Anti-fogging agent composition, anti-fogging article having anti-fogging coating film

Abstract

To provide an antifogging agent composition capable of forming an antifogging coating film which maintains antifogging performance, scratch resistance, water resistance, weather resistance, initial transparency and transparency over a long period of time.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 blocked polyisocyanate (A) is a (meth)acrylate copolymer obtained from a monomer mixture containing a monomer (A-1) represented by the general formula (1), a monomer (A-2) represented by the general formula (2) and a monomer (A-3) represented by the general formula (3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antifogging agent composition and an antifogging article having an antifogging coating film. [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 mixture of 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 4).

[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. 2021 / 182331 [Patent Document 2] Japanese Patent Publication No. 2020-164842 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-7677 [Patent Document 4] Japanese Patent Application Laid-Open No. 2008-308661 [Patent Document 5] 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-fog coating film 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, and the ability to maintain transparency over a long period of time is required. Furthermore, depending on the usage environment (e.g., when used outdoors for a long period of time), weather resistance is also required for the anti-fog coating film to maintain its aesthetic appearance for a longer period of time.

[0008] The anti-fog coating films disclosed in Patent Documents 1 and 2 exhibit good initial transparency by increasing the compatibility between the copolymers constituting the anti-fog coating film and colloidal silica. However, due to the low crosslink density of the anti-fog coating film, there is concern that the scratch resistance may be insufficient depending on the application.

[0009] The anti-fog coating films disclosed in Patent Documents 3 and 4 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 4 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 4, a method of adding an ultraviolet absorber (UVA) as described in Patent Document 5 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] Furthermore, the anti-fog coating films disclosed in Patent Documents 1 to 4 may experience progressive whitening of the anti-fog coating film over time due to bleed-out of surfactants, and may not be able to maintain transparency over long periods of time.

[0012] For the reasons described above, none of the anti-fog coating films of the prior art has, in addition to anti-fog performance, all of the coating film performances required under various usage environments, namely scratch resistance, water resistance, weather resistance, initial transparency, and the ability to maintain transparency over a long period of time.

[0013] 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 has antifogging performance, scratch resistance, water resistance, weather resistance, initial transparency, and maintains transparency over a long period of time. [Means for solving the problem]

[0014] 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 blocked polyisocyanate (A) 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 3are 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 R 5 is a residue derived from a blocking agent.) 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. The present invention relates to an antifogging agent composition which is a (meth)acrylate copolymer obtained from a monomer mixture containing a monomer (A-3) represented by the formula:

[0015] 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]

[0016] In the present invention, the following mechanism of action is presumed.

[0017] The anti-fog agent composition of the present invention contains a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D). Because the blocked polyisocyanate (A) contains the monomers (A-1) to (A-3), the anti-fog performance of the anti-fog coating film is primarily due to the properties of the monomer (A-1), the scratch resistance and water resistance of the anti-fog coating film are primarily due to the properties of the monomer (A-2), the weather resistance of the anti-fog coating film is primarily due to the properties of the monomer (A-3), and the compatibility between the blocked polyisocyanate (A) and the colloidal silica (C) is enhanced, thereby achieving the initial transparency of the anti-fog coating film. Furthermore, bleed-out of the surfactant can be suppressed, thereby maintaining transparency over a long period of time. Furthermore, crosslinking of the anti-fog coating film is primarily due to the properties of the monomer (A-2) and the polyol (B). Furthermore, since the antifogging agent composition of the present invention contains the 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

[0018] The antifogging agent composition of the present invention contains a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D).

[0019] <Blocked polyisocyanate (A)> The blocked polyisocyanate (A) of the present invention is a (meth)acrylate copolymer obtained from a monomer mixture, and the monomer mixture contains at least the following monomers (A-1) to (A-3):

[0020] <Monomer (A-1)> The monomer (A-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 3are independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0021] The monomer (A-1) mainly has the function of enhancing the anti-fogging performance of the anti-fogging coating film.

[0022] Examples of the monomer (A-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 selected from R 2 and R 3 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably N,N-dimethyl(meth)acrylamide or N,N-diethyl(meth)acrylamide. The monomer (A-1) may be used alone or in combination of two or more kinds.

[0023] <Monomer (A-2)> The monomer (A-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 residue derived from a blocking agent.

[0024] The monomer (A-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 polyol (B), resulting in enhanced scratch resistance and water resistance.

[0025] In the general formula (2), examples of the residue derived from the blocking agent 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; 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 low-temperature and short-term curing, the residue derived from the blocking agent is preferably a pyrazole, oxime, or dialkyl malonate, and more preferably dimethylpyrazole, diethylpyrazole, acetoxime, methyl ethyl ketoxime, dimethyl malonate, or diethyl malonate. The monomer (A-2) may be used alone or in combination of two or more.

[0026] <Monomer (A-3)> The monomer (A-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.

[0027] The monomer (A-3) primarily functions to enhance the transparency and weather resistance of the anti-fog coating film. While the mechanism of action is unclear, the inclusion of an ultraviolet-absorbing group derived from the monomer (A-3) in the structure of the blocked polyisocyanate (A) improves the compatibility between the blocked polyisocyanate (A) and the colloidal silica (C), thereby enhancing initial transparency and further suppressing surfactant bleed-out, thereby maintaining transparency over a long period of time. Furthermore, copolymerization of the monomer (A-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.

[0028] 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 weather resistance and initial transparency and maintaining transparency over a long period of time. The monomer (A-3) may be used alone or in combination of two or more.

[0029] Specific examples of the monomer (A-3) include those 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 linear or branched alkylene group having 1 to 8 carbon atoms, a benzotriazole derivative 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 2 to 11 carbon atoms, and R 12are independently a hydrogen atom or a methyl group.) A triazine derivative represented by general formula (6): [ka] (In general formula (6), R 13 is a hydrogen atom or a methyl group, and R 14 is a linear alkylene group having 1 or 2 carbon atoms, and R 15 is a hydroxy group or a methoxy group.

[0030] Examples of the benzotriazole derivative represented by the general formula (4) 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.

[0031] Examples of the triazine derivative represented by the general formula (5) 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.

[0032] Examples of the hydroxybenzophenone derivative represented by the general formula (6) 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.

[0033] The monomer mixture may contain, as monomers other than the monomers (A-1) to (A-3), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, Alkyl acrylic monomers such as acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, and n-lauryl acrylate; aromatic vinyl monomers such as styrene, vinyl toluene, and α-methylstyrene; aromatic acrylic monomers such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; (meth)acryloyloxyethyl trimethylammonium chloride, (meth)acryloylaminopropyl trimethylammonium chloride Vinyl monomers containing quaternary ammonium salts such as methyl methacrylate; acrylic monomers containing light-stable groups such as 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate; alicyclic acrylic monomers such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, and maleic acid. and their ammonium salts, organic amine salts, and alkali metal salts; sulfonic acid group-containing vinyl monomers such as styrene sulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, and 3-sulfopropyl (meth)acrylate, and their ammonium salts, organic amine salts, and alkali metal salts; phosphate group-containing vinyl monomers such as 2-(meth)acryloyloxyethyl acid phosphate, and their ammonium salts, organic amine salts, and alkali metal salts;Examples of suitable monomers include bifunctional acrylic 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; 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, diacetone (meth)acrylamide, and the like.

[0034] The proportion of the monomer (A-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.

[0035] The proportion of the monomer (A-2) in the monomer mixture is preferably 15% by weight or more and 60% by weight or less, more preferably 20% by weight or more and even more preferably 25% by weight or more from the viewpoint of improving scratch resistance and water resistance, and more preferably 50% by weight or less and even more preferably 40% by weight or less from the viewpoint of improving anti-fogging performance.

[0036] The proportion of the monomer (A-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 viewpoints of improving weather resistance and initial transparency and maintaining transparency over a long period of time, 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.

[0037] <Method for producing blocked polyisocyanate (A)> The blocked polyisocyanate (A) of the present invention is a copolymer obtained by copolymerizing the above-mentioned monomer mixture. The structure of the blocked polyisocyanate (A) 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, can be used to obtain the blocked polyisocyanate (A). 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 antifogging agent composition can be used directly after polymerization.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] The weight average molecular weight (Mw) of the blocked polyisocyanate (A) is preferably 3,000 or more, more preferably 5,000 or more, from the viewpoint of imparting water resistance to the anti-fog coating film, and is preferably 200,000 or less, more preferably 150,000 or less, from the viewpoint of improving the coatability and handleability of the anti-fog agent composition.

[0043] The weight average molecular weight (Mw) of the blocked polyisocyanate (A) 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

[0044] <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 reacting with the blocked polyisocyanate (A) to crosslink molecules.

[0045] The polyol (B) is preferably a low-molecular-weight polyol (B-1) from the viewpoint of improving scratch resistance, and more preferably a combination of the low-molecular-weight polyol (B-1) and an acrylic polyol (B-2) from the viewpoint of suppressing bleed-out of the surfactant and maintaining transparency over a long period of time.

[0046] Examples of the low molecular weight polyol (B-1) include alkylene polyols such as ethanediol, propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, methylpropanediol, neopentyl glycol, butylethylpropanediol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, and tris(2-hydroxyethyl) isocyanurate; alkylene polyols such as ethanediol and propanediol, and carboxylic acids such as maleic acid and phthalic acid, or caprolactam. Examples of suitable low-molecular-weight polyols include polyester polyols obtained by reacting alkylene carbonates such as ethylene carbonate or trimethylene carbonate with alkylene polyols such as ethanediol or propanediol; polycarbonate polyols obtained by reacting alkylene polyols such as glycerin or pentaerythritol with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran; and polyurethane polyols obtained by reacting alkylene polyols such as ethanediol or propanediol with polyisocyanates. The polyol (B-1) is preferably an alkylene polyol, polyester polyol, polycarbonate polyol, or polyurethane polyol from the viewpoint of improving scratch resistance and weather resistance. The low-molecular-weight polyol (B-1) may be used alone or in combination of two or more.

[0047] Commercially available low molecular weight polyols (B-1) include, for example, trade names: "Placcel 205," "Placcel 208," "Placcel 210," "Placcel 303," "Placcel 305," "Placcel 308," "Placcel 309," "Placcel 312," "Placcel 320," "Placcel 410," "Placcel 616T," and "Placcel CD205PL" (all manufactured by Daicel Corporation), trade names: "Duranol T5650E," "Duranol T5650E," "Duranol G3450J," and "Duranol T4671" (all manufactured by Asahi Kasei Corporation), trade names: "Exenol 420," "Exenol 430," "Exenol 720," and "Exenol 1030" (all manufactured by AGC Corporation), and trade names: "FLEXOREZ UD-320" and "FLEXOREZ UD-320-100," "FLEXOREZ188," and "FLEXOREZ XM-366" (all manufactured by Kusumoto Chemicals Co., Ltd.).

[0048] The acrylic polyol (B-2) is preferably a (meth)acrylate polymer containing a hydroxyl group-containing (meth)acrylate monomer or a (meth)acrylate copolymer containing a hydroxyl group-containing (meth)acrylate monomer. The acrylic polyol (B-2) may be used alone or in combination of two or more.

[0049] From the viewpoint of maintaining transparency for a long period of time, the acrylic polyol (B-2) is a polyol represented by the general formula (7): [ka] (In general formula (7), R 16 is a hydrogen atom or a methyl group, and R 17 and R 18 are independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and a monomer (b-1) represented by general formula (8): [ka] (In general formula (8), R 19is a hydrogen atom or a methyl group, and R 20 is a straight or branched chain having 2 to 4 carbon atoms.) and a monomer (b-2) represented by general formula (9): [ka] (In general formula (9), R 21 is a hydrogen atom or a methyl group, and R 22 is a straight-chain, branched-chain or cyclic alkyl group having 1 to 12 carbon atoms.

[0050] 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. The monomer (b-1) is selected from the group consisting of R 17 and R 18 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, 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.

[0051] Examples of the monomer (b-2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. From the viewpoint of improving scratch resistance, the monomer (b-2) is preferably 2-hydroxyethyl (meth)acrylate. The monomer (b-2) may be used alone or in combination of two or more.

[0052] Examples of the monomer (b-3) include alkyl acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, and n-lauryl acrylate; and alicyclic acrylic monomers such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. From the viewpoint of improving water resistance, the monomer (b-3) is preferably a methyl acrylate having a substituent selected from the group consisting of R 22 is preferably a linear, branched or cyclic alkyl group having a carbon number of 2 to 8. The monomer (b-3) may be used alone or in combination of two or more kinds.

[0053] The monomer mixture containing the monomer (b-1), the monomer (b-2) and the monomer (b-3) may contain, as other monomers than the monomers (b-1) to (b-3), aromatic vinyl monomers such as styrene, vinyltoluene and α-methylstyrene; aromatic acrylic monomers such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; vinyl monomers containing quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride and (meth)acryloylaminopropyltrimethylammonium chloride. Monomers: acrylic monomers containing a light-stable group such as 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate; acrylic monomers containing a UV-absorbing group such as [3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]methyl (meth)acrylate and 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate; carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, and maleic acid, and their derivatives. Ammonium salts, organic amine salts, alkali metal salts; sulfonic acid group-containing vinyl monomers such as styrene sulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth)acrylate, and their ammonium salts, organic amine salts, alkali metal salts; phosphate group-containing vinyl monomers such as 2-(meth)acryloyloxyethyl acid phosphate, and their ammonium salts, organic amine salts, alkali metal salts; 1,6-hexanediol di(meth)acrylate Bifunctional acrylic monomers such as 1,9-nonanediol (meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and glycerin di(meth)acrylate; 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, diacetone (meth)acrylamide, and dicyclopentenyloxyethyl (meth)acrylate can be used.

[0054] The polyol (B) is preferably 5 parts by weight or more and 250 parts by weight or less relative to 100 parts by weight of the blocked polyisocyanate (A). From the viewpoint of improving scratch resistance and water resistance, the polyol (B) 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 blocked polyisocyanate (A). From the viewpoint of improving anti-fogging performance, the polyol (B) is more preferably 80 parts by weight or less, and even more preferably 50 parts by weight or less. When two or more types of polyol (B) are used in combination, the total weight of the polyols may be used as the weight of the polyol (B).

[0055] Furthermore, the blocked polyisocyanate (A) and the polyol (B) preferably have an NCO equivalent / OH equivalent ratio (hereinafter referred to as NCO / OH ratio) of the isocyanate equivalent (NCO equivalent) generated after deblocking of the blocking agent of the blocked isocyanate group contained in the blocked polyisocyanate (A) to the hydroxyl group equivalent (OH equivalent) of the polyol (B) in the range of 0.2 to 3.5. From the viewpoint of improving water resistance, the NCO / OH ratio is more preferably 0.3 or more, and even more preferably 0.5 or more. When two or more types of polyol (B) are used in combination, the weighted average of the OH equivalents of the respective polyols may be used as the OH equivalent of the polyol (B).

[0056] When the low-molecular-weight polyol (B-1) and the acrylic polyol (B-2) are used in combination, the weight ratio thereof ((B-1) / (B-2) ratio) is preferably 0.25 or more, more preferably 0.5 or more, from the viewpoint of improving scratch resistance, and is preferably 4.0 or less, more preferably 3.5 or less, from the viewpoint of maintaining transparency over a long period of time.

[0057] The molecular weight of the low-molecular-weight polyol (B-1) is preferably 2000 or less. From the viewpoint of improving scratch resistance, the molecular weight of the low-molecular-weight polyol (B-1) is more preferably 1800 or less, and even more preferably 1500 or less. The hydroxyl value of the low-molecular-weight polyol (B-1) is preferably 100 mgKOH / g or more and 800 mgKOH / g or less. From the viewpoint of improving scratch resistance, the hydroxyl value of the low-molecular-weight polyol (B-1) is more preferably 120 mgKOH / g or more, and even more preferably 150 mgKOH / g or more. And from the viewpoint of improving anti-fogging performance, it is more preferably 600 mgKOH / g or less, and even more preferably 500 mgKOH / g or less.

[0058] The weight average molecular weight (Mw) of the acrylic polyol (B-2) is preferably 3000 or more and 200,000 or less.The hydroxyl value of the acrylic polyol (B-2) is preferably 50 mgKOH / g or more and 350 mgKOH / g or less.

[0059] The proportion of the monomer (b-1) is preferably 30% by weight or more and 80% by weight or less, based on 100 parts by weight of the total of the monomers (b-1), (b-2), and (b-3). The proportion of the monomer (b-1) is more preferably 35% by weight or more, based on 100 parts by weight of the total of the monomers (b-1), (b-2), and (b-3), from the viewpoints of improving anti-fogging performance and maintaining transparency over a long period of time, and more preferably 70% by weight or less, from the viewpoints of improving scratch resistance and water resistance.

[0060] The proportion of the (b-2) is preferably 10% by weight or more and 60% by weight or less, based on 100 parts by weight of the total of the monomers (b-1), (b-2), and (b-3). The proportion of the (b-2) is more preferably 15% by weight or more, based on 100 parts by weight of the total of the monomers (b-1), (b-2), and (b-3), from the viewpoint of improving scratch resistance and water resistance, and more preferably 50% by weight or less, from the viewpoint of improving anti-fogging performance.

[0061] The proportion of the monomer (b-3) is preferably 5% by weight or more and 40% by weight or less, based on 100 parts by weight of the total of the monomers (b-1), (b-2), and (b-3). The proportion of the monomer (b-3) is more preferably 10% by weight or more, based on 100 parts by weight of the total of the monomers (b-1), (b-2), and (b-3), from the viewpoint of improving water resistance, and is preferably 35% by weight or less, from the viewpoint of improving anti-fogging performance.

[0062] <Method for producing acrylic polyol (B-2)> The acrylic polyol (B-2) of the present invention is a polymer obtained by polymerizing a hydroxyl group-containing (meth)acrylate monomer or a copolymer obtained by copolymerizing a (meth)acrylate monomer containing a hydroxyl group-containing (meth)acrylate monomer. The copolymer structure of the acrylic polyol (B-2) may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graphene 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, can be used to obtain the acrylic polyol (B-2). However, radical polymerization is preferred from the viewpoints of ease of industrial productivity and a wide range of performance aspects. 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] The weight average molecular weight (Mw) of the acrylic polyol (B-2) 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

[0068] <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.

[0069] Examples of commercially available colloidal silica (C) include those 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.).

[0070] 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 the initial 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 initial transparency of the anti-fog coating film, the particulate shape is preferred.

[0071] The amount of the colloidal silica (C) is preferably 20 parts by weight or more and 800 parts by weight or less relative to 100 parts by weight of the blocked polyisocyanate (A). From the viewpoint of improving scratch resistance and water resistance, the amount of the colloidal silica (C) is more preferably 50 parts by weight or more, and even more preferably 70 parts by weight or more relative to 100 parts by weight of the blocked polyisocyanate (A), and from the viewpoint of improving initial transparency, the amount is more preferably 500 parts by weight or less, and even more preferably 300 parts by weight or less.

[0072] <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.

[0073] 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.

[0074] 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.

[0075] Examples of the nonionic surfactant include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; Examples of suitable surfactants include 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; fluorine-containing nonionic surfactants such as perfluoroalkylamine oxide, perfluoroalkenylamine oxide, perfluoroalkylethylene oxide adduct, perfluoroalkenylethylene oxide adduct, 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, and cellulose ethers. The nonionic surfactants may be used alone or in combination of two or more.

[0076] 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.

[0077] From the viewpoint that good anti-fogging performance can be obtained with a relatively small amount of surfactant (D), it is preferable to use an anionic surfactant alone, a combination of an anionic surfactant and a cationic surfactant, or a combination of an anionic surfactant and an amphoteric surfactant. In particular, when the anionic surfactant is a fluorine-containing anionic surfactant, it can more effectively reduce the surface tension of the anti-fogging coating film with respect to water, thereby achieving higher anti-fogging performance.

[0078] 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 blocked polyisocyanate (A). 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 blocked polyisocyanate (A). From the viewpoint of improving initial transparency, the surfactant (D) is more preferably 30 parts by weight or less and even more preferably 20 parts by weight or less.

[0079] The antifogging agent composition of the present invention may contain a dilution solvent from the viewpoint of improving coating workability.

[0080] 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 blocked polyisocyanate (A). 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.

[0081] 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.

[0082] Examples of the curing catalyst include fatty acid alkali metal salts 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 fluorine alkyl fatty acid sodium 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, 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.

[0083] 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).

[0084] 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.

[0085] Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyether-modified polydimethylpolysiloxane, polyether macromer-modified acrylate, acrylic polymer, and acrylic silicone polymer.

[0086] Commercially available leveling agents include, for example, 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", "BYK-370", "BYK-377", "BYK-378", "BYK-3455", and "BYK-3560" (all manufactured by BYK-Chemie Co., Ltd.). Examples of such leveling agents include product names such as "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.), and product names such as "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 leveling agent may be used, or two or more types may be used in combination.

[0087] 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 blocked polyisocyanate (A).

[0088] 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 blocked polyisocyanate (A).

[0089] <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.

[0090] 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.

[0091] 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.

[0092] The drying is usually carried out at a temperature of 20 to 50° C. for 0.5 to 10 minutes.

[0093] 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.

[0094] 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.

[0095] 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]

[0096] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0097] Example 1 <Production of Blocked Polyisocyanate (A)> A reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube was charged with 119 parts by weight of 3-methoxy-3-methylbutanol 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 (A-1), 30 parts by weight of dimethylpyrazole-blocked 2-isocyanatoethyl acrylate (trade name: "Karends AOI-BP", manufactured by Showa Denko K.K.) as monomer (A-2), 10 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 (A-3), and 15 parts by weight of 3-methoxy-3-methylbutanol, 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 10 parts by weight of 3-methoxy-3-methylbutanol were added dropwise over 3 hours. After the dropwise addition was completed, the mixture was stirred for 30 minutes, and then a solution of 0.29 parts by weight of Perhexyl ND dissolved in 4.0 parts by weight of 3-methoxy-3-methylbutanol was added dropwise over 30 minutes. After the dropwise addition was completed, the mixture was stirred for 1 hour and then cooled to produce a solution of blocked polyisocyanate (A). The weight-average molecular weight of the blocked polyisocyanate (A) was measured by gel permeation chromatography and found to be 30,000. The solids content of this blocked polyisocyanate (A) solution was 40.0%. The NCO equivalent of the blocked polyisocyanate (A) was calculated to be 237 × 100 / 30 = 790, based on the fact that 100 parts by weight of the blocked polyisocyanate (A) contained 30 parts by weight of AOI-BP (monomer (A-2)) and the molecular weight of AOI-BP was 237 g / mol.

[0098] <Production of Antifogging Agent Composition> The mixture was 250 parts by weight (solid content 40%) of the blocked polyisocyanate (A) obtained above, 30 parts by weight of polycaprolactone polyol (trade name: "Placcel 308", manufactured by Daicel Corporation) as polyol (B), 650 parts by weight of water-dispersed silica sol (trade name: "Snowtex O", manufactured by Nissan Chemical Industries, Ltd., active ingredient 20% by weight) as colloidal silica (C), 7.0 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 Co., Ltd.) as surfactant (D). An antifogging agent composition was prepared by mixing 4.0 parts by weight of BYK Ingredients, Inc. (as a curing catalyst), 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 Japan Co., Ltd.) (as a leveling agent), and 1,222 parts by weight of propylene glycol monomethyl ether (as a diluent). Since the average hydroxyl value (OHV) of PLACCEL 308 was 195, the OH equivalent of polyol (B) was calculated to be 56.1 (molecular weight of KOH) × 1,000 / 195 = 288. Furthermore, the NCO / OH ratio was calculated as follows: {Parts by weight of (A) (converted into active ingredient) / NCO equivalent of (A)} / {Parts by weight of (B) (converted into active ingredient) / OH equivalent of (B)}={100 / 790} / {30 / 288}=1.22. When two or more types of polyol (B) are used in combination, the weighted average of the hydroxyl values ​​of the individual polyols can be used to calculate the hydroxyl value of polyol (B).

[0099] <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.

[0100] The test pieces obtained above were used to carry out the evaluation methods (1) to (6) below, and the results are shown in Table 1.

[0101] <(1) 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 steam 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.

[0102] <(2) 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.

[0103] <(3) 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.

[0104] <(4) 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

[0105] <(5) Initial Transparency Assessment> 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

[0106] <(6) Long-term Transparency Assessment> The test piece was left to stand at 80°C and 85% RH for 240 hours, and then at room temperature for 24 hours. The haze value of the anti-fog coating film appearance 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 problem, B+ is preferable, and A is more preferable. 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

[0107] In the production of the antifogging agent composition, when two or more types of polyol (B) were used in combination, the acrylic polyol (B-2) was produced by the following method.

[0108] <Synthesis example B-2-1> <Production of Acrylic Polyol (B-2)> A reaction vessel equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser was charged with 287.1 parts by weight of propylene glycol monomethyl ether as the polymerization solvent and heated to 75°C while blowing in nitrogen gas. Next, a solution containing 50 parts by weight of N,N-dimethylacrylamide as monomer (b-1), 25 parts by weight of 2-hydroxyethyl acrylate as monomer (b-2), and 25 parts by weight of cyclohexyl acrylate as monomer (b-3) was added dropwise over 3 hours, along with a solution of 0.6 parts by weight of Perhexyl ND as a radical polymerization initiator dissolved in 10 parts by weight of propylene glycol monomethyl ether. After the 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 2.0 parts by weight of propylene glycol monomethyl ether was added dropwise over 30 minutes. After the addition was completed, the mixture was stirred for 1 hour and then cooled to produce a solution of acrylic polyol (B-2). The weight-average molecular weight of the acrylic polyol (B-2) was measured by gel permeation chromatography and found to be 12,000. The solids content of the acrylic polyol (B-2) solution was 25.0%. Since 25 parts by weight of HEA (monomer (b-2)) was contained in 100 parts by weight of the acrylic polyol (B-2) and the molecular weight of HEA was 116 g / mol, the hydroxyl value of the acrylic polyol (B-2) was calculated as 1 (number of OH groups in HEA) / 116 × 56.1 (molecular weight of KOH) × 1000 × 25 / 100 = 121 mg KOH / g. The OH equivalent of the acrylic polyol (B-2) was calculated as 116 × 100 / 25 = 464.

[0109] <Synthesis examples B-2-2~B-2-4> In each synthesis example, solutions of acrylic polyol (B-2) of Synthesis Examples B-2-2 to B-2-4 were produced in the same manner as in Synthesis Example B-2-1, except that the monomers in Synthesis Example B-2-1 were changed to the monomers and their blending ratios shown in Table 1.

[0110] [Table 1]

[0111] <Examples 2 to 31 and Comparative Examples 1 to 6> <Production of anti-fogging agent composition and fabrication of anti-fogging article> Anti-fog agent compositions of Examples 2 to 31 and Comparative Examples 1 to 6 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 5. Furthermore, anti-fog articles (test pieces) having the anti-fog coating films of Examples 2 to 31 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1.

[0112] Tables 2 to 5 show the results obtained by using the test pieces obtained above and the evaluation methods (1) to (6) above.

[0113] [Table 2]

[0114] [Table 3]

[0115] [Table 4]

[0116] [Table 5]

[0117] In Tables 1 to 5, the monomers (A-1) to (A-3) and the monomers (b-1) to (b-3) are: DMAA is N,N-dimethylacrylamide; DEAA, N,N-diethylacrylamide; NIPAM, Ni-propylacrylamide; HEA, 2-hydroxyethyl acrylate; CHA is cyclohexyl acrylate; AOI-BP: dimethylpyrazole-blocked 2-isocyanatoethyl acrylate (trade name: "Karenz AOI-BP", manufactured by Showa Denko K.K., molecular weight: 237); MOI-BP is dimethylpyrazole-blocked 2-isocyanatoethyl methacrylate (trade name: "Karends MOI-BP", manufactured by Showa Denko K.K., molecular weight: 251); MOI-BM is methyl ethyl ketone oxime-blocked 2-isocyanatoethyl acrylate (trade name: "Karends MOI-BM", manufactured by Showa Denko K.K., molecular weight: 242); RUVA-93 refers to 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (trade name: "RUVA-93", manufactured by Otsuka Chemical Co., Ltd.);

[0118] In Tables 2 to 5, the polyol (B) and the low molecular weight polyol (B-1) are: UD-320 is a urethane diol (trade name: FLEXOREZ UD-320, manufactured by Kusumoto Chemicals Co., Ltd., active ingredient 82% by weight, OHV 350 mg KOH / g, molecular weight 500, number of functional groups 2); PCL308 is polycaprolactone polyol (trade name: "Placcel 308", manufactured by Daicel Corporation, OHV: 190 to 200 mg KOH / g, molecular weight: 850, number of functional groups: 3); PCL312 is polycaprolactone polyol (trade name: "Placcel 312", manufactured by Daicel Corporation, OHV: 130-140 mg KOH / g, molecular weight: 1250, number of functional groups: 3); PCL410 refers to polycaprolactone polyol (trade name: "Placcel 410", manufactured by Daicel Corporation, OHV: 216 to 232 mg KOH / g, molecular weight: 1000, number of functional groups: 4);

[0119] In Tables 2 to 5, 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).

[0120] In Tables 2 to 5, 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.).

[0121] In Tables 2 to 5, the leveling agents are BYK-333 refers to polyether-modified polydimethylsiloxane (trade name: "BYK-333", manufactured by BYK Japan Co., Ltd.).

[0122] In Table 5, 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 Japan Ltd., active ingredient 85% by weight).

[0123] As shown in Tables 2 to 4, the antifogging agent compositions of Examples 1 to 31 can form antifogging coating films that have antifogging performance, scratch resistance, water resistance, weather resistance, initial transparency, and maintain transparency over a long period of time.

[0124] On the other hand, as shown in Table 5, in Comparative Example 1, the blocked polyisocyanate (A) did not contain the monomer (A-1), resulting in a decrease in anti-fog performance. In Comparative Example 2, the blocked polyisocyanate (A) did not contain the monomer (A-2), resulting in a decrease in scratch resistance and water resistance. Furthermore, the lack of crosslinking caused the anti-fog coating film to dissolve in the anti-fog performance and weather resistance tests. In Comparative Example 3, the blocked polyisocyanate (A) did not contain the monomer (A-3), resulting in a decrease in weather resistance and initial and aging transparency. In Comparative Example 4, Tinuvin 400 was added as a UVA to the composition of Comparative Example 3, and although the weather resistance improved, the initial and aging transparency were insufficient. In Comparative Example 5, the blocked polyisocyanate (B) did not contain the polyol (B), resulting in a decrease in scratch resistance and water resistance. Furthermore, the lack of crosslinking caused the anti-fog coating film to dissolve in the anti-fog performance and weather resistance tests. In Comparative Example 6, the colloidal silica (C) was not contained, and therefore the scratch resistance was reduced.

Claims

1. A composition comprising a blocked polyisocyanate (A), a polyol (B), colloidal silica (C), and a surfactant (D), The blocked polyisocyanate (A) 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 residue derived from a blocking agent, and 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.

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

3. 3. The antifogging agent composition according to claim 1, wherein the polyol (B) is 5 parts by weight or more and 250 parts by weight or less, the colloidal silica (C) is 20 parts by weight or more and 800 parts by weight or less, and the surfactant (D) is 1 part by weight or more and 35 parts by weight or less, relative to 100 parts by weight of the blocked polyisocyanate (A).

4. 4. The antifogging agent composition according to claim 1, wherein the polyol (B) comprises a low-molecular-weight polyol (B-1) and an acrylic polyol (B-2), and the low-molecular-weight polyol (B-1) has a molecular weight of 2,000 or less and a hydroxyl value of 100 mgKOH / g or more and 800 mgKOH / g or less.

5. The acrylic polyol (B-2) is represented by the general formula (4): 【Chemistry 4】 (In general formula (4), R ８ is a hydrogen atom or a methyl group, and R ９ and R １０ are independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; General formula (5): 【Transformation 5】 (In general formula (5), R １１ is a hydrogen atom or a methyl group, and R １２ is a straight or branched chain having 2 to 4 carbon atoms; and General formula (6): 【Transformation 6】 (In general formula (6), R １３ is a hydrogen atom or a methyl group, and R １４ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.

6. 6. The antifogging agent composition according to claim 4, wherein the weight ratio of the low-molecular-weight polyol (B-1) to the acrylic polyol (B-2) ((B-1) / (B-2) ratio) is 0.25 or more and 4.0 or less.

7. 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 6.

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