0 to 8.)

[0058] In the above general formula (2), X is preferably a functional group represented by general formula (3) where n is 0, from the viewpoint of improving the adhesion of the anti-fogging coating film. Furthermore, Y is preferably a functional group represented by a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group, from the viewpoint of improving the transparency of the anti-fogging coating film.

[0059] The mass ratio of the glycidyl group-containing compound (C) to the total of the copolymer (A) and colloidal silica (B) is preferably 0.02 or more and 0.2 or less. From the viewpoint of improving adhesion after high temperature and high humidity tests during low-temperature curing of the anti-fogging coating film, the glycidyl group-containing compound (C) is more preferably 0.03 or more, and even more preferably 0.05 or more, relative to the total of the copolymer (A) and colloidal silica (B). From the viewpoint of improving the transparency of the anti-fogging coating film, the glycidyl group-containing compound (C) is more preferably 0.15 or less, and even more preferably 0.1 or less, relative to the total of the copolymer (A) and colloidal silica (B). In other words, the mass ratio of the glycidyl group-containing compound (C) to the total of the copolymer (A) and colloidal silica (B) is more preferably 0.03 or more and 0.15 or less, and even more preferably 0.05 or more and 0.1 or less.

[0060] <Blocked Polyisocyanate Curing Agent (D)> The anti-fogging agent composition of the present invention preferably contains a blocked polyisocyanate curing agent (D) when the copolymer (A) contains the monomer (a-5) as a thermosetting monomer. The blocked polyisocyanate curing agent (D) is a compound having two or more blocked isocyanate groups. The blocked polyisocyanate curing agent (B) may be used alone or two or more types may be used in combination.

[0061] Examples of the blocked polyisocyanate curing agent (B) include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and polyisocyanate derivatives such as their biuret form, isocyanurate form, and trimethylolpropane adduct form, which are produced by blocking (protecting) the isocyanate groups contained in these polyisocyanate derivatives with a blocking agent.

[0062] The blocked polyisocyanate curing agent (D) is preferably a derivative of an aliphatic diisocyanate, a derivative of an alicyclic diisocyanate, or a derivative of an aromatic diisocyanate, from the viewpoint of mainly increasing the crosslinking density of the cured coating film, making it less likely to produce water stains, and improving water resistance. A derivative of an aliphatic diisocyanate or a derivative of an alicyclic diisocyanate is more preferred, and a derivative of a hexamethylene diisocyanate or a derivative of isophorone diisocyanate is even more preferred.

[0063] Examples of the blocking agents include, for example, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, and 1-methoxy-2-propanol; oximes such as formamide oxime, acetal oxime, aceto oxime, methyl ethyl ketoxime, diacetyl mono oxime, benzophenone oxime, and cyclohexanone oxime; pyrazoles such as dimethylpyrazole, diethylpyrazole, and diisopropylpyrazole; and dialkyl malonates such as dimethyl malonate, diethyl malonate, dipropyl malonate, and dibutyl malonate. From the viewpoint of being able to cure at low temperatures and in a short time, pyrazoles, oximes, and dialkyl malonates are preferred as the blocking agent, and dimethylpyrazole, diethylpyrazole, aceto oxime, methyl ethyl ketoxime, dimethyl malonate, and diethyl malonate are more preferred.

[0064] Examples of commercially available blocked polyisocyanates (D) include: product names: "TRIXENE BI 7951", "TRIXENE BI 7960", "TRIXENE BI 7961", "TRIXENE BI 7982", "TRIXENE BI 7991", "TRIXENE BI 7992" (all manufactured by LANXESS), product names: "Aqua BI200", "Aqua BI220" (both manufactured by Baxenden), product names: "Meikanate DX", "Meikanate BOF", "Meikanate AD", "Meikanate NS-1", "Meikanate BZ", "Meikanate UQ-10" (all manufactured by Meisei Kasei Co., Ltd.), product name: "Duranate Examples include "MF-K60B", "Duranate SSB-70P", "Duranate SBN-70D", "Duranate SBL-100", "Duranate MF-B60B", "Duranate 17B-60P", "Duranate TPA-B80E", "Duranate E402-B80B", "Duranate WM44-L70G", "Duranate WHB10-N65G", and "Duranate WLT10-N60G" (all manufactured by Asahi Kasei Corporation). Among these, "TRIXENE BI 7960", "TRIXENE BI 7982", "Meikanate NS-1", "Meikanate BZ", "Meikanate UQ-10", "Duranate MF-K60B", "Duranate SSB-70P", "Duranate SBN-70D", "Duranate SBL-100", "Duranate WM44-L70G", "Duranate WHB10-N65G", and "Duranate WLT10-N60G" are preferred, "TRIXENE BI 7960", "TRIXENE BI 7982", "Meikanate BZ", and "Duranate MF-K60B" are more preferred, and "TRIXENE BI 7960", "Meikanate "BZ" is even more preferable.

[0065] The blocked polyisocyanate curing agent (D) is preferably 1 to 40 parts by mass per 100 parts by mass of the copolymer (A). From the viewpoint of increasing the crosslinking density of the cured coating film, making it less likely to produce water stains, and improving water resistance, the blocked polyisocyanate curing agent (D) is more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, per 100 parts by mass of the copolymer (A), and from the viewpoint of improving transparency, anti-fogging properties, and adhesion, it is more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less.

[0066] The anti-fogging composition of the present invention may further contain a diluent.

[0067] The diluent solvent is used to adjust the solid content and viscosity of the anti-fogging agent composition to be suitable for coating. From the viewpoint of improving the transparency of the anti-fogging coating film, water, ethanol, 1-propanol, 2-propanol, propylene glycol monomethyl ether, diacetone alcohol, 3-methoxybutanol, and 3-methoxy-3-methylbutanol are preferred as the diluent solvent. The suitable solid content and viscosity for coating vary depending on the coating method, but in the case of the spray coating method, the total solid content of the copolymer (A) and colloidal silica (B) in the anti-fogging 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.

[0068] The anti-fogging composition of the present invention may contain a curing catalyst to promote heat curing at low temperatures and in a short time.

[0069] The curing catalyst can be appropriately used depending on the crosslinking system of the copolymer (A), and examples include alkyl sulfonic acid compounds such as sulfuric acid:fluorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, and 1-propanesulfonic acid, aryl sulfonic acid compounds such as benzenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, 4-ethylbenzenesulfonic acid, p-chlorobenzenesulfonic acid, m-xylene-4-sulfonic acid, 3-pyridinesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and 1-pyrenesulfonic acid. From the viewpoint of excellent curability and not easily leaving water stains, aryl sulfonic acid compounds with a benzyl structure or naphthalene structure are preferred as the curing catalyst. Examples of the curing catalysts include alkali metal salts of fatty acids such as sodium laurate, potassium laurate, calcium laurate, barium laurate, sodium oleate, potassium oleate, calcium oleate, barium oleate, sodium stearate, potassium stearate, calcium stearate, barium stearate, and sodium fluorinated alkyl fatty acid salts; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; aromatic sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and naphthalenesulfonic acid; and tertiary amines such as tetramethylbutanediamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonene. Among these, from the viewpoint of improving low-temperature curing properties, alkali metal salts of fatty acids are preferred, with sodium laurate, potassium laurate, calcium laurate, barium laurate, sodium oleate, potassium oleate, calcium oleate, barium oleate, sodium stearate, potassium stearate, calcium stearate, and barium stearate being preferred, and sodium laurate, potassium laurate, sodium oleate, potassium oleate, sodium stearate, and potassium stearate being more preferred. The curing catalyst may be used alone or in combination of two or more types.

[0070] When the curing catalyst is used, the mass ratio of the curing catalyst to the copolymer (A) is preferably 0.1 or higher, and more preferably 0.3 or higher, from the viewpoint of promoting curing and improving water stain resistance and water resistance. Furthermore, the mass ratio is preferably 3 or lower, and more preferably 1 or lower, from the viewpoint of not deteriorating the anti-fogging properties and water stain resistance.

[0071] The anti-fogging agent composition of the present invention may contain a leveling agent, from the viewpoint of making the surface of the anti-fogging coating film smoother.

[0072] Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyether-modified polydimethylpolysiloxane, polyether macromer-modified acrylate, acrylic polymer, and acrylic silicone polymer.

[0073] Examples of commercially available leveling agents include product names: "BYK-300", "BYK-320", "BYK-306", "BYK-307", "BYK-310", "BYK-313", "BYK-315N", "BYK-320", "BYK-322", "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-342", "BYK-345", "BYK- 346", BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-1770, BYK-3455, BYK-3560 (all manufactured by Big Chemie Co., Ltd.), Product names: KP-323, KP-341, KP-104, KP-110, KP-112, KF-351A, KF-352A, KF-353, "KF-354L", "KF-355A", "KF-651A", "KF-945", "KF-640", "KF-642", "KF643" (all manufactured by Shin-Etsu Silicone Co., Ltd.), Product names: "Disparon 1970", "Disparon 230", "Disparon 1711EF", "Disparon 1761", "Disparon LS-001", "Disparon LS-050", "Disparon LS-460", "Disparon L Examples include "S-480" (manufactured by Kusumoto Kasei Co., Ltd.), "Polyflow KL100", "Polyflow KL400HF", "Polyflow KL401", "Polyflow KL402", "Polyflow KL406", "Polyflow KL700", "Polyflow KL900", "Polyflow LE-304", "Polyflow LE302N", "Polyflow LE604", and "Polyflow LE605" (manufactured by Kyoeisha Chemical Co., Ltd.). The leveling agents may be used alone or in combination of two or more types.

[0074] When using the leveling agent, the mass ratio of the leveling agent to the copolymer (A) is preferably 0.1 or higher, and more preferably 0.5 or higher, from the viewpoint of improving the smoothness of the anti-fogging coating. Furthermore, the mass ratio is preferably 5 or lower, and more preferably 2 or lower, from the viewpoint of not deteriorating the anti-fogging properties and water streak resistance.

[0075] The anti-fogging composition of the present invention may contain, as necessary, various conventional additives such as surfactants, antioxidants, ultraviolet absorbers, and light stabilizers. The amount of each of these other components can be added in the conventional amounts, but is usually 10 parts by mass or less per 100 parts by mass of the copolymer (A).

[0076] <Anti-fogging articles> The anti-fogging articles of the present invention are obtained by applying the anti-fogging agent composition to a substrate (object to be coated) using a painting method that is used for ordinary paints, and then heating and curing it to form an anti-fogging coating on the surface of the substrate (object to be coated). In addition, a drying step may be provided before the heating and curing step in order to volatilize and dry the solvent contained in the anti-fogging coating immediately after application.

[0077] The aforementioned substrate (object to be coated) can be any known resin substrate, regardless of its type, but examples include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc.

[0078] When coating the substrate (object to be coated), it is preferable to remove any foreign matter adhering to the surface of the object to be coated before coating in order to improve the wettability of the anti-fogging agent composition to the object to be coated and to prevent repelling. Examples of such methods include dust removal with high-pressure air or ionized air, ultrasonic cleaning with detergent aqueous solution or alcohol solvent, wiping with alcohol solvent, etc., and cleaning with ultraviolet light and ozone. Examples of coating methods include immersion method, flow coating method, roll coating method, bar coating method, spray coating method, etc.

[0079] The drying process is typically carried out at a temperature of 20 to 50°C for 0.5 to 10 minutes.

[0080] When the substrate is a resin member, it is preferable to set the heating temperature to a temperature below the thermal distortion temperature of the resin member. The heating time is affected by the heating temperature and should be set appropriately. The anti-fogging agent composition of the present invention can be cured under heating conditions of 120°C or higher, like conventional anti-fogging agent compositions, but it can also be cured under low-temperature heating conditions of about 90°C to 105°C for about 5 to 30 minutes, which is useful from the viewpoint of reducing energy consumption.

[0081] From the viewpoint of obtaining good anti-fogging properties and a good coating appearance, the thickness of the anti-fogging coating is preferably about 0.5 to 10 μm, and more preferably about 1 to 5 μm.

[0082] The aforementioned anti-fogging articles are more effectively applicable to articles used in environments where condensation is likely to occur, and their use is not limited in any way. Examples of such anti-fogging articles include vehicle lighting equipment for automobiles (headlights, auxiliary headlights, side marker lights, license plate lights, taillights, parking lights, reverse lights, turn signals, auxiliary turn signals, hazard lights, etc.), eyeglasses, windows, mirrors, etc.

[0083] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0084] <Example 1> <Production of Copolymer (A)> Using a reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 90 g of 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd.) was charged as the polymerization solvent, stirring was started, and the mixture was heated to 80°C while blowing in nitrogen gas. Next, the following monomer solution and polymerization initiator solution were added dropwise to this reaction vessel over 2 hours. Monomer solution: A solution prepared by mixing 40 g of N,N-dimethylacrylamide as monomer (a-1), 40 g of N-methylolacrylamide as monomer (a-2), 20 g of benzyl acrylate as monomer (a-3), and 30 g of 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd.) as the polymerization solvent. - Polymerization initiator solution: A solution prepared by mixing 0.71 g of t-hexyl peroxypivalate ("Perhexyl PV", manufactured by NOF Corporation, 70% by mass of active ingredient) as a polymerization initiator with 30 g of 3-methoxy-3-methylbutanol as a polymerization solvent. After the dropwise addition of the monomer solution and polymerization initiator solution was completed, the solution in the reaction vessel was stirred for 3 hours to produce a copolymer (A) solution with a copolymer (A) concentration of 40% by mass. The number-average molecular weight of copolymer (A) was measured by gel permeation chromatography under the above measurement conditions and was found to be 80,000.

[0085] <Preparation of Anti-Fogging Composition> To 250 g of the copolymer (A) solution obtained above (100 g of copolymer), 1500 g of water-dispersible silica sol ("Snowtex OS," manufactured by Nissan Chemical Corporation, 20% by mass of active ingredient) as colloidal silica (B) (300 g as solid content), 20 g of "EX-141," manufactured by Nagase ChemteX Corporation as glycidyl group-containing compound (C), and 2700 g of isopropyl alcohol as a solid content adjusting solvent were added. Furthermore, 1 g of polyether-modified polydimethylsiloxane ("BYK333," manufactured by Shin-Etsu Silicone Co., Ltd.) was added as a leveling agent and mixed to produce the anti-fogging composition.

[0086] <Preparation of Anti-Fog Articles> The anti-fog composition obtained above was applied to a 3 mm thick polycarbonate (PC) resin plate by spray coating so that the thickness of the anti-fog coating film after curing was approximately 1 μm. The plate was then heat-cured at 120°C for 20 minutes to prepare anti-fog articles (test pieces) with an anti-fog coating film. However, for the <Evaluation of Adhesion After High Temperature and High Humidity Test During Low Temperature Curing> described below, instead of heat-curing at 120°C for 20 minutes as described above, heat-curing at 100°C for 30 minutes was performed to prepare anti-fog articles (test pieces) with an anti-fog coating film.

[0087] Table 1 shows the results obtained using the test specimens described above, based on the following evaluation method.

[0088] <<Initial Performance>> <Transparency Evaluation> In accordance with the test method for total light transmittance of plastic materials (JIS-K7361-1), the haze value of the test piece was measured using a haze meter ("HAZE METER HDN5000", manufactured by Nippon Denshoku Industries, Ltd.) (light source: white LED, luminous flux: 14 mm, temperature: 25°C, humidity: 50%) and evaluated in the following four stages. An evaluation of △ or higher indicates no practical problems, ○ is preferable, and ◎ is preferable. The haze value of a 3 mm thick PC resin plate was 0.30. ◎: 0.30 or higher, less than 0.40 ○: 0.40 or higher, less than 0.60 △: 0.60 or higher, less than 0.80 ×: 0.80 or higher

[0089] <Evaluation of Anti-Fogging Properties> A test specimen was placed 5 cm above the surface of a hot water bath maintained at 80°C, with the anti-fogging coating surface facing downwards. Steam from the hot water bath was continuously irradiated onto a predetermined 5 cm x 5 cm area of ​​the anti-fogging coating, and the presence or absence of fogging for 10 seconds after steam irradiation was visually evaluated on the following four scales. An evaluation of △ or higher indicates no practical problems, ○ is preferable, and ◎ is even preferable. ◎: A water film is formed immediately after steam irradiation, and no fogging occurs. ○: Momentary fogging is observed immediately after steam irradiation, but a water film is quickly formed and no further fogging occurs. △: Fogging is observed immediately after steam irradiation, but a water film is formed and no further fogging occurs. ×: Fogging is observed immediately after steam irradiation, and no water film is formed.

[0090] <Evaluation of Adhesion> <Evaluation of Initial Adhesion> On a 1 cm x 1 cm area of ​​the anti-fogging coating surface, 100 grid lines were created by making cuts with a utility knife at 1 mm intervals in both the vertical and horizontal directions. Cellophane tape was firmly pressed onto these grid lines, and the end of the tape was peeled off in one swift motion at a 45° angle. The condition of the grid lines was then visually evaluated in the following four stages. Note that an evaluation of △ or higher indicates no practical problems, ○ is preferable, and ◎ is even preferable. ◎: No peeling observed at all. ○: 1% or more and less than 20% peeling observed. △: 20% or more and less than 50% peeling observed. ×: 50% or more peeling observed.

[0091] <Evaluation of Water Droplet Marks> The test specimen was placed 5 cm above the surface of a warm water bath maintained at 80°C, with the anti-fog coating surface facing downwards. Steam from the warm water bath was continuously irradiated onto a predetermined 5 cm x 5 cm area of ​​the anti-fog coating for 10 seconds. Then, the test specimen was placed vertically to induce water dripping, and the specimen was left to stand at room temperature horizontally to dry. After drying, the presence or absence of water drop marks was visually evaluated on the following four scales. Note that an evaluation of △ or higher indicates no practical problems, ○ is preferable, and ◎ is even preferable. ◎: No water drop marks are visible at all. ○: Water drop marks are barely visible. △: Water drop marks are not noticeable. ×: Water drop marks are noticeable.

[0092] <Evaluation of adhesion after high-temperature and high-humidity test during low-temperature curing> Using test pieces obtained by heat curing at 100°C for 30 minutes, the anti-fogging coating was left to stand for 240 hours in an environment of 80°C and 50% RH. Then, the adhesion of the anti-fogging coating was evaluated in four stages using the same procedure as for the initial adhesion evaluation described above. An evaluation of △ or higher indicates no practical problems, ○ is more preferable, and ◎ is even more preferable. ◎: No peeling observed at all. ○: Peeling of 1% or more and less than 20% observed. △: Peeling of 20% or more and less than 50% observed. ×: Peeling of 50% or more observed.

[0093] <Examples 2-16, Comparative Examples 1-5> <Production of Copolymer (A), Production of Antifogging Composition, and Preparation of Antifogging Articles> In each example and comparative example, the copolymer (A) and antifogging composition of Examples 2-16 and Comparative Examples 1-5 were prepared 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 listed in Tables 1-2. Furthermore, antifogging articles (test pieces) having the antifogging coating of Examples 2-16 and Comparative Examples 1-5 were prepared in the same manner as in Example 1.

[0094] The same evaluation as in Example 1 was performed using the test specimens obtained above. The results are shown in Tables 1 and 2.

[0095]

[0096]

[0097] In Tables 1-2, monomers (a-1) to (a-3) are as follows: DMAA represents N,N-dimethylacrylamide; DEAA represents N,N-diethylacrylamide; N-MAA represents N-methylolacrylamide; 2-MA represents N-methoxymethylacrylamide; GMA represents glycidyl methacrylate; BZA represents benzyl acrylate; BZMA represents benzyl methacrylate; PO-A represents phenoxyethyl acrylate; P2-HA represents phenoxydiethylene glycol acrylate; PO represents phenoxyethyl methacrylate; HEA represents 2-hydroxyethyl acrylate; HEMA represents 2-hydroxyethyl methacrylate; HBA represents 2-hydroxybutyl acrylate; t-BMA represents t-butyl methacrylate.

[0098] In Tables 1 and 2, colloidal silica (B) is as follows: ST-OS is an aqueous acidic silica sol with an average particle size of 8-10 nm (product name: "Snowtex OS", manufactured by Nissan Chemical Corporation, 20% by mass of active ingredient); ST-O is a water-soluble acidic silica sol with an average particle size of 10-15 nm (product name: "Snowtex O", manufactured by Nissan Chemical Corporation, 20% by mass of active ingredient); ST-NS is an aqueous basic silica sol with an average particle size of 8-10 nm (product name: "Snowtex NS", manufactured by Nissan Chemical Corporation, 20% by mass of active ingredient); ST-N is an aqueous basic silica sol with an average particle size of 10-15 nm (product name: "Snowtex N", manufactured by Nissan Chemical Corporation, 20% by mass of active ingredient).

[0099] In Tables 1 and 2, the glycidyl group-containing compound (C) is as follows: EX-141 is phenylglycidyl ether (product name: "Denacol EX-141", manufactured by Nagase ChemteX Corporation); EX-142-IM is o-phenylphenol glycidyl ether (product name: "Denacol EX-142-IM", manufactured by Nagase ChemteX Corporation); EX-145 is phenol (EO) 5-glycidyl ether (product name: "Denacol EX-145", manufactured by Nagase ChemteX Corporation); EX-146 is p-tert-butylphenylglycidyl ether (product name: "Denacol EX-146", manufactured by Nagase ChemteX Corporation); EX-201 is resorcinol diglycidyl ether (product name: "Denacol"). EX-201 (manufactured by Nagase ChemteX Corporation); is indicated. The structure of the glycidyl group-containing compound (C) is shown in Table 3.

[0100]

[0101] In Tables 1 and 2, p-TSA represents p-toluenesulfonic acid; and DNNDSA represents dinonylnaphthalenedisulfonic acid.

[0102] In Tables 1 and 2, as surfactants, Rapizol A-80 is a diester sulfosuccinate (product name: "Rapizol A-80", manufactured by NOF Corporation, active ingredient 80% by mass); Tween-80 is polysorbate 80.

[0103] In Tables 1 and 2, BYK333, as a leveling agent, refers to polyether-modified polysiloxane (trade name: BYK333, manufactured by Bic Chemie).

[0104] <Examples 17-38> <Production of copolymer (A), production of antifogging agent composition, and production of antifogging articles> In each example, the copolymer (A) and antifogging agent composition of Examples 17-38 were prepared 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 listed in Tables 4-5. Furthermore, antifogging articles (test pieces) having the antifogging coating of Examples 17-38 were prepared in the same manner as in Example 1.

[0105] The same evaluation as in Example 1 was performed using the test specimens obtained above. The results are shown in Tables 4 and 5.

[0106]

[0107]

[0108] In Tables 4-5, monomers (a-5) and (a-6) are as follows: FA1DDM is caprolactone-modified 2-hydroxyethyl acrylate (product name: "Praxel FA1DDM", manufactured by Daicel Corporation, average number of moles of caprolactone added: 1); FA2D is caprolactone-modified 2-hydroxyethyl acrylate (product name: "Praxel FA2D", manufactured by Daicel Corporation, average number of moles of caprolactone added: 2); FM1 is caprolactone-modified 2-hydroxyethyl methacrylate (product name: "Praxel FM1", manufactured by Daicel Corporation, average number of moles of caprolactone added: 1); FM2D is caprolactone-modified 2-hydroxyethyl methacrylate (product name: "Praxel FM2D", manufactured by Daicel Corporation, average number of moles of caprolactone added: 2); FM3 represents caprolactone-modified 2-hydroxyethyl methacrylate (trade name: "Praxel FM3", manufactured by Daicel Corporation, average number of moles of caprolactone added: 3); BMA represents n-butyl methacrylate; EHMA represents 2-ethylhexyl methacrylate; LA represents lauryl acrylate; LMA represents lauryl methacrylate; CHA represents cyclohexyl acrylate; CHMA represents cyclohexyl methacrylate.

[0109] In Tables 4-5, as the blocked polyisocyanate curing agent (D), BI7960 is a blocked polyisocyanate compound of a derivative of 1,6-hexamethylene diisocyanate and 3,5-dimethylpyrazole (trade name: "TRIXENE BI 7960", manufactured by LANXESS, active ingredient 70% by mass, isocyanate content in the product 10.20%); BI 7982 is a blocked polyisocyanate compound of a derivative of 1,6-hexamethylene diisocyanate and 3,5-dimethylpyrazole (trade name: "TRIXENE BI 7982", manufactured by LANXESS, active ingredient 70% by mass, isocyanate content in the product 10.20%); BI220 is a blocked polyisocyanate compound of a derivative of 1,6-hexamethylene diisocyanate and 3,5-dimethylpyrazole (trade name: "TRIXENE Aqua BI 220G", manufactured by Baxenden, active ingredient 40% by mass, isocyanate content in the product 4.2%); BZ is an aliphatic nonionic blocked polyisocyanate (trade name: "Meikanate BZ", manufactured by Meisei Chemical Industry Co., Ltd., active ingredient 20% by mass); WM44-L70G is a hexamethylene diisocyanate-type blocked polyisocyanate (trade name: "Duranate WM44-L70G, active ingredient 70% by mass", manufactured by Asahi Kasei Corporation).

[0110] Note that the ingredients in Tables 4 and 5 that are common to Tables 1 and 3 are the same as those in Tables 1 and 3.

Claims

1. An anti-fogging agent composition containing a copolymer (A), colloidal silica (B), and a glycidyl group-containing compound (C), wherein the copolymer (A) is at least a monomer represented by the general formula (1): (In the general formula (1), R １ is a hydrogen atom or a methyl group, and R ２ and R ３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms in the carbon chain.) is a (meth)acrylate copolymer obtained from a monomer mixture containing the monomer (a-1), and the glycidyl group-containing compound (C) is represented by the general formula (2): (In the general formula (2), X is a functional group represented by the general formula (3) where n is 0 to 8, and Y is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms in the carbon chain, a phenyl group, or a functional group represented by the general formula (3) where n is 0 to 8.) An anti-fogging agent composition characterized by being a glycidyl group-containing compound represented by the formula.

2. The anti-fogging composition according to claim 1, characterized in that the copolymer (A) is a (meth)acrylate copolymer (A1) obtained from a monomer mixture comprising a monomer (a-1) represented by the general formula (1) and a crosslinkable monomer (a-2) containing an N-methylol group, an N-alkoxymethyl group, or an epoxy group.

3. The anti-fogging composition according to claim 1, wherein the copolymer (A) is a (meth)acrylate copolymer (A2) obtained from a monomer mixture containing a monomer (a-1) represented by the general formula (1) and a monomer (a-5) containing a hydroxyl group, and further comprises a blocked polyisocyanate curing agent (D).

4. The monomer (a-5) containing the hydroxyl group has the general formula (7): (In general formula (7), R ９ R is a hydrogen atom or a methyl group, １０ A monomer represented by the linear or branched alkylene group having 1 to 8 carbon atoms, or general formula (8): (In general formula (8), R １１ The anti-fogging agent composition according to claim 3, characterized in that it is a monomer represented by (where is a hydrogen atom or a methyl group, and n is an integer from 1 to 10).

5. The monomer mixture is of general formula (4): (In general formula (4), R ４ The anti-fogging composition according to any one of claims 1 to 4, characterized in that it contains a monomer (a-3) having an aromatic group represented by ( ), where is a hydrogen atom or a methyl group, V is a linear or branched alkylene group having 0 to 4 carbon atoms, or a (poly)alkylene oxide chain having 1 to 4 repeating units, and W is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a hydroxyl group.

6. An anti-fogging article characterized by having an anti-fogging coating film formed on a substrate from an anti-fogging agent composition according to any one of claims 1 to 4.

7. An anti-fogging article characterized by having an anti-fogging coating film formed on a substrate from the anti-fogging agent composition described in claim 5.

Images