Photocurable composition, cured product thereof, and member

Abstract

To provide a photocurable composition that can be applied to an interior building material, a water-related member, and the like, and can improve poor appearance of a cured coating film more than before; a cured product of the photocurable composition; and a member comprising the cured product.SOLUTION: A photocurable composition comprises a curable component and a photopolymerization initiator, wherein the curable component includes component (A): a (meth)acrylate monomer having two or more functional groups, component (B): an acid-modified (meth)acrylate monomer and / or a hydroxy group-containing (meth)acrylamide, and component (C): a (meth)acrylic-modified sulfonate.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present embodiment relates to a photocurable composition, a cured product thereof, and a member. [Background technology]

[0002] 2. Description of the Related Art In the case of interior components, wet area components and the like, the surfaces of coating films on the components have been rendered hydrophilic by curing a curable composition with energy rays. [Patent Document 1] JP 2013-71118 A Summary of the Invention

[0003] Therefore, an object of the present disclosure is to provide a photocurable composition that can be applied to interior components, water-related components, and the like, and that can further improve poor appearance of a cured coating film, a cured product thereof, and a component comprising the cured product.

[0004] As a result of extensive investigations, the present inventors have found that in a photocurable composition, (A) component: a difunctional or higher (meth)acrylate monomer, (B) component: an acid-modified (meth)acrylate monomer and / or a hydroxyl group-containing (meth)acrylamide, and (C) component: (meth)acrylic modified sulfonate, It has been found that the above-mentioned problems can be solved by using a curable component containing the following: Furthermore, this photocurable composition can impart hydrophilicity to a cured coating film without using fluorine or silicone, which are known to deteriorate anti-slip properties, or surfactants, which are known to deteriorate chemical resistance, and can therefore impart stain resistance, chemical resistance, anti-slip properties, and easy cleaning properties to the surface of the cured coating film, making it suitable for use in interior components, wet area components, etc. Furthermore, since this photocurable composition is capable of suppressing haze in the cured coating film (i.e., has high transparency), it can be widely used for decorative substrates used in interior components and water-related components. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] That is, this embodiment has the following aspects. [1] A composition comprising a curable component and a photopolymerization initiator, The curable component is (A) component: a difunctional or higher (meth)acrylate monomer, (B) component: an acid-modified (meth)acrylate monomer and / or a hydroxyl group-containing (meth)acrylamide, and (C) component: (meth)acrylic modified sulfonate, 1. A photocurable composition comprising: [2] The photocurable composition according to [1], wherein the component (A) contains a di- or higher functional hydroxyl group-containing (meth)acrylate monomer (a1). [3] The photocurable composition according to [1] or [2], wherein the curable component further contains a component (D): a monofunctional hydroxyl group-containing (meth)acrylate monomer. [4] The photocurable composition according to any one of [1] to [3], wherein the proportion of the component (B) based on the total amount of the curable components is 0.01 to 20 mass %. [5] The photocurable composition according to any one of [1] to [4], wherein the component (A) has an average number of functional groups of 2 to 4. [6] The photocurable composition according to any one of [1] to [5], wherein the component (B) contains an acid-modified (meth)acrylate monomer. [7] The photocurable composition according to any one of [1] to [6], wherein the hydroxyl group-containing (meth)acrylamide in the component (B) is hydroxyethylacrylamide. [8] A cured product of the photocurable composition according to any one of [1] to [7]. [9] A member comprising the cured product according to [8].

[10] The component described in [9], which is an interior component or a water-related component.

[0006] Conventional methods for imparting antifouling properties, chemical resistance, anti-slip properties, or easy cleaning properties are often accompanied by poor appearance of the cured coating film. According to the present embodiment, it is possible to provide a photocurable composition and a cured product thereof that can improve poor appearance of a cured coating film more than ever before, and a member including the cured product.

[0007] An embodiment of the present invention will be described in detail below. The present invention is not limited to the following embodiment, and can be modified as appropriate without impairing the effects of the present embodiment. Each configuration and their combinations in each embodiment are merely examples, and addition, omission, substitution, and other modifications of the configuration are possible as appropriate within the scope of the gist of the present embodiment. The present embodiment is not limited to the embodiments, but is limited only by the claims. Each feature disclosed herein may be combined with any other feature disclosed herein. In cases where a specific description given for one embodiment also applies to other embodiments, the description may be omitted in the other embodiments. In this embodiment, the expression "X to Y" for a numerical range means "X or more and Y or less."

[0008] [Photocurable composition] The first embodiment of this embodiment is as follows: Contains a curable component and a photopolymerization initiator, The curable component is (A) component: a difunctional or higher (meth)acrylate monomer, (B) component: an acid-modified (meth)acrylate monomer and / or a hydroxyl group-containing (meth)acrylamide, and (C) component: (meth)acrylic modified sulfonate, According to the first embodiment, it is possible to provide a photocurable composition which can improve poor appearance of a cured coating film more than ever before.

[0009] <Curing component> The photocurable composition according to the first embodiment is (A) component: a difunctional or higher (meth)acrylate monomer, (B) component: an acid-modified (meth)acrylate monomer and / or a hydroxyl group-containing (meth)acrylamide, and (C) component: (meth)acrylic modified sulfonate, The curable component comprises:

[0010] (Component (A): Difunctional or higher (meth)acrylate monomer) The curable component contains component (A): a di- or higher functional (meth)acrylate monomer. In the photocurable composition according to the first embodiment, the (meth)acrylate monomer as the component (A) may include both an acrylate and a methacrylate. In the photocurable composition according to the first embodiment, the (meth)acrylate monomer as the component (A) may be used either alone or in combination of two or more kinds. In the photocurable composition according to the first embodiment, the term "bifunctional or higher" refers to the average number of functional groups (average number of functional groups) contained in component (A) being 2 or more. In the photocurable composition according to the first embodiment, the term "functional group" refers to a photopolymerizable functional group. In one embodiment, the average number of functional groups of the component (A) may be 2 to 6, 2 to 5, 2 to 4, or 3 to 4. When the average number of functional groups is within the above range, the appearance finish of the cured coating film is more likely to be improved.

[0011] In one embodiment, the molecular weight (g / mol) of the component (A): di- or higher functional (meth)acrylate monomer is preferably 100-600, more preferably 150-600, even more preferably 150-500, and particularly preferably 150-400.

[0012] Among the above-mentioned (A) component: difunctional or higher (meth)acrylate monomers, non-limiting examples of difunctional (meth)acrylate monomers include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 4,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol tricyclodecane diacrylate, and dicyclopentanyl diacrylate.

[0013] Among the difunctional or higher functional (meth)acrylate monomers of component (A), non-limiting examples of trifunctional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, tris(2-acryloxyethyl)isocyanurate, and ε-caprolactone modified tris(2-acryloxyethyl)isocyanurate.

[0014] Among the difunctional or higher (meth)acrylate monomers of component (A) above, non-limiting examples of tetrafunctional (meth)acrylate monomers include trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and alkyl-modified dipentaerythritol tetra(meth)acrylate.

[0015] Among the difunctional or higher (meth)acrylate monomers of the component (A), non-limiting examples of pentafunctional (meth)acrylate monomers include dipentaerythritol penta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate.

[0016] Among the difunctional or higher functional (meth)acrylate monomers of the component (A), non-limiting examples of hexafunctional (meth)acrylate monomers include dipentaerythritol hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0017] In one embodiment, the component (A) is more preferably one or more difunctional or higher (meth)acrylate monomers selected from the group consisting of pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, and ethoxylated glycerin triacrylate.

[0018] The amount of component (A) in the photocurable composition according to the first embodiment may be 40 to 99.9 mass%, 50 to 99.9 mass%, 60 to 99.9 mass%, 70 to 99.9 mass%, 80 to 99.9 mass%, or 90 to 99.9 mass%, relative to 100 mass% of the total amount of the curable components.

[0019] In one embodiment, from the viewpoint of the finished appearance of the cured coating film, the component (A) preferably contains a difunctional or higher functional hydroxyl-containing (meth)acrylate monomer (a1). The number of hydroxyl groups in the hydroxyl-containing (meth)acrylate monomer (a1) is not particularly limited and may be 1 to 10 or 1 to 5. In one embodiment, the difunctional or higher hydroxyl group-containing (meth)acrylate monomer (a1) contained in the component (A) may use one type alone, or two or more types in combination. In one embodiment, the difunctional or higher hydroxyl group-containing (meth)acrylate monomer (a1) is preferably one or more difunctional or higher hydroxyl group-containing (meth)acrylate monomers selected from the group consisting of hydroxyl group-containing bifunctional (meth)acrylate compounds such as isocyanuric acid ethylene oxide modified diacrylate and glycerol epichlorohydrin modified 1,6-hexanediol diacrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, and other polyfunctional hydroxyl group-containing (meth)acrylate compounds such as trifunctional or higher hydroxyl group-containing (meth)acrylates. In one embodiment, the difunctional or higher hydroxyl group-containing (meth)acrylate monomer (a1) is preferably pentaerythritol tetraacrylate, pentaerythritol triacrylate, or a mixture thereof, and more preferably a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate.

[0020] When the component (A) contains a difunctional or higher hydroxyl group-containing (meth)acrylate monomer (a1), the difunctional or higher hydroxyl group-containing (meth)acrylate monomer (a1) may be 40 to 99.9 mass%, 50 to 99.9 mass%, 60 to 99.9 mass%, 70 to 99.9 mass%, 80 to 99.9 mass%, 90 to 99.9 mass%, or 100 mass%, with the total amount of the component (A) being 100 mass%.

[0021] (Component (B): Acid-modified (meth)acrylate monomer and / or hydroxyl group-containing (meth)acrylamide) The curable component contains component (B): an acid-modified (meth)acrylate monomer and / or a hydroxyl group-containing (meth)acrylamide. In the photocurable composition according to the first embodiment, the hydroxyl group-containing (meth)acrylate monomer as the component (B) may include both acrylate and methacrylate. In the photocurable composition according to the first embodiment, the acid-modified (meth)acrylate monomer and the hydroxyl group-containing (meth)acrylamide as the component (B) may each be used alone or in combination of two or more kinds. In the photocurable composition according to the first embodiment, the component (B): acid-modified (meth)acrylate monomer does not include one in which the acid-modified portion is in the form of a salt. In one embodiment, the component (B): the acid-modified (meth)acrylate monomer has an acid value (mgKOH / g) of preferably 80-800, more preferably 200-500, and particularly preferably 250-400. In one embodiment, non-limiting examples of the component (B): acid-modified (meth)acrylate monomer are preferably one or more acid-modified (meth)acrylate monomers selected from the group consisting of carboxylic acid-modified (meth)acrylates, phosphoric acid-modified (meth)acrylates, polybasic acid (succinic acid, phthalic acid, etc.)-modified (meth)acrylates, and sulfonic acid-modified (meth)acrylates. In one embodiment, preferred non-limiting examples of the hydroxyl group-containing (meth)acrylamide component (B) are one or more hydroxyl group-containing (meth)acrylamides selected from the group consisting of hydroxyalkyl(meth)acrylamide having an alkyl group with 1 to 10 carbon atoms, N-hydroxyethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxy(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, and 8-hydroxyoctyl(meth)acrylate. In one embodiment, the component (B) is preferably one or more acid-modified (meth)acrylate monomers. In one embodiment, the component (B) is preferably an acid-modified (meth)acrylate monomer in which the acid component is one or more selected from carboxylic acid, phosphoric acid, and succinic acid, and / or a hydroxyalkyl (meth)acrylamide in which the alkyl group has 1 to 5 carbon atoms, more preferably one or more acid-modified (meth)acrylate monomers and / or hydroxyl group-containing (meth)acrylamides selected from the group consisting of β-carboxyethyl acrylate, phosphoric acid-modified methacrylate, phosphoric acid-modified acrylate, 2-acryloyloxyethyl succinic acid, and hydroxyethyl acrylamide, and particularly preferably one or more acid-modified (meth)acrylate monomers selected from the group consisting of β-carboxyethyl acrylate, phosphoric acid-modified methacrylate, phosphoric acid-modified acrylate, and 2-acryloyloxyethyl succinic acid.

[0022] The amount of the (B) component in the photocurable composition according to the first embodiment may be 0.01 to 40 mass%, 0.01 to 35 mass%, 0.01 to 30 mass%, 0.01 to 25 mass%, 0.01 to 20 mass%, 0.01 to 15 mass%, or 0.01 to 10 mass%, relative to 100 mass% of the total amount of the curable components. In one embodiment, the (B) component is blended in an amount of preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 1 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass, per 100 parts by mass of the (A) component.

[0023] (Component (C): (meth)acrylic modified sulfonate) The curable component includes component (C): a (meth)acrylic-modified sulfonate. In the photocurable composition according to the first embodiment, the (meth)acrylic-modified sulfonate salt as (C) may be used alone or in combination of two or more kinds. In the photocurable composition according to the first embodiment, the component (C): the (meth)acrylic-modified sulfonate, the acid-modified portion is in the form of a salt. In one embodiment, non-limiting examples of the component (C): (meth)acrylic-modified sulfonate are preferably one or more (meth)acrylic-modified sulfonates selected from the group consisting of potassium 3-sulfopropyl acrylate, potassium 3-sulfopropyl methacrylate, 2-((meth)acryloyloxy)ethanesulfonic acid, 3-((meth)acryloyloxy)propane-1-sulfonic acid, and sodium or potassium salts of acrylamido-tertiary-butylsulfonic acid. In one embodiment, the component (C) is more preferably one or more (meth)acrylic-modified sulfonates selected from the group consisting of potassium 3-sulfopropyl acrylate, potassium 3-sulfopropyl methacrylate, and mixtures thereof.

[0024] The component (C) in the photocurable composition according to the first embodiment may be 0.01 to 5 mass%, 0.01 to 4 mass%, 0.01 to 3 mass%, 0.01 to 2.5 mass%, 0.01 to 2 mass%, 0.01 to 1.5 mass%, or 0.01 to 1 mass%, relative to 100 mass% of the total amount of the curable components. In one embodiment, the (C) component is blended in an amount of preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, even more preferably 0.5 to 2 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass, per 100 parts by mass of the (A) component.

[0025] (Component (D): Monofunctional hydroxyl group-containing (meth)acrylate monomer) In one embodiment, from the viewpoint of improving chemical resistance, the curable component may contain, in addition to the components (A) to (C), a component (D): a monofunctional hydroxyl-containing (meth)acrylate monomer. The number of hydroxyl groups in the component (D) is not particularly limited and may be 1 to 10 or 1 to 5. In one embodiment, the monofunctional hydroxyl group-containing (meth)acrylate monomer as the component (D) may be used alone or in combination of two or more. In one embodiment, non-limiting examples of the component (D): monofunctional hydroxyl group-containing (meth)acrylate monomer are preferably one or more monofunctional hydroxyl group-containing (meth)acrylate monomers selected from the group consisting of hydroxyl group-containing monofunctional (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, bisphenol A diglycidyl mono(meth)acrylate, and hydrogenated versions of these epoxy acrylates. In one embodiment, the component (D) is more preferably one or more monofunctional hydroxyl group-containing (meth)acrylate monomers selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and mixtures thereof.

[0026] In one embodiment, when the photocurable composition contains component (D), the component (D) may be 0.01 to 50 mass%, 0.01 to 30 mass%, 0.01 to 25 mass%, 0.01 to 20 mass%, 0.01 to 15 mass%, or 0.01 to 1 mass%, relative to 100 mass% of the total amount of the curable components. In one embodiment, when the photocurable composition contains the component (D), the component (D) is preferably blended in an amount of 5 to 30 parts by mass, more preferably 5 to 25 parts by mass, even more preferably 5 to 20 parts by mass, and particularly preferably 10 to 20 parts by mass, per 100 parts by mass of the component (A).

[0027] <Photopolymerization initiator> The photocurable composition according to the first embodiment further contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (e.g., Nippon Kayaku Co., Ltd., trade name "KAYACURE (registered trademark) EPA"), 2,4-diethylthioxanthone (e.g., Nippon Kayaku Co., Ltd., trade name "KAYACURE DETX"), 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1 (e.g., Ciba-Geigy Co., Ltd., trade name "Irgacure (registered trademark) 907), 1-hydroxycyclohexyl phenyl ketone (for example, IGM's product name "Omn184", etc.), 2-amino-2-benzoyl-1-phenylalkane compounds such as 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane, aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 4,4'-bis(diethylamino)benzophenone, 2,2'- Examples of the compound include imidazole compounds such as bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (for example, Hodogaya Chemical Co., Ltd., trade name "B-CIM" etc.), halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine, and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran 2-yl-ethenyl)-1,3,4-oxadiazole. These compounds may be used alone or in combination of two or more. If necessary, a photosensitizer may be added.

[0028] The content of the photopolymerization initiator in the photocurable composition is preferably 1 to 5 mass %, more preferably 2.5 to 5 mass %, and even more preferably 4 to 5 mass %, based on the total mass of the curable composition. When the content of the photopolymerization initiator is within the above range, the curable composition according to the present embodiment can be appropriately cured by ultraviolet light, which will be described later, or the like.

[0029] (Other additives) The photocurable composition according to the present embodiment may contain any component (other additives) other than the curable component and the photopolymerization initiator. The other additives are not particularly limited, and any additive that can be blended in the photocurable composition and / or the thermo-curable composition may be blended. For example, a radical polymerization initiator other than the photopolymerization initiator, an ultraviolet absorber, a reaction accelerator, a light stabilizer, a surface conditioner, etc. may be blended.

[0030] ·UV absorber As the ultraviolet absorbing agent, known or commonly used ones can be used, and although there is no particular limitation, examples thereof include cyanoacrylate-based, dihydroxybenzophenone-based, benzotriazole-based, triazine-based, and benzophenone-based ultraviolet absorbing agents.

[0031] Examples of cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and ethyl-2-cyano-3,3-diphenylacrylate. Examples of dihydroxybenzophenone-based ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, (2,4-dihydroxyphenyl)-phenylmethanone, hydroxymethoxybenzophenonesulfonic acid, 2-(2H-benzotriazol-2-yl)-4-methyl, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl), and 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl. Examples of benzotriazole-based ultraviolet absorbers include 2-(2H-benzotriazole-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole-2-yl)-6-tertiarybutyl-4-methylphenol, and 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]. Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoloxy)ethoxy]phenol, 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, 2-(4-((2-hydroxy-3-(2'ethyl)hexyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy, and the like. An example of the benzophenone-based ultraviolet absorbing agent is [2-hydroxy-4-(octyloxy)phenyl]phenylmethanone. The ultraviolet absorbing agent may be used alone or in combination of two or more kinds.

[0032] Light stabilizer The light stabilizer may be any known or conventional light stabilizer, and is not particularly limited. Examples of the light stabilizer include 2,2,6,6-tetraalkyl-4-piperidyl esters (e.g., 2,2,6,6-tetramethyl-4-piperidyl esters), 4-alkoxy-2,2,6,6-tetraalkylpiperidines (e.g., 4-(C1-10 alkoxy)-2,2,6,6-piperidines such as 4-methoxy-2,2,6,6-tetramethylpiperidine; 4-(C6-10 aryloxy)-2,2,6,6-piperidines such as 4-phenoxy-2,2,6,6-tetramethylpiperidine; 4-(C6-10 aryl)-(C1-4 alkyl)-2,2,6,6-tetramethylpiperidines such as 4-benzyloxy-2,2,6,6-tetramethylpiperidine), bis( 2,2,6,6-tetraalkyl-4-piperidyloxy)alkanes [for example, bis(2,2,6,6-tetramethyl-4-piperidyloxy)(C2-6alkanes) such as 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane], tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate; bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; reaction products of 1,2,3,4-butanetetracarboxylic acid tetramethyl ester with 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, and the like. The light stabilizers may be used alone or in combination of two or more kinds.

[0033] Reaction accelerator The reaction accelerator may be any known or conventional one, and is not particularly limited. Examples of the reaction accelerator include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate, formate salt, tetraphenylborate salt, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate, formate salt, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris(dimethylamine), Examples of the reaction accelerator include tertiary amines such as N,N-dimethylcyclohexylamine, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole, phosphoric acid esters, phosphines such as triphenylphosphine and tris(dimethoxy)phosphine, phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate, zinc octylate, tin octylate, and zinc stearate, and metal chelates such as aluminum acetylacetone complex. The reaction accelerator may be used alone or in combination of two or more.

[0034] Compositions combining (meth)acryloyl group-modified sulfonates and (meth)acryloyl monomers have been known in the past, but as described above, they often cause poor appearance of the cured coating film. The present inventors have found that poor compatibility between the resin composition and the sulfonate causes poor appearance of the cured coating film. The photocurable composition according to the present embodiment can improve poor appearance of the cured coating film more than before by combining the (A) and (C) components with the (B) component. Furthermore, since the curable component contains a relatively low molecular weight compound, the viscosity is low and the flowability is likely to be good. In one embodiment, the viscosity of the photocurable composition at 25°C may be 1 to 1000 mPa.s, or 1 to 500 mPa.s. If the viscosity of the photocurable composition is within the above range, it is possible to form a film with good adhesion, and to form a film by spraying or curtain coating, and the finish of the coating film is likely to be good.

[0035] <Method for producing photocurable composition> The photocurable composition according to the first embodiment can be produced by mixing the above-mentioned curable component, the photopolymerization initiator, and, if necessary, the above-mentioned other additives and solvent. The photocurable composition according to the first embodiment has a higher compatibility between the resin components (components (A) and (B)) and the component (C), so it is possible to reduce the amount of solvent used to dissolve the component (C) or to prepare a composition without using a solvent. When using a solvent, it is preferable to use a hydrophilic solvent such as a lower alcohol or 2-methoxyethanol. As a means for mixing, known or conventional means, for example, various mixers such as a dissolver or homogenizer, a kneader, a roll, a bead mill, a self-revolving stirring device, etc., can be used. Conditions such as temperature and rotation speed during mixing are not particularly limited and can be set appropriately.

[0036] The photocurable composition according to the first embodiment can improve the appearance of the cured coating film by photocuring. Such a photocurable composition can be suitably used as various members, particularly as interior members or water-related members. It should be noted that the use of the photocurable composition is not limited to interior members and water-related members.

[0037] [Cured product] The second embodiment of this embodiment is a cured product of the photocurable composition according to the first embodiment. The photocurable composition according to the first embodiment can be cured by light irradiation. The cured product according to the second embodiment includes not only the above-mentioned photocurable composition irradiated with light such as ultraviolet light or active energy rays to promote the curing reaction, but also a completely cured product. In addition, the cured product of this embodiment also includes a "semi-cured product" obtained by irradiating the photocurable composition with light and curing it to the extent that it loses fluidity.

[0038] The cured product according to this embodiment can be obtained as a cured coating film, for example, by applying the photocurable composition according to the first embodiment to an object such as a substrate, and then photocuring the composition.

[0039] As described above, the photocurable composition of the present invention can be applied to the surface of a substrate as a coating liquid by using a diluting solvent as necessary. The coating method is not particularly limited, and a known method can be adopted, such as gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion coating, spin coating, etc.

[0040] (light curing) The photocuring is preferably carried out by irradiation with active energy rays such as ultraviolet rays or electron beams. Examples of light sources used for ultraviolet irradiation include high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, etc. The ultraviolet irradiation time can be adjusted as desired between several seconds and several tens of seconds depending on the type of light source, the distance between the light source and the coated surface, and other conditions. On the other hand, in the case of electron beam irradiation, it is preferable to use an electron beam having an energy in the range of, for example, 50 to 1000 KeV, and to set the dose at 2 to 5 Mrad. Usually, an irradiation source with a lamp output of about 80 to 300 W / cm is used.

[0041] The thickness of the cured coating film is not particularly limited and can be adjusted as desired depending on the application, for example, in the range of 10 to 1000 μm, preferably 300 to 500 μm.

[0042] The object (subject) to which the photocurable composition is applied is not particularly limited in shape, material, etc., and examples of the material include resin, metal, glass, wood, paper, etc. Examples of resins include polyvinyl chloride, polypropylene, polyethylene, polyethylene terephthalate (PET), polycarbonate, acrylonitrile butadiene styrene (ABS), polypropylene sulfide, nylon-6, etc. Examples of metals include aluminum, SUS, iron, copper, etc. The substrate may be a substrate having a metal vapor deposition on the surface of resin, glass, wood, paper, etc., or the coated surface of the substrate may be subjected to a release treatment or the like.

[0043] In one embodiment, the haze of a 20 μm-thick cured coating film measured under the following conditions is preferably 1.2% or less, and more preferably 1% or less. <Haze measurement conditions> The photocurable composition is applied to a PET film substrate (e.g., Cosmoshine (registered trademark) A4160 (100 μm), manufactured by Toyobo Co., Ltd.) to a thickness of 20 μm, and then irradiated with a UV lamp to form a cured coating film. The haze of the resulting cured coating film is measured using a haze meter (e.g., NDH 4000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0044] [Part] The third embodiment of this embodiment is a member having the cured product according to the second embodiment. Such a member is not particularly limited, but is preferably an interior member or a water-related member. Hereinafter, details of the interior member and the water-related member will be described as one aspect of the member.

[0045] <Interior materials> In the third embodiment of this embodiment, the term "interior components" refers to all components that can be used in manufacturing walls, floors, ceilings, etc., regardless of whether they are finishing materials that cover the surface of the interior or base materials that serve as a base for installing finishing materials. Non-limiting examples include flooring, tatami mats, wallpaper, tiles, painted walls, structural plywood, etc.

[0046] <Water-related components> In the third embodiment of this embodiment, the term "wet-related components" refers to all components that can be used in places where water or hot water is used, such as a bathroom, toilet, washroom, pool, etc. Non-limiting examples include ceilings, walls, sinks, hoses, pipes, valves, etc. in a bathroom, toilet, washroom, pool, etc. EXAMPLES

[0047] The present embodiment will be described in more detail below with reference to examples, but the interpretation of the present invention is not limited to these examples.

[0048] [material] The materials used in the examples and comparative examples are as follows. <Component (A)> DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (monomer (a1)) in a ratio of approximately 1:3 (manufactured by Daicel Allnex Co., Ltd., average functionality approximately 5.2) PETRA: A mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate (monomer (a1)) in a ratio of approximately 2:3 (manufactured by Daicel Allnex Co., Ltd., average functionality 3.4) TMPTA: Trimethylolpropane triacrylate (manufactured by Daicel Allnex Co., Ltd., average functionality 3) EBECRYL® 40: Ethoxylated pentaerythritol tetra(meth)acrylate (manufactured by Daicel Allnex Corporation, average functionality 4) EBECRYL160: Ethoxylated trimethylolpropane triacrylate (manufactured by Daicel Allnex Co., Ltd., average functionality 3) NK Ester A-GLY-3E: Ethoxylated glycerin triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., average functionality 3) <(B) component> β-CEA: β-carboxyethyl acrylate (containing 20% ​​acrylic acid) (manufactured by Daicel Allnex Co., Ltd.) EBECRYL168: Phosphate-modified methacrylate (manufactured by Daicel-Allnex Co., Ltd., acid value: 290 mg KOH / g) EBECRYL170: Phosphate-modified acrylate (manufactured by Daicel Allnex Co., Ltd., acid value: 300 mg KOH / g) NK Ester A-SA: 2-Acryloyloxyethyl succinic acid (Shinnakamura Chemical Co., Ltd., acid value: 260 mg KOH / g) HEAA: N-(2-hydroxyethyl)acrylamide (KJ Chemicals, Inc.) <(C) component> SPAAK: 3-sulfopropyl potassium acrylate (Sigma-Aldrich) SPMAK: 3-sulfopropyl potassium methacrylate (Tokyo Chemical Industry Co., Ltd.) <(D) component> HEMA: 2-hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.) HPMA: 2-hydroxypropyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.) HBA: 4-hydroxybutyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) <Surface conditioner> BYK-UV3535: One-end modified non-silicone modified polyether surface conditioner (BYK, Big Chemie Japan Co., Ltd.) <Photopolymerization initiator> Omnirad® 127: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (IGM Resins BV) Benzophenone: Benzophenone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <Dilution solvent> Methoxyethanol: 2-Methoxyethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0049] [Examples 1 to 17 and Comparative Examples 1 to 8] Using the above materials, each component was weighed into an brown screw cap bottle in the ratio shown in Tables 1 to 3, and heated at 70° C. for 1 hour. Stirring and degassing were performed using a stirring and degassing device ("Mazerustar (registered trademark), Kurabo Industries, Ltd.), and dissolution was confirmed visually to obtain each photocurable composition according to the examples and comparative examples. Each of the photocurable compositions according to the examples and comparative examples was photocured by the following steps to obtain a cured coating film. (1) Coating process Each photocurable composition was applied onto a glass plate (70 mm×150 mm×1.0 mm) using a wire bar coater No. 14-18. (2) Drying process The sample was placed in an oven at 70° C. for 15 minutes to dry the dilution solvent (2-methoxyethanol). (3) Photo-curing process Under a nitrogen gas atmosphere, a conveyor-type ultraviolet (UV) irradiator (light source: high-pressure mercury lamp) was used, and the ultraviolet intensity was 300 mW / cm. 2 , Accumulated light intensity: 1000mJ / cm 2 The resin was photocured under the following conditions.

[0050] For each of the photocurable compositions and each of the cured coating films according to the Examples and Comparative Examples, evaluation of the cured coating film appearance, haze measurement, water contact angle measurement, and chemical resistance evaluation were carried out under the following conditions. The results are shown in Tables 1 to 3.

[0051] <Appearance evaluation of cured coating film> The appearance of each cured coating film was judged by visual inspection. The symbols in Tables 1 to 3 have the following meanings. A: No salt precipitation, no cloudiness, and no problems with leveling. B: No problems with salt precipitation or leveling, but slight cloudiness. C: No salt precipitation, but leveling is problematic and there is slight cloudiness. D: Salt precipitation was observed, there were problems with leveling, and the material was cloudy.

[0052] <Haze measurement> Using a haze meter ("NDH 4000", manufactured by Nippon Denshoku Industries Co., Ltd.), the photocurable composition was applied to a PET film substrate (Cosmoshine A4160 (100 μm), manufactured by Toyobo Co., Ltd.) to a film thickness of 20 μm, and a cured coating film was formed by irradiating with a UV lamp. The haze of each of the obtained cured coating films was measured using a haze meter ("NDH 4000", manufactured by Nippon Denshoku Industries Co., Ltd.). In Tables 1 to 3, when the haze (%) was less than 1.0, the cured coating film was not cloudy, when the haze (%) was 1.0 to 1.2, the cured coating film was slightly cloudy, and when the haze (%) exceeded 1.2, cloudiness was observed in the cured coating film.

[0053] <Water contact angle measurement> Using a contact angle meter (Drop Master DM700, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle was measured 1 second after a drop (a drop of ion-exchanged water (2 μl)) was detected on the cured coating surface.

[0054] <Chemical resistance evaluation> (1) Hair dye, mouthwash Approximately 0.2 g of hair dye (Bigen Creamtone (registered trademark) 7G, manufactured by Hoyu Co., Ltd.) and mouthwash (Isodine (registered trademark), manufactured by Mundipharma Co., Ltd.) were placed on each cured coating film, and then the films were left to stand for 24 hours at 23°C and a relative humidity of 50% RH, after which any traces of contamination were visually inspected. The numbers in Tables 1 to 3 have the following meanings: 5. No traces of contamination 4. There were slight traces of contamination. 3. There were traces of contamination. 2. Contamination marks were confirmed and clear coloring was observed. 1. Traces of contamination were found and had penetrated into the base material. (2) Oil-based marker Using an oil-based marker ("Twin Marker", Pilot Corporation), an ink mark of approximately 5 cm was made on each cured coating film, which was then dried at room temperature for 5 minutes. After that, the ink mark was rubbed with absorbent cotton soaked in ion-exchanged water and visually checked to see whether it could be removed. The numbers in Tables 1 to 3 have the following meanings: 5. The ink could be removed without leaving any traces. 4. There were some areas where ink marks remained. 3. Ink marks were found in some areas. 2. There were some areas where the ink stains could be removed, but more than 50% of the ink stains remained. 1. Ink stains could not be removed

[0055] [Table 1]

[0056] [Table 2]

[0057] [Table 3]

[0058] As shown in Tables 1 to 3, Examples 1 to 17, which satisfy the constitution of the photocurable composition according to the first embodiment, gave cured coating films with better appearances. That is, it was found that the photocurable composition according to the first embodiment can improve the poor appearance of cured coating films more than conventional ones. Examples 1 to 17, which satisfy the constitution of the photocurable composition according to the first embodiment, gave a cured coating film having a water contact angle of less than 30°. That is, the photocurable composition according to the first embodiment can impart hydrophilicity without using fluorine or silicone, which are known to deteriorate anti-slip properties, or surfactants, which are known to deteriorate chemical resistance, and can impart antifouling properties, chemical resistance, anti-slip properties, and easy cleaning properties to the cured coating film surface. The photocurable composition which can give such a cured coating film can be suitably used for interior members, water-related members, etc. In Tables 1 to 3, when the haze (%) was less than 1.0, the cured coating film was not cloudy, when the haze (%) was 1.0 to 1.2, the cured coating film was slightly cloudy, and when the haze (%) exceeded 1.2, the cured coating film was cloudy. As shown in Tables 1 to 3, Examples 1 to 17, which satisfy the constitution of the photocurable composition according to the first embodiment, gave cured coating films with reduced haze (i.e., high transparency). In other words, it was found that the photocurable composition according to the first embodiment has properties that can be widely applied to substrates with designs. Examples 1 to 17, which satisfy the constitution of the photocurable composition according to the first embodiment, showed stronger chemical resistance, particularly against oil-based marker. In other words, it was found that the photocurable composition according to the first embodiment can give a cured coating film having stronger chemical resistance.

Claims

1. Contains a curable component and a photopolymerization initiator, The curable component is Component (A): a difunctional or higher functional (meth)acrylate monomer, Component (B): hydroxyl group-containing (meth)acrylamide, and Component (C): (meth)acrylic modified sulfonate, Including, A photocurable composition, wherein a ratio of the (A) component is 40 to 99.9 mass%, a ratio of the (B) component is 0.01 to 40 mass%, and a ratio of the (C) component is 0.01 to 4 mass%, relative to a total amount of the curable components.

2. Contains a curable component and a photopolymerization initiator, The curable component is Component (A): a difunctional or higher functional (meth)acrylate monomer, Component (B): a carboxy group-containing (meth)acrylate monomer, and Component (C): (meth)acrylic modified sulfonate, Including, A photocurable composition, wherein a ratio of the (A) component is 40 to 99.9 mass%, a ratio of the (B) component is 0.01 to 40 mass%, and a ratio of the (C) component is 0.01 to 5 mass%, relative to a total amount of the curable components.

3. Contains a curable component and a photopolymerization initiator, The curable component is Component (A): a difunctional or higher functional (meth)acrylate monomer, (B) component: hydroxyethyl acrylamide, and Component (C): (meth)acrylic modified sulfonate, Including, A photocurable composition, wherein a ratio of the (A) component is 40 to 99.9 mass%, a ratio of the (B) component is 0.01 to 40 mass%, and a ratio of the (C) component is 0.01 to 5 mass%, relative to a total amount of the curable components.

4. The photocurable composition according to claim 1 , wherein the component (A) comprises a di- or higher functional hydroxyl group-containing (meth)acrylate monomer (a1).

5. The photocurable composition according to claim 1 , wherein the curable component further comprises component (D): a monofunctional hydroxyl group-containing (meth)acrylate monomer.

6. 4. The photocurable composition according to claim 1, wherein a ratio of the component (B) to a total amount of the curable components is 0.01 to 20 mass %.

7. The photocurable composition according to any one of claims 1 to 3, wherein the average number of functional groups of the component (A) is 2 to 4.

8. 2. The photocurable composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylamide in component (B) is hydroxyethylacrylamide.

9. A cured product of the photocurable composition according to claim 1 .

10. A member comprising the cured product according to claim 9.

11. The member according to claim 10, which is an interior member or a water-related member.

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