Anti-fog agent composition and anti-fog article having anti-fog coating film

Abstract

To provide an antifogging agent composition capable of forming an antifogging coating film having excellent transparency, antifogging performance, scratch resistance, water resistance, and weather resistance.SOLUTION: There is provided an antifogging agent composition which comprises a blocked polyisocyanate (A), a polyol (B), a colloidal silica (C) and a surfactant (D), wherein the polyol (B) is a (meth)acrylate copolymer obtained from a monomer mixture containing a monomer (B-1) represented by the general formula (1), a monomer (B-2) represented by the general formula (2), a monomer (B-3) represented by the general formula (3) and a monomer (B-4) represented by the general formula (B-4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antifogging agent composition and an antifogging article having an antifogging coating. [Background technology]

[0002] When the surface of a transparent material such as glass or plastic falls below the dew point, moisture in the air turns into tiny droplets that adhere to the surface. The droplets scatter light, causing the surface to become cloudy, which can impair the transparency of the material and prevent it from performing its intended function.

[0003] As a method for preventing the occurrence of the above-mentioned fogging (anti-fogging), a method is known in which a solution containing a hydrophilic resin, a surfactant, etc. is applied to the surface of a substrate to form an anti-fogging coating film (a dried coating film or a hardened coating film) (Patent Documents 1 to 3).

[0004] In this method, the surfactant contained in the anti-fog coating film reduces the contact angle of the adhering water droplets, preventing light scattering, thereby exhibiting the anti-fog effect. Furthermore, in this method, the surfactant rapidly reduces the contact angle of the water droplets, allowing the anti-fog effect to be exhibited quickly. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2020 / 217969 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-7677 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-308661 [Patent Document 4] Japanese Patent Application Laid-Open No. 2003-334894 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the applications of anti-fog coatings have expanded to include a wide range of applications, such as window glass, windshields for automobiles and aircraft, reflectors, safety glasses, sunglasses, security cameras, in-vehicle cameras, optical sensors, etc. As the applications expand, anti-fog coatings are now required to have various coating properties in addition to anti-fog performance.

[0007] For example, in applications such as protective eyewear, in addition to anti-fogging performance, scratch resistance is required because the anti-fogging coating may be damaged when touched by a human hand or when cleaning dirt from eyeglass lenses. Furthermore, when applied to components for optical applications, extremely high transparency is required. Furthermore, depending on the usage environment (e.g., when used outdoors for a long period of time), in addition to anti-fogging performance, weather resistance is also required for the anti-fogging coating to maintain its aesthetic appearance for a longer period of time.

[0008] The anti-fog coating film disclosed in Patent Document 1 exhibits good anti-fog properties by using a copolymer, colloidal silica, and a specific surfactant that constitute the anti-fog coating film. However, the strength of the anti-fog coating film is low, and there is concern that the scratch resistance may be insufficient depending on the application.

[0009] The anti-fog coating films disclosed in Patent Documents 2 and 3 exhibit good scratch resistance by increasing the crosslinking density through the use of a polyol with a high hydroxyl value in the resin composition that constitutes the anti-fog coating film. However, there was concern that the transparency would be insufficient for use in optical applications due to the insufficient compatibility between metal oxides such as colloidal silica and copolymers such as acrylic polymers.

[0010] In addition, the anti-fog coating films disclosed in Patent Documents 1 to 3 have concerns that when used outdoors for a long period of time, the anti-fog coating films may deteriorate and turn yellow or white due to insufficient weather resistance of the resin compositions that make up the anti-fog coating films. To improve the weather resistance of the anti-fog coating films disclosed in Patent Documents 1 to 3, a method of adding an ultraviolet absorber (UVA) as described in Patent Document 4 can be used. However, simply adding UVA makes it difficult to maintain long-term weather resistance because UVA is likely to leach out of the anti-fog coating film when exposed to sunlight, rain, or the like outdoors.

[0011] For the reasons described above, none of the anti-fog coating films in the prior art has all of the coating film properties required under various usage environments, namely transparency, scratch resistance, water resistance, and weather resistance, in addition to anti-fog performance.

[0012] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an antifogging agent composition capable of forming an antifogging coating film that is excellent in transparency, antifogging performance, scratch resistance, water resistance, and weather resistance. [Means for solving the problem]

[0013] That is, the present invention provides an antifogging agent composition comprising a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D), The polyol (B) is represented by the general formula (1): [ka] (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, and General formula (2): [ka] (In general formula (2), R 4 is a hydrogen atom or a methyl group, and R5 is a linear or branched alkylene group having from 2 to 6 carbon atoms, and X is an oxygen atom or -NH-; General formula (3): [ka] (In general formula (3), R 6 is a hydrogen atom or a methyl group, and R 7 is an ultraviolet absorbing group.) and a monomer (B-3) represented by General formula (4): [ka] (In general formula (4), R 8 is a hydrogen atom or a methyl group, and R 9 is a linear, branched, or cyclic hydrocarbon group having 1 to 22 carbon atoms.

[0014] The present invention also relates to an anti-fogging article having an anti-fogging coating film formed from the anti-fogging agent composition. [Effects of the Invention]

[0015] In the present invention, the following mechanism of action is presumed.

[0016] The anti-fog agent composition of the present invention contains a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D). The polyol (B) contains the monomers (B-1) to (B-4). Therefore, the anti-fog performance of the anti-fog coating film is primarily determined by the properties of the monomer (B-1). The scratch resistance and water resistance of the anti-fog coating film are primarily determined by the properties of the monomer (B-2). The weather resistance of the anti-fog coating film and the compatibility between the polyol (B) and the colloidal silica (C) are primarily determined by the properties of the monomer (B-3). The transparency of the anti-fog coating film is primarily determined by the compatibility between the blocked polyisocyanate (A) and the polyol (B) is primarily determined by the properties of the monomer (B-4). Furthermore, crosslinking of the anti-fog coating film is primarily determined by the properties of the monomer (B-2) and the blocked polyisocyanate (A). Furthermore, since the antifogging agent composition of the present invention contains colloidal silica (C), it is possible to further improve the scratch resistance and water resistance of the antifogging coating film. DETAILED DESCRIPTION OF THE INVENTION

[0017] The antifogging agent composition of the present invention contains a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D).

[0018] <Blocked polyisocyanate (A)> The blocked polyisocyanate (A) of the present invention is a blocked polyisocyanate compound obtained by reacting at least one polyisocyanate compound selected from the group consisting of diisocyanates and derivatives thereof with a thermally dissociable blocking agent.

[0019] Examples of the diisocyanate include aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate; alicyclic diisocyanates such as 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; and aromatic diisocyanates such as xylylene diisocyanate, tolylene-2,6-diisocyanate, and diphenylmethane diisocyanate. Examples of the diisocyanate derivatives include those synthesized using the aliphatic diisocyanates, alicyclic diisocyanates, and / or aromatic diisocyanates as starting materials, such as biuret derivatives, adducts with trimethylolpropane, isocyanurates, and allophanates, as well as aliphatic diisocyanate derivatives, alicyclic diisocyanate derivatives, and aromatic diisocyanate derivatives. The polyisocyanate compounds may be used singly or in combination of two or more.

[0020] From the viewpoint of increasing the crosslink density of the cured coating film and improving the scratch resistance, the polyisocyanate compound is preferably a derivative of an aliphatic diisocyanate, a derivative of an alicyclic diisocyanate, or a derivative of an aromatic diisocyanate, more preferably a derivative of an aliphatic diisocyanate or a derivative of an alicyclic diisocyanate, and even more preferably a derivative of 1,6-hexamethylene diisocyanate or a derivative of isophorone diisocyanate.

[0021] The blocked polyisocyanate compound is obtained by reacting the polyisocyanate compound with a thermally dissociable blocking agent. The thermally dissociable blocking agent is a compound that blocks (protects) the isocyanate groups of the polyisocyanate compound. The term "thermally dissociable" refers to the property of being dissociated from the blocked polyisocyanate compound by heating.

[0022] The thermally dissociable blocking agent is a compound having one active hydrogen atom in the molecule, and examples thereof include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, and 1-methoxy-2-propanol; oximes such as formamide oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime; and pyrazoles such as dimethylpyrazole, diethylpyrazole, and diisopropylpyrazole. The residue derived from the blocking agent is preferably a pyrazole or an oxime, more preferably dimethylpyrazole, diethylpyrazole, acetoxime, or methyl ethyl ketoxime, from the viewpoint of low temperature and short time curing. The blocked polyisocyanate (A) may be used alone or in combination of two or more.

[0023] Examples of commercially available blocked polyisocyanates (A) include those sold under the trade names "TRIXENE BI 7951," "TRIXENE BI 7960," "TRIXENE BI 7961," "TRIXENE BI 7982," "TRIXENE BI 7991," and "TRIXENE BI 7992" (all manufactured by LANXESS), and those sold under the trade names "DURANATE MF-K60B," "DURANATE SSB-70P," "DURANATE SBN-70D," "DURANATE MF-B60B," "DURANATE 17B-60P," "DURANATE TPA-B80E," "DURANATE E402-B80B," and "DURANATE WM44-L70G" (all manufactured by Asahi Kasei Corporation).

[0024] <Polyol (B)> The polyol (B) of the present invention is a compound having two or more hydroxyl groups in one molecule, and has the function of forming a crosslinked structure in the copolymer by crosslinking between molecules through a reaction with the blocked polyisocyanate (A). The polyol (B) is also a (meth)acrylate copolymer obtained from a monomer mixture, and the monomer mixture contains at least the following monomers (B-1) to (B-4):

[0025] <Monomer (B-1)> The monomer (B-1) of the present invention is represented by the general formula (1): [ka] (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.

[0026] The monomer (B-1) mainly has the function of enhancing the anti-fogging performance of the anti-fogging coating film.

[0027] Examples of the monomer (B-1) include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, Ni-propyl(meth)acrylamide, Nn-butyl(meth)acrylamide, Ni-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide. From the viewpoint of improving anti-fogging performance, the monomer (A-1) is preferably an N,N-dialkyl(meth)acrylamide-based monomer, and more preferably N,N-dimethyl(meth)acrylamide or N,N-diethyl(meth)acrylamide. The monomer (B-1) may be used alone or in combination of two or more.

[0028] The monomer (B-2) of the present invention is represented by the general formula (2): [ka] (In general formula (2), R 4 is a hydrogen atom or a methyl group, and R 5 is a linear or branched alkylene group having 2 to 6 carbon atoms, and X is an oxygen atom or -NH-.

[0029] The monomer (B-2) mainly functions to enhance the scratch resistance and water resistance of the anti-fog coating film, and in this case, a crosslinked structure is formed between the molecules by reaction with the blocked polyisocyanate (A), resulting in enhanced scratch resistance and water resistance.

[0030] Examples of the monomer (B-2) include 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, 2-hydroxyethyl acrylamide, 4-hydroxybutyl acrylamide, 6-hydroxyhexyl acrylamide, 2-hydroxyethyl methacrylamide, 3-hydroxypropyl methacrylamide, and 5-hydroxypentyl methacrylamide. Among these, from the viewpoint of scratch resistance, R 5 is preferably a linear monomer having 2 to 4 carbon atoms, and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, and 2-hydroxyethyl methacrylamide are more preferred. At least one type of the monomer (B-2) may be used, or two or more types may be used in combination.

[0031] <Monomer (B-3)> The monomer (B-3) of the present invention is represented by the general formula (3): [ka] (In general formula (3), R 6 is a hydrogen atom or a methyl group, and R 7 is an ultraviolet absorbing group.

[0032] The monomer (B-3) primarily functions to enhance the transparency and weather resistance of the anti-fog coating film. Although the mechanism of action is unknown, the inclusion of an ultraviolet-absorbing group derived from the monomer (B-3) in the structure of the polyol (B) improves the compatibility between the polyol (B) and the colloidal silica (C), thereby enhancing transparency. Furthermore, copolymerization of the monomer (B-3) chemically fixes a compound with ultraviolet-absorbing properties in the resin composition, thereby preventing UVA leaching from the anti-fog coating film and enhancing weather resistance.

[0033] In the general formula (3), examples of the ultraviolet absorbing group include benzotriazole-based ultraviolet absorbing groups, triazine-based ultraviolet absorbing groups, and hydroxybenzophenone-based ultraviolet absorbing groups. Among these, benzotriazole-based ultraviolet absorbing groups and triazine-based ultraviolet absorbing groups are preferred from the viewpoint of improving transparency and weather resistance. The monomer (B-3) may be used alone or in combination of two or more.

[0034] Specific examples of the monomer (B-3) include those represented by the general formula (5): [ka] (In general formula (5), R 10 is a hydrogen atom or a methyl group, and R 11 is a linear or branched alkylene group having 1 to 8 carbon atoms, a benzotriazole derivative represented by the general formula (6): [ka] (In general formula (6), R 12 is a hydrogen atom or a methyl group, and R 13 is a linear or branched alkylene group having 2 to 11 carbon atoms, and R 14 are independently a hydrogen atom or a methyl group.) A triazine derivative represented by general formula (7): [ka] (In general formula (7), R 15 is a hydrogen atom or a methyl group, and R 16 is a linear alkylene group having 1 or 2 carbon atoms, and R 17 is a hydroxy group or a methoxy group.

[0035] Examples of the benzotriazole derivative represented by the general formula (5) include [3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]methyl (meth)acrylate, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propyl (meth)acrylate, 3-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propyl (meth)acrylate, 4-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]butyl (meth)acrylate, and 8-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]octyl (meth)acrylate. The benzotriazole derivative is preferably [3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]methyl(meth)acrylate or 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl(meth)acrylate from the viewpoint of improving anti-fogging performance.

[0036] Examples of the triazine derivative represented by the general formula (6) include 2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl (meth)acrylate, 2-[4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]ethyl (meth)acrylate, 3-[4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]-2-methylpropyl (meth)acrylate, and 11-[4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]undecyl (meth)acrylate. The triazine derivative is preferably 2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl (meth)acrylate from the viewpoint of improving anti-fogging performance.

[0037] Examples of the hydroxybenzophenone derivative represented by the general formula (7) include (3-benzoyl-2-hydroxy-6-methoxyphenyl)methyl (meth)acrylate, 2-(3-benzoyl-2,6-dihydroxyphenyl)ethyl (meth)acrylate, etc. From the viewpoint of improving anti-fogging performance, the benzophenone derivative is preferably (3-benzoyl-2-hydroxy-6-methoxyphenyl)methyl (meth)acrylate.

[0038] <Monomer (B-4)> The monomer (B-4) of the present invention is represented by the general formula (4): [ka] (In general formula (4), R 8 is a hydrogen atom or a methyl group, and R 9 is a straight-chain, branched-chain, or cyclic hydrocarbon group having 1 to 22 carbon atoms.

[0039] In the general formula (4), examples of the linear, branched, or cyclic hydrocarbon group having 1 to 22 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-amyl, i-amyl, t-amyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-nonyl, isobornyl, lauryl, myristyl, cetyl, stearyl, and behenyl; alicyclic hydrocarbon groups such as cyclohexyl, isobornyl, dicyclopentenyl, dicyclopentenyloxyethyl, and dicyclopentanyl; alkenyl groups such as allyl and oleyl; and aromatic hydrocarbon groups such as phenyl, benzyl, and phenoxyethyl. From the viewpoint of enhancing the water resistance of the anti-fogging film, the hydrocarbon group is preferably a linear, branched, or cyclic hydrocarbon group having 2 to 18 carbon atoms, and more preferably a linear, branched, or cyclic hydrocarbon group having 4 to 16 carbon atoms. The monomer (B-4) may be used alone or in combination of two or more types.

[0040] The monomer (B-4) mainly functions to enhance the transparency of the anti-fog coating film. Although the mechanism of action is unknown, the inclusion of a hydrocarbon group derived from the monomer (B-4) in the structure of the polyol (B) improves the compatibility between the blocked polyisocyanate (A) and the polyol (B), thereby enhancing transparency.

[0041] The monomer mixture may contain, as other monomers in addition to the monomers (B-1) to (B-4), aromatic vinyl monomers such as styrene, vinyl toluene, and α-methyl styrene; vinyl monomers containing quaternary ammonium salts such as (meth)acryloyloxyethyl trimethyl ammonium chloride and (meth)acryloylaminopropyl trimethyl ammonium chloride; light-stable group-containing acrylic monomers such as 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate; carboxy 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; styrene sulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 3 ... - Sulfonic acid group-containing vinyl monomers such as sulfopropyl (meth)acrylate, and their ammonium salts, organic amine salts, and alkali metal salts; phosphoric acid group-containing vinyl monomers such as 2-(meth)acryloyloxyethyl acid phosphate, and their ammonium salts, organic amine salts, and alkali metal salts; bifunctional monomers such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol (meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and glycerin di(meth)acrylate. acrylic monomers; alkoxysilyl group-containing vinyl monomers such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, and vinyltrimethoxysilane; epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, vinyl glycidyl ether, and allyl glycidyl ether; amino group-containing vinyl monomers such as dimethylaminopropyl (meth)acrylamide and dimethylaminoethyl (meth)acrylate; (meth)acryloylmorpholine, and diacetone (meth)acrylamide can be used.

[0042] The proportion of the monomer (B-1) in the monomer mixture is preferably 30% by weight or more and 80% by weight or less, more preferably 40% by weight or more and even more preferably 45% by weight or more from the viewpoint of improving anti-fogging performance, and more preferably 70% by weight or less and even more preferably 65% ​​by weight or less from the viewpoint of improving scratch resistance and water resistance.

[0043] The proportion of the monomer (B-2) in the monomer mixture is preferably 5% by weight or more and 30% by weight or less, more preferably 8% by weight or more and even more preferably 10% by weight or more from the viewpoint of improving scratch resistance and water resistance, and more preferably 25% by weight or less and even more preferably 20% by weight or less from the viewpoint of improving anti-fogging performance.

[0044] The proportion of the monomer (B-3) in the monomer mixture is preferably 1% by weight or more and 40% by weight or less, more preferably 3% by weight or more and even more preferably 5% by weight or more from the viewpoint of improving transparency and weather resistance, and more preferably 30% by weight or less and even more preferably 25% by weight or less from the viewpoint of improving anti-fogging performance.

[0045] The proportion of the monomer (B-4) in the monomer mixture is preferably 5% by weight or more and 50% by weight or less, more preferably 8% by weight or more and even more preferably 10% by weight or more from the viewpoint of improving transparency, and more preferably 35% by weight or less and even more preferably 30% by weight or less from the viewpoint of improving anti-fogging properties.

[0046] <Method for producing polyol (B)> The polyol (B) of the present invention is a copolymer obtained by copolymerizing the monomer mixture. The structure of the polyol (B) may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. However, a random copolymer is preferred from the viewpoints of improving the effects of the antifogging agent composition, including antifogging performance, and of easily preparing the antifogging agent composition. Various known polymerization methods, such as radical polymerization, cationic polymerization, cationic living polymerization, and anionic living polymerization, are used to obtain the polyol (B). However, radical polymerization is preferred from the viewpoints of ease of industrial productivity and a wide range of performance aspects. Examples of radical polymerization methods include conventional bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization. However, solution polymerization is preferred because the polymerized product can be used as an antifogging agent composition directly.

[0047] Examples of polymerization solvents used in the solution polymerization method include alcohol-based solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, and diacetone alcohol; glycol ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-butanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran and dioxane; ester-based solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, and ethyl lactate; aromatic solvents such as benzene, toluene, and xylene; amide-based solvents such as formamide and dimethylformamide; and water. The polymerization solvents may be used alone or in combination.

[0048] In addition, it is preferable to use a polymerization solvent having a boiling point of less than 180°C at 1 atmosphere, since solvents with extremely high boiling points may impair adhesion to the substrate due to residual solvent during drying and heat curing of the anti-fog coating film.

[0049] The radical polymerization initiator may be a commonly used organic peroxide, azo compound, or the like. Examples of the organic peroxide include benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-hexanoate, t-butylperoxypivalate, and t-hexylperoxypivalate. Examples of the azo compound include 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. The radical polymerization initiator may be used alone or in combination of two or more.

[0050] The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the monomer mixture. The polymerization is preferably carried out while the radical polymerization initiator is added dropwise to the reaction vessel, as this makes it easier to control the heat generated by polymerization. The temperature at which the polymerization reaction is carried out varies depending on the type of radical polymerization initiator used, but is preferably 30°C to 150°C, more preferably 40°C to 100°C, for industrial production.

[0051] The weight-average molecular weight (Mw) of the polyol (B) is preferably 20,000 or more, more preferably 30,000 or more, from the viewpoint of imparting water resistance to the anti-fog coating film, and is preferably 300,000 or less, more preferably 200,000 or less, from the viewpoint of improving the coatability and handleability of the anti-fog agent composition.

[0052] The weight average molecular weight (Mw) of the polyol (B) can be determined by a GPC method using a sample prepared by dissolving the sample in tetrahydrofuran to prepare a 0.5 wt % solution and filtering the solution through a 0.45 μm membrane filter under the following conditions. <Measurement of weight average molecular weight (Mw)> Analytical equipment: HLC-8320GPC (Tosoh Corporation) Column: TSKgel SuperMultipore HZ-M (2 columns) (Tosoh Corporation) Column size: 4.6 x 150 mm Eluent: tetrahydrofuran Flow rate: 0.35mL / min Detector: differential refractometer Column temperature: 40℃ Standard sample: polystyrene

[0053] The hydroxyl value of the polyol (B) is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, from the viewpoint of imparting scratch resistance and water resistance to the anti-fog coating film, and is preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less, from the viewpoint of imparting anti-fog properties to the anti-fog coating film.

[0054] The amount of the blocked polyisocyanate (A) is preferably 10 parts by weight or more and 90 parts by weight or less relative to 100 parts by weight of the polyol (B). From the viewpoint of improving scratch resistance and water resistance, the amount of the blocked polyisocyanate (A) is more preferably 15 parts by weight or more and even more preferably 20 parts by weight or more relative to 100 parts by weight of the polyol (B). From the viewpoint of improving anti-fogging performance, the amount of the blocked polyisocyanate (A) is more preferably 80 parts by weight or less and even more preferably 50 parts by weight or less.

[0055] Furthermore, the blocked polyisocyanate (A) and the polyol (B) preferably have an NCO / OH ratio (hereinafter referred to as NCO / OH ratio) between the isocyanate group content (NCO) generated after the blocking agent for the blocked isocyanate groups contained in the blocked polyisocyanate (A) is deblocked and the hydroxyl group content (OH) of the polyol (B) in the blocked polyisocyanate (A). From the viewpoint of improving water resistance, the NCO / OH ratio is more preferably 0.2 or more.

[0056] <Colloidal Silica (C)> The colloidal silica (C) of the present invention is in a state in which silica particles represented by the chemical formula SiO2 are dispersed in a medium to form a colloid. Examples of the medium include methanol, ethanol, i-propanol, n-butanol, xylene, dimethylformamide, propylene glycol monomethyl ether, and water. Among these, methanol, ethanol, i-propanol, propylene glycol monomethyl ether, and water are preferred, and i-propanol, propylene glycol monomethyl ether, and water are more preferred. The colloidal silica (C) may also be silica particles whose surfaces have been modified with a surface treatment agent such as a silane compound. The colloidal silica (C) may be used alone or in combination of two or more types.

[0057] Examples of commercially available colloidal silica (C) include products under the trade 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," "Snowtex NXS," "Snowtex NS," "Snowtex N," "Snowtex N-40," "Snowtex CXS," "Snowtex C," "Snowtex CM," "Snowtex AK," "Snowtex AK-L," "Snowtex AK-Y," "IPA-ST," and "PGM-ST" (all manufactured by Nissan Chemical Industries, Ltd.).

[0058] The average particle size of the colloidal silica (C) is preferably in the range of 4 nm to 100 nm. From the viewpoint of improving transparency, the average particle size is more preferably 50 nm or less, and even more preferably 30 nm or less. The average particle size is the average primary particle size and is expressed as the median diameter (D50) of the volume-based particle size distribution measured by dynamic light scattering. The shape of the colloidal silica (C) may be particulate, chain-like, pearl necklace-like, or the like. Among these, from the viewpoint of improving the transparency of the anti-fog coating film, the particulate shape is preferred.

[0059] The amount of the colloidal silica (C) is preferably 5 parts by weight or more and 800 parts by weight or less relative to 100 parts by weight of the polyol (B). From the viewpoint of improving scratch resistance and water resistance, the amount of the colloidal silica (C) is more preferably 10 parts by weight or more and even more preferably 30 parts by weight or more relative to 100 parts by weight of the polyol (B), and from the viewpoint of improving transparency, the amount is more preferably 500 parts by weight or less and even more preferably 200 parts by weight or less.

[0060] <Surfactant (D)> The surfactant (D) of the present invention is at least one selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0061] Examples of the anionic surfactant include fatty acid salts such as fatty acid alkali metal salts, such as sodium oleate and potassium oleate; higher alcohol sulfates, such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates and alkylnaphthalene sulfonates, such as sodium dodecylbenzene sulfonate and sodium alkylnaphthalene sulfonate; polyoxyethylene sulfate salts, such as naphthalene sulfonate-formaldehyde condensates, dialkyl sulfosuccinates, dialkyl phosphate salts, and sodium polyoxyethylene alkylphenyl ether sulfate; and fluorine-containing anionic surfactants, such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphate esters. From the viewpoint of improving anti-fogging performance, the anionic surfactant is preferably a dialkyl sulfosuccinate or a fluorine-containing anionic surfactant. The anionic surfactant may be used alone or in combination of two or more.

[0062] Examples of the cationic surfactant include amine salts such as laurylamine acetate, triethanolamine monoformate, and stearamidoethyl diethylamine acetate; alkyltrimethylammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride; dialkyldimethylammonium salts such as dilauryldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and stearyldimethylbenzylammonium chloride; and hydroxyl-containing ammonium salts such as ricinoleamidopropylethyldimonium ethosulfate, ricinoleamidopropyltrimonium chloride, and ricinoleamidopropyltrimonium methosulfate. From the viewpoint of improving anti-fogging performance, alkyltrimethylammonium salts, dialkyldimethylammonium salts, and hydroxyl-containing ammonium salts are preferred as the cationic surfactant. Furthermore, from the viewpoint of improving anti-fogging durability, hydroxyl-containing ammonium salts are preferred. The cationic surfactants may be used alone or in combination.

[0063] Examples of the nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol; polyoxyethylene sorbitan fatty acid esters such as polypropylene glycol ethylene oxide adduct, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate; phosphate esters such as alkyl phosphate esters and polyoxyethylene alkyl ether phosphate esters; and perfluoroalkyl Examples of fluorine-containing nonionic surfactants include amine oxides, perfluoroalkenylamine oxides, perfluoroalkylethylene oxide adducts, perfluoroalkenylethylene oxide adducts, oligomers having a perfluoroalkyl group and a hydrophilic group, oligomers having a perfluoroalkenyl group and a hydrophilic group, oligomers having a perfluoroalkyl group and a lipophilic group, oligomers having a perfluoroalkenyl group and a lipophilic group, oligomers having a perfluoroalkyl group, a hydrophilic group and a lipophilic group, and oligomers having a perfluoroalkenyl group, a hydrophilic group and a lipophilic group; sugar esters, cellulose ethers, etc. The nonionic surfactants may be used alone or in combination of two or more.

[0064] Examples of the amphoteric surfactant include fatty acid-type amphoteric surfactants such as dimethyl alkyl lauryl betaine, dimethyl alkyl stearyl betaine, lauryl dimethyl aminoacetic acid betaine, and lauric acid amidopropyl dimethyl aminoacetic acid betaine; sulfonic acid-type amphoteric surfactants such as dimethyl alkyl sulfobetaine; alkyl glycine; etc. The amphoteric surfactants may be used alone or in combination of two or more.

[0065] From the viewpoint that good anti-fogging performance can be obtained with a relatively small amount of surfactant (D), an anionic surfactant, a combination of an anionic surfactant and a cationic surfactant, or a combination of an anionic surfactant and an amphoteric surfactant is preferred. In particular, when the anionic surfactant is a fluorine-containing anionic surfactant, the surface tension of the anti-fogging coating film relative to water can be more effectively reduced, thereby achieving higher anti-fogging performance.

[0066] The surfactant (D) is preferably 1 part by weight or more and 35 parts by weight or less relative to 100 parts by weight of the polyol (B). From the viewpoint of improving anti-fogging performance, the surfactant (D) is more preferably 5 parts by weight or more and even more preferably 8 parts by weight or more relative to 100 parts by weight of the polyol (B), and from the viewpoint of improving transparency, the surfactant (D) is more preferably 30 parts by weight or less and even more preferably 20 parts by weight or less.

[0067] The antifogging agent composition of the present invention may contain a dilution solvent from the viewpoint of improving coating workability.

[0068] The dilution solvent is used to adjust the solid content and viscosity of the antifogging agent composition to be suitable for coating. Examples of the dilution solvent include the same solvents as those used as the polymerization solvent for the polyol (B). One type of dilution solvent may be used, or two or more types may be used in combination. The solid content and viscosity suitable for coating vary depending on the coating method. In the case of a spray coating method, the total weight percentage of the blocked polyisocyanate (A), the polyol (B), and the colloidal silica (C) in the antifogging agent composition is preferably 3% by weight or more, more preferably 5% by weight or more, and preferably 30% by weight or less, and more preferably 20% by weight or less.

[0069] The antifogging agent composition of the present invention may contain a curing catalyst from the viewpoint of enabling heat curing at low temperature in a short time.

[0070] Examples of the curing catalyst include 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 fatty acid alkali metal salts such as fluorine alkyl fatty acid sodium salts; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and sodium stearate. Examples include aromatic sulfonic acids such as phthalenesulfonic acid; 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; and metal organic compounds such as tin octoate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, and dibutyltin fatty acid salts. Among these, from the viewpoint of improving low-temperature curing properties, fatty acid alkali metal salts are preferred, 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 are preferred, and sodium laurate, potassium laurate, sodium oleate, potassium oleate, sodium stearate, and potassium stearate are more preferred. The curing catalysts may be used alone or in combination of two or more.

[0071] When the curing catalyst is used, the amount of the curing catalyst is preferably 0.05 parts by weight or more and 10 parts by weight or less, more preferably 0.1 parts by weight or more and 5 parts by weight or less, and even more preferably 1 part by weight or more and 3 parts by weight or less, relative to 100 parts by weight of the blocked polyisocyanate (A).

[0072] A leveling agent may be added to the anti-fogging composition of the present invention from the viewpoint of making the surface of the anti-fogging coating film smoother.

[0073] Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyether-modified polydimethylpolysiloxane, polyether macromer-modified acrylate, acrylic polymer, and acrylic silicone polymer.

[0074] Commercially available leveling agents include, for example, those with trade 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 / 346", "BYK-347", "BYK-348", "BYK-349", and "BYK- 370," "BYK-377," "BYK-378," "BYK-3455," and "BYK-3560" (all manufactured by BYK-Chemie Co., Ltd.), trade 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," and "KF-642" (all manufactured by Shin-Etsu Silicones Co., Ltd.), trade name: "Disparlon" Examples of the leveling agent include Disparlon 1970, Disparlon 230, Disparlon 1711EF, Disparlon 1761, Disparlon LS-001, Disparlon LS-050, Disparlon LS-460, and Disparlon LS-480 (all manufactured by Kusumoto Chemicals Co., Ltd.). One type of the leveling agent may be used, or two or more types may be used in combination.

[0075] When the leveling agent is used, the amount of the leveling agent is preferably 0.05 parts by weight or more and 10 parts by weight or less, more preferably 0.1 parts by weight or more and 5 parts by weight or less, and even more preferably 1 part by weight or more and 3 parts by weight or less, relative to 100 parts by weight of the polyol (B).

[0076] In addition to the above components, the antifogging agent composition of the present invention may contain, as necessary, various conventional additives such as antioxidants, ultraviolet absorbers, light stabilizers, etc. The amount of the other components added may be the conventional amount for each additive, but is usually 20 parts by weight or less per 100 parts by weight of the polyol (B).

[0077] <Anti-fog articles> The anti-fog article of the present invention is one in which the anti-fog agent composition is applied to a substrate (substrate) by a coating method typically used for coatings, followed by heat curing to form an anti-fog coating film on the surface of the substrate (substrate). A drying step can be carried out before the heat curing step in order to volatilize and dry the solvent contained in the anti-fog coating film immediately after application.

[0078] The substrate (object to be coated) may be of any type and is not particularly limited, and examples thereof include resin substrates such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin; inorganic substrates such as glass; etc. The shape of the substrate is also not limited, and examples thereof include films, sheets, and three-dimensional molded products.

[0079] When applying the anti-fog agent composition to the substrate (object to be coated), it is preferable to remove any foreign matter adhering to the surface of the substrate (object to be coated) before application in order to increase the wettability of the anti-fog agent composition to the substrate (object to be coated) and prevent repellency. Examples of methods include dust removal using high-pressure air or ionized air, ultrasonic cleaning with a detergent aqueous solution or an alcohol solvent, wiping using an alcohol solvent, and cleaning with ultraviolet light and ozone. Examples of application methods include dipping, flow coating, roll coating, bar coating, and spray coating.

[0080] The drying is usually carried out at a temperature of 20 to 50° C. for 0.5 to 10 minutes.

[0081] When the substrate is a resin member, the heating temperature is preferably set to a temperature equal to or lower than the thermal distortion temperature of the resin member. The heating time is affected by the heating temperature and should be set appropriately. For example, when the heating temperature is 120°C, the heating time is preferably 30 minutes or more, and more preferably 60 minutes or more.

[0082] The thickness of the anti-fog coating film is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, from the viewpoint of obtaining good anti-fog performance and good coating film appearance.

[0083] The anti-fogging article is more suitable for use in an environment where condensation is likely to occur, and its use is not limited in any way. Examples of the anti-fogging article include automotive vehicle lighting fixtures (headlights, auxiliary headlights, width lights, license plate lights, tail lights, parking lights, back-up lights, turn signals, auxiliary turn signals, emergency flashers, etc.), general window glass, automobile and aircraft windshields, reflectors, protective glasses, sunglasses, security cameras, in-vehicle cameras, and optical sensors. [Example]

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0085] Example 1 <Production of Polyol (B)> A reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube was charged with 240 parts by weight of diacetone alcohol as a polymerization solvent, and heated to 75° C. while blowing in nitrogen gas. Next, a solution obtained by mixing 60 parts by weight of N,N-dimethylacrylamide as monomer (B-1), 15 parts by weight of 2-hydroxyethyl acrylate as monomer (B-2), 15 parts by weight of 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (trade name: "RUVA-93", manufactured by Otsuka Chemical Co., Ltd.) as monomer (B-3), 10 parts by weight of cyclohexyl acrylate and 35 parts by weight of diacetone alcohol as monomer (B-4), and a solution obtained by dissolving 1.4 parts by weight of t-hexylperoxyneodecanoate (trade name: "Perhexyl ND", manufactured by NOF Corporation, active ingredient 70% by weight) as a radical polymerization initiator in 20 parts by weight of diacetone alcohol were added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred for 30 minutes, and then a solution of 0.3 parts by weight of Perhexyl ND dissolved in 5 parts by weight of diacetone alcohol was added dropwise. After the dropwise addition was completed, the mixture was stirred for 1 hour and 30 minutes, and then cooled to produce a solution of polyol (B). The weight average molecular weight of polyol (B) was measured by gel permeation chromatography and found to be 90,000. The solids content of this polyol (B) solution was 25.0%. The hydroxyl value (theoretical value) of polyol (B) was 72.5 mg KOH / g.

[0086] <Production of Antifogging Agent Composition> A mixture of 400 parts by weight (25% solids) of the polyol (B) obtained above and 57 parts by weight of a blocked polyisocyanate compound of a 1,6-hexamethylene diisocyanate derivative and 3,5-dimethylpyrazole (trade name: "TRIXENE BI 7960", manufactured by LANXESS, active ingredient 70% by weight, isocyanate content in the product 10.20%) as the blocked polyisocyanate (A), 150 parts by weight of isopropyl alcohol-dispersed silica sol (trade name: "IPA-ST", manufactured by Nissan Chemical Industries, Ltd., active ingredient 30% by weight) as the colloidal silica (C), 5.0 parts by weight of a fluorine-containing anionic surfactant (trade name: "Ftergent 100", manufactured by Neos Corporation) and ricinoleamidopropylethyldimonium ethosulfate (trade name: "Lipoquat R", manufactured by VANTAGE Specialty Chemicals, Ltd.) as the surfactant (D) was used. An anti-fogging agent composition was prepared by mixing 5.0 parts by weight of (A) (manufactured by BYK Ingredients, Inc.), 1.5 parts by weight of potassium oleate as a curing catalyst, 1.5 parts by weight of polyether-modified polydimethylsiloxane (trade name: "BYK-333", manufactured by BYK-Chemie) as a leveling agent, and 1222 parts by weight of diacetone alcohol as a diluent. The NCO / OH ratio was calculated as follows: {parts by weight of (A) × NCO content of (A) / 42.0} / {parts by weight of (B) (as active ingredient) × hydroxyl value of (B) / 561} = {57 × 10.20 / 42.0} / {100 × 72.5 / 561} = 1.07

[0087] <Preparation of anti-fogging article> In an environment set at 25°C and a relative humidity of 30% RH, the anti-fog agent composition obtained above was spray-coated onto a polycarbonate (PC) resin plate so that the thickness of the anti-fog coating film after curing would be approximately 2 to 3 μm, and the coating was then heat-cured at 120°C for 60 minutes to produce an anti-fog article (test piece) with an anti-fog coating film.

[0088] The test pieces obtained above were used to carry out the evaluation methods (1) to (5) below, and the results are shown in Table 1.

[0089] <(1) 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 Co., Ltd.) (light source: white LED, luminous flux: 14 mm, temperature: 25°C, humidity: 50%) and rated on the following four-point scale. A rating of B- or higher indicates no practical problems, B+ is preferable, and A is more preferable. The haze value of a 3 mm thick PC resin plate was 0.30. A: Haze value is 0.30 or more and less than 0.40 B+: Haze value is 0.40 or more and less than 0.50 B-: Haze value is 0.50 or more and less than 0.60 C: Haze value is 0.60 or more

[0090] <(2) Evaluation of anti-fogging performance> The test piece was placed with the anti-fog coating side facing downwards at a height of 2 cm above the water surface of a hot water bath maintained at 80°C, and steam from the hot water bath was continuously irradiated onto the anti-fog coating. 10 seconds after irradiation, the presence or absence of fogging was visually evaluated on the following four-point scale. A rating of B- or higher was acceptable for practical use, B+ was preferable, and A was even more preferable. A: A water film is formed immediately after steam irradiation and the glass does not become cloudy. B+: A momentary clouding is observed immediately after steam irradiation, but a water film quickly forms and the clouding does not occur. B-: Clouding is observed immediately after irradiation, but a water film forms and the clouding does not occur. C: Clouding was observed immediately after steam irradiation, and no water film was formed.

[0091] <(3) Evaluation of Scratch Resistance> A cotton ball (2.5cm x 6cm) soaked in 1cc of i-propanol was placed on the surface of the anti-fog coating under a 500g load, and the ball was rubbed back and forth 10 times using a rubbing tester (Gakushin-type rubbing fastness tester AB-301, manufactured by Tester Sangyo Co., Ltd.). The anti-fog coating surface was then visually observed and rated on the following three-point scale. A rating of B or higher was acceptable for practical use, and A was preferable. A: There is no change in appearance from before the test. B: A few streak-like scratches are observed in part of the anti-fog coating film. C: Streaky scratches are observed throughout the anti-fog coating film.

[0092] <(4) Evaluation of water resistance> The test piece was immersed in ion-exchanged water maintained at 40°C for 240 hours, and then left to stand at room temperature for 24 hours, after which the appearance of the anti-fog coating film was visually evaluated on the following four-point scale: A rating of B- or higher indicates no practical problem, B+ is preferable, and A is more preferable. A: There is no change in appearance from before the test. B+: The surface of the anti-fog coating is slightly rough. B-: The surface of the anti-fog coating is rough, or slight whitening or stains are observed. C: The anti-fog coating is partially or completely dissolved, or there is clear whitening or staining.

[0093] <(5) Weather resistance evaluation> An accelerated weathering tester ("Sunshine Weather Meter S80" manufactured by Suga Test Instruments Co., Ltd.) was used, and the irradiation intensity was 78.5 W / m 2 After the test was carried out for 1000 hours under conditions of a black panel temperature of 63°C, humidity of 50% RH, and 12 minutes of rainfall during 60 minutes, the YI value (yellowing index) of the test piece was measured (measurement method: ASTM D1925) using a spectrophotometer (SPECTROPHOTO METER CM-5, manufactured by Konica Minolta, Inc.) and evaluated on the following four-point scale: A rating of B- or higher means no practical problem, B+ is preferable, and A is more preferable. A: YI value is less than 2.0 B+: YI value less than 3.0 B-: YI value is less than 4.0 C: YI value is 4.0 or more

[0094] <Examples 2 to 25 and Comparative Examples 1 to 7> <Production of anti-fogging agent composition and fabrication of anti-fogging article> Anti-fog agent compositions of Examples 2 to 24 and Comparative Examples 1 to 7 were produced in the same manner as in Example 1, except that the raw materials of Example 1 were changed to the raw materials and their blending amounts shown in Tables 1 to 3. Furthermore, anti-fog articles (test pieces) having the anti-fog coating films of Examples 2 to 24 and Comparative Examples 1 to 7 were produced in the same manner as in Example 1.

[0095] Tables 1 to 3 show the results obtained by using the test pieces obtained above and the evaluation methods (1) to (5) above.

[0096] [Table 1]

[0097] [Table 2]

[0098] [Table 3]

[0099] In Tables 1 to 3, the blocked polyisocyanate (A) is BI 7960 is a blocked polyisocyanate compound of a 1,6-hexamethylene diisocyanate derivative 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 refers to a blocked polyisocyanate compound of a 1,6-hexamethylene diisocyanate derivative and 3,5-dimethylpyrazole (trade name: "TRIXENE BI 7982", manufactured by LANXESS, active ingredient 70% by mass, isocyanate content in the product 10.20%).

[0100] In Tables 1 to 3, the monomers (B-1) to (B-4) are: DMAA is N,N-dimethylacrylamide; DEAA, N,N-diethylacrylamide; IPAA, N-isopropylacrylamide; HEA is 2-hydroxyethyl acrylate (hydroxyl value 483.2 mg KOH / g); HEMA is 2-hydroxyethyl methacrylate (hydroxyl value 431.2 mg KOH / g); HEAA is 2-hydroxyethylacrylamide (hydroxyl value 487.4 mg KOH / g); HBA is 4-hydroxybutyl acrylate (hydroxyl value 389.1 mg KOH / g); RUVA-93 is 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (trade name: "RUVA-93", manufactured by Otsuka Chemical Co., Ltd.); CHA is cyclohexyl acrylate; LA indicates lauryl acrylate;

[0101] In Tables 1 to 3, colloidal silica (C) is ST-OXS is a water-dispersed silica sol with an average particle size of 4 to 6 nm (trade name: "Snowtex OXS", manufactured by Nissan Chemical Industries, Ltd., active ingredient 10% by weight); ST-O is a water-dispersed silica sol with an average particle size of 10 to 15 nm (trade name: "Snowtex O", manufactured by Nissan Chemical Industries, Ltd., active ingredient 20% by weight); IPA-ST is an IPA-dispersed silica sol with an average particle size of 10 to 15 nm ("Product name: IPA-ST", manufactured by Nissan Chemical Industries, Ltd., active ingredient 30% by weight); ST-OL refers to a water-dispersed silica sol having an average particle size of 40 to 50 nm (trade name: Snowtex OL, manufactured by Nissan Chemical Industries, Ltd., active ingredient 20% by weight).

[0102] In Tables 1 to 3, surfactant (D) is F100 is a fluorine-containing anionic surfactant (trade name: "Ftergent 100", manufactured by Neos Co., Ltd.); Lipoquat R refers to ricinoleamidopropylethyldimonium ethosulfate (trade name: "Lipoquat R", manufactured by VANTAGE Specialty Ingredients, Inc.).

[0103] In Tables 1 to 3, the leveling agents are BYK-333 refers to polyether-modified polydimethylsiloxane (trade name: "BYK-333", manufactured by BYK-Chemie).

[0104] In Table 3, other additives include: Tinuvin 400 refers to a mixture of 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (trade name: "Tinuvin 400", manufactured by BASF, active ingredient 85% by weight).

[0105] As shown in Tables 1 and 2, the antifogging agent compositions of Examples 1 to 25 can form antifogging coating films that are excellent in transparency, antifogging performance, scratch resistance, water resistance, and weather resistance.

[0106] On the other hand, as shown in Table 3, in Comparative Example 1, the absence of blocked polyisocyanate (A) resulted in decreased scratch resistance and water resistance. Furthermore, the absence of crosslinking resulted in the anti-fog coating film dissolving in the anti-fog performance and weather resistance tests. In Comparative Example 2, the absence of monomer (B-1) in polyol (B) resulted in decreased anti-fog performance. In Comparative Example 3, the absence of monomer (B-2) in polyol (B) resulted in decreased scratch resistance and water resistance. Furthermore, the absence of crosslinking resulted in the anti-fog coating film dissolving in the anti-fog performance and weather resistance tests. In Comparative Example 4, the absence of monomer (B-3) in polyol (B) resulted in decreased transparency and weather resistance. In Comparative Example 5, Tinuvin 400 was added as a UVA to the composition of Comparative Example 4, and although weather resistance was improved, transparency was insufficient. In Comparative Example 6, the absence of monomer (B-4) in polyol (B) resulted in decreased transparency. In Comparative Example 7, the scratch resistance was reduced because colloidal silica (C) was not contained.

Claims

1. A composition comprising a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D), The polyol (B) is represented by the general formula (1): 【Chemistry 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, General formula (2): 【Chemistry 2】 (In general formula (2), R ４ is a hydrogen atom or a methyl group, and R ５ is a linear or branched alkylene group having from 2 to 6 carbon atoms, and X is an oxygen atom or —NH—; General formula (3): 【Transformation 3】 (In general formula (3), R ６ is a hydrogen atom or a methyl group, and R ７ is an ultraviolet absorbing group; General formula (4): 【Chemistry 4】 (In general formula (4), R ８ is a hydrogen atom or a methyl group, and R ９ is a linear, branched, or cyclic hydrocarbon group having 1 to 22 carbon atoms.

2. In the general formula (3), R ７ 2. The antifogging agent composition according to claim 1, wherein is a benzotriazole-based ultraviolet absorbing group or a triazine-based ultraviolet absorbing group.

3. 3. The anti-fogging agent composition according to claim 1, wherein the blocked polyisocyanate (A) is a blocked polyisocyanate compound obtained by reacting at least one polyisocyanate compound selected from the group consisting of diisocyanates and derivatives thereof with a thermally dissociable blocking agent, and the blocking agent is a pyrazole or an oxime.

4. 4. The antifogging agent composition according to claim 1, wherein the blocked polyisocyanate (A) is contained in an amount of 10 parts by weight or more and 90 parts by weight or less, the colloidal silica (C) is contained in an amount of 5 parts by weight or more and 800 parts by weight or less, and the surfactant (D) is contained in an amount of 1 part by weight or more and 35 parts by weight or less, relative to 100 parts by weight of the polyol (B).

5. An anti-fogging article having an anti-fogging coating film formed from the anti-fogging agent composition according to any one of claims 1 to 4.

Images