Curable composition, cured product thereof, and article

Abstract

The purpose of the present invention is to provide a novel composition that makes it possible to produce a cured product that has excellent hydrophilicity and water resistance. The present invention is: a curable composition that is characterized by including a radical-polymerizable carboxylic acid amine salt compound (A) that is a neutralization product of a radical-polymerizable carboxylic acid compound (a1) and an amine compound (a2) and an epoxy compound (B) and / or a silane coupling compound (C), at least one of the radical-polymerizable carboxylic acid compound (a1) and the amine compound (a2) having at least 5 carbons; or a curable composition that is characterized by including a neutral polymer (X) of a polymer (x1) that has a structural unit derived from a radical-polymerizable carboxylic acid compound (a1) and an amine compound (x2) and an epoxy compound (B) and / or a silane coupling compound (C).

Description

Curable composition, cured product thereof, and article

[0001] The present invention relates to a curable composition, a cured product thereof, and an article.

[0002] It is known that forming a hydrophilic layer having a certain level of water resistance and moisture resistance on the surface of an article can provide anti-fogging, anti-fouling, anti-static, antibacterial, etc. Such hydrophilic layers are used in a variety of fields, ranging from everyday items such as eyeglasses, helmets, bathroom mirrors, automobile lamps, heat exchangers for air conditioners, camera lenses, and endoscopes, to building materials, transportation equipment, home appliances, precision electronic devices, and medical equipment.

[0003] Known methods for forming the hydrophilic layer on the surface of an article include thermoplastic molding of a thermoplastic resin kneaded with a hydrophilizing agent, applying a chemical treatment such as alkali treatment to the resin surface to make it hydrophilic, applying a curable composition that produces a hydrophilic cured product to the surface and curing it, and forming a fine three-dimensional structure or unevenness on the surface by methods such as nanoimprinting. Among these, the method of applying a curable composition that produces a hydrophilic cured product to the surface and curing it is a widely used method because it allows for the formation of a hydrophilic layer on the surface of various articles using a relatively simple device.

[0004] In order to achieve a certain level of water resistance and moisture resistance, curable compositions that produce hydrophilic cured products are almost always designed to contain a reactive compound that forms a covalently crosslinked compound, or the reactive compound itself has a hydrophilic structure, or to contain a hydrophilic non-reactive substance, or to contain a surfactant, etc. As the hydrophilic inorganic substance, inorganic oxide fine particles such as silica and alumina are often used.

[0005] Furthermore, various structures have been proposed as hydrophilic structures possessed by hydrophilic organic substances, such as sulfonate structures (e.g., Patent Document 1), polyhydric alcohol structures (e.g., Patent Document 2), betaine structures (e.g., Patent Document 3), polyethylene glycol structures (e.g., Patent Document 4), and polyacrylamide structures (e.g., Patent Document 5), and various organic low-molecular-weight, oligomeric, and polymeric compounds having such hydrophilic structures have been used. Carboxylate structures have also been proposed and used as hydrophilic structures, and many forms have been proposed in which polymeric compounds having carboxylate structures are used as components of curable compositions, such as a form in which a carboxylate polymer is crosslinked with a crosslinking agent (e.g., Patent Document 6) or a form in which a carboxylate polymer is added as a water-absorbing substance (e.g., Patent Document 7).

[0006] On the other hand, salts of (meth)acrylic acid are widely used as highly polymerizable carboxylates in a variety of applications. However, they are water-soluble and dissolve only in highly polar organic substances. In addition, they are powdery and not film-forming in the absence of a solvent, making them difficult to use as a curing component in curable compositions that are applied to and cured on the surface of an article. Salts of 2-(meth)allyloxymethylacrylic acid have been proposed as highly polymerizable carboxylates that can overcome these issues. These salts are compatible with various organic substances and have film-forming properties even in the absence of a solvent, demonstrating their potential for use in a variety of applications (e.g., Patent Documents 8 to 10).

[0007] International Publication No. 2013 / 054877 JP 2011-213904 A International Publication No. 2017 / 018146 JP 2007-063325 A Japanese Patent Application Laid-Open No. 2012-007033 A Japanese Patent Application Laid-Open No. 2021-066785 International Publication No. 2016 / 021458 JP 2012-107208 A Japanese Patent Application Laid-Open No. 2013-216737 A Japanese Patent Application Laid-Open No. 2013-231164 A

[0008] As described above, cured products having hydrophilicity and water resistance are used in a variety of applications, and new materials capable of forming cured products having excellent properties required for various applications are desired. In view of the above-described current situation, an object of the present invention is to provide a new composition capable of providing a cured product having excellent hydrophilicity and water resistance.

[0009] The present inventors conducted extensive research to achieve the above-mentioned object and found that a curable composition containing a specific radically polymerizable carboxylic acid amine salt compound, which is a neutralization product of a radically polymerizable carboxylic acid compound and an amine compound, and at least one of an epoxy compound and a silane coupling compound, which undergo a thermal addition reaction or a thermal condensation reaction with an active hydroxyl group, can provide a curable composition that can give a cured product that exhibits both good water resistance and hydrophilicity. Furthermore, the present inventors also found that a curable composition containing a neutralized polymer of a polymer having structural units derived from a radically polymerizable carboxylic acid compound and an amine compound, and at least one of an epoxy compound and a silane coupling compound can also provide a cured product that exhibits both good water resistance and hydrophilicity, thereby completing the present invention. Specifically, the present invention is described in the following [1] to [7]. [1] A curable composition comprising a radically polymerizable carboxylic acid amine salt compound (A) which is a neutralization product of a radically polymerizable carboxylic acid compound (a1) and an amine compound (a2), and an epoxy compound (B) and / or a silane coupling compound (C), wherein at least one of the radically polymerizable carboxylic acid compound (a1) and the amine compound (a2) has 5 or more carbon atoms. [2] The curable composition according to [1] above, wherein the radically polymerizable group of the radically polymerizable carboxylic acid amine salt compound (A) is a (meth)acryloyl group and / or a 2-(meth)allyloxymethylacryloyl group. [3] A curable composition comprising a neutralized polymer (X) of a polymer (x1) having structural units derived from the radically polymerizable carboxylic acid compound (a1) and an amine compound (x2), and an epoxy compound (B) and / or a silane coupling compound (C). [4] The curable composition according to [3] above, wherein the radically polymerizable carboxylic acid compound (a1) is a compound having a (meth)acryloyl group and / or a 2-(meth)allyloxymethylacryloyl group. [5] The curable composition according to [3] or [4] above, wherein the amine compound (x2) includes an amine compound having a hydroxyl group. [6] A cured product of the curable composition according to any one of [1] to [5] above. [7] An article having the cured product according to [6] above on its surface.

[0010] By using the curable composition of the present invention, a water-resistant hydrophilic layer can be easily formed on the surface of various articles. In addition, the curable composition of the present invention can be easily designed to be suitable for a variety of fields, from daily necessities, building materials, transportation equipment, home appliances, precision electronic equipment to medical equipment.

[0011] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope of the present invention. A combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of the present invention. Furthermore, (meth)acrylic means acrylic or methacrylic. (Meth)acrylate means acrylate or methacrylate. (Meth)acryloyl means acryloyl or methacryloyl. (Meth)allyl means allyl or methallyl.

[0012] <Curable composition (1)> The curable composition of the first aspect of the present invention comprises a radically polymerizable carboxylic acid amine salt compound (A) which is a neutralization product of a radically polymerizable carboxylic acid compound (a1) and an amine compound (a2), and an epoxy compound (B) and / or a silane coupling compound (C), wherein at least one of the radically polymerizable carboxylic acid compound (a1) or the amine compound (a2) has a carbon number of 5 or more. The curable composition of the first aspect of the present invention is hereinafter also referred to as "curable composition (1)".

[0013] The curable composition (1) of the present invention can provide a cured product with excellent water resistance and hydrophilicity. The reason for this is presumed to be as follows. In the curable composition of the present invention, in addition to the radical polymerization reaction of the radically polymerizable carboxylic acid amine salt compound, the carboxyl and amino groups generated from the carboxylic acid amine salt structure by thermal dissociation trigger a reaction in which the epoxy group of the epoxy compound or the alkoxysilyl group of the silane coupling compound forms a covalent bond with an active hydrogen group. The combination of the radical polymerization reaction and the reaction forming a covalent bond with the active hydrogen group forms a strong crosslinked body, resulting in a cured product with excellent water resistance. Meanwhile, the carboxylic acid amine salt structure and the amino and hydroxyl groups newly formed in the reaction forming a covalent bond with the active hydrogen group exhibit excellent hydrophilicity. Since at least one of the radically polymerizable carboxylic acid compounds or amine compounds has 5 or more carbon atoms, the compatibility of the radically polymerizable carboxylic acid amine salt compound with the epoxy compound or the silane coupling compound is good, resulting in a cured product with good appearance and excellent water resistance and hydrophilicity. Therefore, the curable composition of the present invention can provide a cured product with excellent water resistance and hydrophilicity. Each component contained in the curable composition of the present invention will be described below.

[0014] [Radical Polymerizable Carboxylic Acid Amine Salt Compound (A)] The radical polymerizable carboxylic acid amine salt compound (A) in the present invention is a neutralized product of a radical polymerizable carboxylic acid compound (a1) and an amine compound (a2). The radical polymerizable carboxylic acid amine salt compound (A) can be obtained by neutralizing one or more protonic acids containing at least the radical polymerizable carboxylic acid compound (a1) with one or more bases containing at least the amine compound (a2). The protonic acid may be completely or partially neutralized. When partially neutralized, a mixture of a salt compound and a protonic acid is produced. The protonic acid and the base are specifically described below in the order of the radical polymerizable carboxylic acid compound (a1), the other protonic acid (a1'), the amine compound (a2), and the other base (a2').

[0015] (Radical Polymerizable Carboxylic Acid Compound (a1)) The radical polymerizable carboxylic acid compound (a1) is a compound having one or more carboxy groups and one or more radically polymerizable groups in the same molecule. When the compound has two or more radically polymerizable groups, the radically polymerizable groups may be one type or two or more types. The radically polymerizable group may be any unsaturated bond that is radically polymerizable, and is preferably a carbon-carbon double bond, and more preferably a carbon-carbon double bond that has been activated by bonding a functional group thereto.

[0016] Examples of carbon-carbon double bonds activated by the attachment of a functional group include carbon-carbon double bonds having a carbonyl group attached, carbon-carbon double bonds having a cyano group attached, carbon-carbon double bonds having a nitrogen atom attached, carbon-carbon double bonds having an aromatic ring attached, carbon-carbon double bonds having an oxygen atom attached, carbon-carbon double bonds having conjugated carbon-carbon double bonds attached, and carbon-carbon double bonds having a halogen atom attached, but the present invention is not limited to these examples. Among these, carbon-carbon double bonds having a carbonyl group attached, carbon-carbon double bonds having a nitrogen atom attached, and carbon-carbon double bonds having an aromatic ring attached are preferred, carbon-carbon double bonds having a carbonyl group attached and carbon-carbon double bonds having an aromatic ring attached are more preferred, and carbon-carbon double bonds having a carbonyl group attached are even more preferred. Preferred carbon-carbon double bonds having a carbonyl group attached include a (meth)acryloyl group and a 2-(meth)allyloxymethylacryloyl group.

[0017] Examples of compounds having one carboxy group and one or more radically polymerizable groups in the same molecule include (meth)acrylic acid; 2-(meth)allyloxymethylacrylic acid; aromatic vinyl compounds such as 4-vinylbenzoic acid; 2-alkoxymethylacrylic acids such as 2-methoxymethylacrylic acid and 2-ethoxymethylacrylic acid; monoesters of α-β unsaturated dicarboxylic acids such as maleic acid monomethyl ester, fumaric acid monomethyl ester, and itaconic acid monomethyl ester; (meth)acrylic acid esters with terminal carboxylation such as 2-carboxyethyl acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and (meth)acrylate 3-carboxypropyl; polybasic acid adducts of polyvalent acrylates having one hydroxyl group such as succinic anhydride adduct of pentaerythritol triacrylate and phthalic anhydride adduct of pentaerythritol triacrylate; etc.

[0018] Examples of compounds having two or more carboxy groups and one or more radically polymerizable groups in the same molecule include α-β unsaturated dicarboxylic acids such as 2,2'-(oxydimethylene)diacrylic acid, maleic acid, fumaric acid, and itaconic acid; trimellitic anhydride adducts of hydroxyl group-containing (meth)acrylic acid esters, such as trimellitic anhydride adducts of 2-hydroxyethyl (meth)acrylate and trimellitic anhydride adducts of 4-hydroxybutyl (meth)acrylate; polybasic acid adducts of polyvalent acrylates having two or more hydroxyl groups, such as succinic anhydride adducts of dipentaerythritol tetraacrylate and phthalic anhydride adducts of dipentaerythritol tetraacrylate; and polycarboxylic acid polymers having radically polymerizable groups introduced into their side chains, such as the polymers in which glycidyl methacrylate is added to some of the carboxy groups of a (meth)acrylic acid copolymer, as described in JP 2019-019199 A.

[0019] Among these, the radical polymerizable carboxylic acid compound (a1) is preferably a compound having one carboxy group and one or more radical polymerizable groups in the same molecule, from the viewpoint of improving the solubility and viscosity of the radical polymerizable carboxylic acid amine salt compound (A).

[0020] (Other Protonic Acids (a1')) Examples of the other protonic acids include any organic or inorganic protonic acids. From the viewpoint of compatibility with various organic substances and film-forming properties, organic acids are preferred. Examples include non-radically polymerizable carboxylic acids such as acetic acid, propionic acid, pivalic acid, 2-ethylhexanoic acid, and benzoic acid; organic phosphoric acids such as 2-ethylhexyl acid phosphate and 2-methacryloyloxyethyl acid phosphate; and organic sulfonic acids such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and p-styrenesulfonic acid.

[0021] From the viewpoint of improving the radical polymerizability of the curable composition and the water resistance of the cured product, organic acids having a radical polymerizable group, such as 2-methacryloyloxyethyl acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid, and p-styrenesulfonic acid, are preferred.

[0022] (Amine Compound (a2)) The amine compound (a2) is a compound having one or more amino groups in the same molecule. When the amine compound (a2) contains two or more amino groups, the amino groups may be one type or two or more types. The amino group may be any of primary to tertiary amino groups, with primary or secondary being preferred from the viewpoint of enhancing hydrophilicity and tertiary being preferred from the viewpoint of improving compatibility with low-polarity compounds.

[0023] Specific examples of the amine compound (a2) include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, tris(2-aminoethyl)amine, hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 3,6,9,12-tetraoxa-tetradecane-1,14diamine, trishydroxymethylaminomethane, 2-amino-2-methyl-1,3-propanediol, N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, isophoronediamine, 2,5 (or 2,6)-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6 (or 2,7)-bis(aminomethyl)bicyclo[3, 2,1]octane, 2,5 (or 2,6)-bis(aminomethyl)-7-dimethylbicyclo[2,2,1]heptane, 2,6-bis(aminomethyl)adamantane, m-xylylenediamine, p-phenylenediamine, bis(4-aminophenyl)methane, 1,4 (or 2,6 or 2,7)-bis(aminomethyl)naphthalene, diallylamine, piperazine, aminoethylpiperazine, bisaminopropylpiperazine, 2,4,6-triamino-1,3,5 -triazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, diazabicycloundecene, diazabicyclononene, diazabicyclooctane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, polyethyleneimine, diallylamine polymer, etc. One or more types of the amine compound (a2) may be appropriately selected depending on the purpose and application.

[0024] Among these, from the viewpoint of improving the water resistance of the resulting cured product, amines having at least an active hydrogen group other than an amino group, a radically polymerizable group, or a functional group that undergoes a thermal addition or thermal condensation reaction with an active hydrogen group, such as trishydroxymethylaminomethane, 2-amino-2-methyl-1,3-propanediol, N,N'-bis(2-hydroxyethyl)ethylenediamine, diallylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc. are preferred. Furthermore, from the viewpoint of promoting the reaction of an epoxy group or an alkoxysilyl group to form a covalent bond with an active hydrogen group, amines having an amidine structure or an amine having a bicyclocyclic tertiary amine structure, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, diazabicycloundecene, diazabicyclononene, and diazabicyclooctane, are also preferred.

[0025] (Another Base (a2')) As the other base, any organic or inorganic base can be used. Examples of inorganic bases include metal oxides or hydroxides, such as oxides or hydroxides of elements in Group 1 of the periodic table, such as lithium, sodium, and potassium; elements in Group 2 of the periodic table, such as magnesium, calcium, and barium; transition metal elements in Groups 3 to 11 of the periodic table, such as lanthanum, zirconium, iron, cobalt, nickel, and copper; and typical metal elements in Groups 12 to 15 of the periodic table, such as zinc, aluminum, tin, lead, and bismuth. From the viewpoint of being able to make the solution colorless, oxides or hydroxides of the typical metal elements and metals belonging to Groups 3 and 4 of the periodic table are preferred, and from the viewpoints of availability and toxicity, oxides or hydroxides of lithium, sodium, potassium, magnesium, calcium, zinc, and aluminum are more preferred.

[0026] Preferred examples of the organic base include ammonia and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and hexadecyltrimethylammonium hydroxide.

[0027] In the present invention, at least one of the radical polymerizable carboxylic acid compounds (a1) or the amine compounds (a2) has a carbon number of 5 or more. By using such a carbon number, the compatibility of the radical polymerizable carboxylic acid amine salt compound (A) with common organic substances is improved, and a uniform liquid curable composition can be obtained. From the viewpoint of achieving a low viscosity of the curable composition even with a reduced amount of volatile solvent, the carbon number is preferably 5 to 30, more preferably 5 to 25, and even more preferably 5 to 20. Note that, "at least one of the radical polymerizable carboxylic acid compounds (a1) or the amine compounds (a2) has a carbon number of 5 or more" means that at least one of the one or more radical polymerizable carboxylic acid compounds (a1) and the amine compounds (a2) contained in the curable composition of the present invention has a carbon number of 5 or more.

[0028] The number of carbon atoms in the radically polymerizable carboxylic acid compound (a1) is preferably 3 to 30, more preferably 3 to 20, even more preferably 3 to 15, preferably 5 to 30, more preferably 5 to 25, even more preferably 5 to 20, still more preferably 5 to 15, and particularly preferably 5 to 10, from the viewpoints of polymerization activity and balancing hydrophilicity and water resistance.

[0029] The number of carbon atoms in the amine compound (a2) is preferably 4 to 30, more preferably 5 to 25, and even more preferably 6 to 20, from the viewpoint of balancing hydrophilicity and compatibility.

[0030] The content of the structure derived from the radically polymerizable carboxylic acid compound (a1) contained in the curable composition (1) of the present invention is preferably 3 to 90 mass%, more preferably 5 to 85 mass%, and even more preferably 10 to 80 mass%, based on 100 mass% of the curable composition.

[0031] The amount of the structure derived from the amine compound (a2) contained in the curable composition (1) of the present invention is preferably 3 to 90 mass%, more preferably 5 to 85 mass%, and even more preferably 10 to 80 mass%, based on 100 mass% of the curable composition.

[0032] The method and apparatus for measuring the content of the structure derived from the radical polymerizable carboxylic acid compound (a1) and the content of the structure derived from the amine compound (a2) are preferably selected appropriately depending on the structure and properties of the compounds. For example, when the molecular weight is 1000 or more, measurement is preferably performed by SEC (size exclusion chromatography). When the molecular weight is a low-molecular-weight compound of less than 1000, measurement is preferably performed by ion chromatography, capillary electrophoresis, gas chromatography, or the like. １ In particular, as a method and apparatus for measuring the content of a structure derived from a radically polymerizable carboxylic acid compound (a1) having a molecular weight of less than 1000, capillary electrophoresis is preferred from the viewpoints of ease of preparation of a measurement sample and measurement sensitivity, and as a method and apparatus for measuring the content of a structure derived from an amine compound (a2) having a molecular weight of less than 1000, it is preferred to selectively use capillary electrophoresis and gas chromatography depending on the presence or absence of a functional group that reacts with a component contained in the electrophoresis running solution used in capillary electrophoresis.

[0033] The content of the radical polymerizable carboxylic acid amine salt compound (A) in the curable composition (1) is preferably 5 to 90 mass %, more preferably 10 to 85 mass %, and even more preferably 15 to 80 mass %.

[0034] [Epoxy compound (B), silane coupling compound (C)] The curable composition (1) of the present invention further contains an epoxy compound (B) and / or a silane coupling compound (C). These compounds undergo a thermal addition reaction or a thermal condensation reaction with an active hydrogen group. The curable composition (1) of the present invention is more preferably in a form containing at least one epoxy compound (B) and at least one silane coupling compound (C), or in a form containing at least one compound belonging to both the epoxy compound (B) and the silane coupling compound (C) (i.e., a compound having at least one epoxy group and at least one alkoxysilyl group in the same molecule).

[0035] (Epoxy Compound (B)) In the curable composition (1) of the present invention, carboxyl groups and amino groups are generated from the carboxylic acid amine salt structure upon thermal dissociation. By including the epoxy compound (B), the generated carboxyl groups and amino groups trigger a reaction in which the epoxy group of the epoxy compound forms a covalent bond with an active hydrogen group. This reaction overlaps with the radical polymerization reaction of the radically polymerizable carboxylic acid amine salt compound (A), forming a stronger crosslinked body and resulting in a cured product with excellent water resistance. Meanwhile, the newly formed amino groups and hydroxyl groups in the reaction to form a covalent bond with the carboxylic acid amine salt structure or the active hydrogen group exhibit excellent hydrophilicity. Therefore, the curable composition of the present invention can provide a cured product with excellent water resistance and hydrophilicity.

[0036] The epoxy compound (B) is a compound having one or more epoxy groups in the same molecule, and the type of the epoxy group may be one type or two or more types. The epoxy compound (B) may be a low molecular weight compound, an oligomer, or a high molecular weight compound.

[0037] The number of carbon atoms in the epoxy compound (B) is preferably 5 to 90, more preferably 7 to 80, and even more preferably 10 to 70, from the viewpoint of enabling the viscosity of the curable composition to be low even when the amount of the volatile solvent is reduced.

[0038] Specific examples of the epoxy compound (B) include glycidyl (meth)acrylate, 2-ethylhexyl glycidyl ether, p-tert-butylphenyl glycidyl ether, N-glycidyl phthalimide, methoxypolyethylene glycol monoglycidyl ether, lauryloxypolyethylene glycol monoglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, lauryloxypolyethylene glycol glycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and sorbitol polyglycidyl ether. compounds having a glycidyl group, such as diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, phenol novolac type polyglycidyl ether, o-cresol novolac type polyglycidyl ether, triglycidyl isocyanurate, 4,4'-methylenebis(N,N-diglycidylaniline), 3-glycidyloxypropyltrimethoxysilane, radical (co)polymers of compounds having a radical polymerizable group and a glycidyl group (glycidyl (meth)acrylate, etc.); and compounds having an alicyclic epoxy group, such as (3,4-epoxycyclohexyl)methyl (meth)acrylate, (3,4-epoxycyclohexylmethyl)3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinyl-1-cyclohexene, bis(3,4-epoxycyclohexylmethyl)adipate, 4-vinylcyclohexene dioxide, and radical (co)polymers of compounds having a radical polymerizable group and an alicyclic epoxy group (e.g., (3,4-epoxycyclohexyl)methyl (meth)acrylate). Among these, compounds having a glycidyl group are preferred from the viewpoint of reactivity.

[0039] The curable composition (1) of the present invention may contain one or more epoxy compounds (B). The content of the epoxy compound (B) in the curable composition is preferably 1% by mass or more and 90% by mass or less, more preferably 2% by mass or more and 85% by mass or less, and even more preferably 3% by mass or more and 80% by mass or less, based on 100% by mass of the curable composition.

[0040] (Silane Coupling Compound (C)) In the curable composition (1) of the present invention, a carboxy group and an amino group are generated from the carboxylic acid amine salt structure by thermal dissociation, and by containing the silane coupling compound (C), the generated carboxy group and amino group act as a trigger to cause a reaction in which the alkoxysilyl group forms a covalent bond with an active hydrogen group. This reaction overlaps with the radical polymerization reaction of the radical polymerizable carboxylic acid amine salt compound (A), and therefore a stronger crosslinked body is formed, resulting in a cured product with excellent water resistance.

[0041] The silane coupling compound (C) is a compound having one or more alkoxysilyl groups in the same molecule, and the type of the alkoxysilyl group may be one type or two or more types. The silane coupling compound (C) may be a low molecular weight compound, an oligomer, or a high molecular weight compound.

[0042] Examples of compounds having an alkoxysilyl group include tetramethoxysilane, tetraethoxysilane, hydrolysis / polycondensation oligomer of tetramethoxysilane, hydrolysis / polycondensation oligomer of tetraethoxysilane, 3-(trimethoxysilyl)propyl(meth)acrylate, 3-[dimethoxy(methyl)silyl]propyl(meth)acrylate, 3-(triethoxysilyl)propyl(meth)acrylate, 3-[diethoxy(methyl)silyl]propyl(meth)acrylate, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy ... Examples of suitable low molecular weight compounds include silane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, bis[3-(trimethoxysilyl)propyl]amine, and 1,6-bis(trimethoxysilyl)hexane; and polymeric compounds such as radical (co)polymers of compounds having a radical polymerizable group and an alkoxysilyl group, such as alkoxysilyl-terminated polydimethylsiloxane, 3-(trimethoxysilyl)propyl(meth)acrylate, and 3-(triethoxysilyl)propyl(meth)acrylate.

[0043] Among these, from the viewpoint of improving crosslinking efficiency, compounds having two or more alkoxysilyl groups in the same molecule, such as hydrolysis / polycondensation oligomers of tetramethoxysilane, hydrolysis / polycondensation oligomers of tetraethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, bis[3-(trimethoxysilyl)propyl]amine, 1,6-bis(trimethoxysilyl)hexane, alkoxysilyl-terminated polydimethylsiloxane, radical (co)polymers of compounds having a radical polymerizable group and an alkoxysilyl group, such as 3-(trimethoxysilyl)propyl(meth)acrylate and 3-(triethoxysilyl)propyl(meth)acrylate; Compounds having one or more alkoxysilyl groups and one or more radically polymerizable groups in the same molecule, such as 3-(trimethoxysilyl)propyl(meth)acrylate, 3-[dimethoxy(methyl)silyl]propyl(meth)acrylate, 3-(triethoxysilyl)propyl(meth)acrylate, and 3-[diethoxy(methyl)silyl]propyl(meth)acrylate; compounds having one or more alkoxysilyl groups and one or more active hydrogen groups in the same molecule, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; Compounds having one or more alkoxysilyl groups and one or more functional groups that undergo a thermal addition reaction with an active hydrogen group in the same molecule, such as 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride, are preferred.

[0044] The content of the silane coupling compound (C) in the curable composition (1) is preferably 1 mass% or more and 90 mass% or less, more preferably 2 mass% or more and 85 mass% or less, and even more preferably 3 mass% or more and 80 mass% or less, based on 100 mass% of the curable composition.

[0045] [Other Components] The curable composition (1) of the present invention may contain other components in addition to the above-mentioned radical polymerizable carboxylic acid amine salt compound (A), epoxy compound (B), and silane coupling compound (C). The other components are not particularly limited as long as they do not adversely affect the effects of the present invention, and may be appropriately selected from known components depending on the application and purpose. Preferred examples include radical polymerizable compounds having hydrophilic functional groups or structures, polyfunctional radical polymerizable compounds, low-viscosity radical polymerizable compounds, compounds that undergo thermal addition reaction or thermal condensation reaction with active hydrogen groups (excluding the above-mentioned epoxy compound (B) and silane coupling agent (C)), resins having hydrophilic functional groups or structures, surfactants, inorganic fine particles, radical polymerization initiators, radical polymerization inhibitors, solvents, etc.

[0046] (Radical polymerizable compound having hydrophilic functional group or structure) When the curable composition (1) contains a radical polymerizable compound having a hydrophilic functional group or structure, the compound can have an intermolecular interaction with the cation contained in the curable composition, or can promote the reaction when a compound that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group is used, thereby further improving the water resistance and hydrophilicity of the cured product.

[0047] The radical polymerizable compound having the hydrophilic functional group or structure has a hydrophilic functional group or structure and also has a radical polymerizable group. The radical polymerizable compound may have only one type of hydrophilic functional group or structure in the same molecule, or may have two or more types. Furthermore, the radical polymerizable compound may have only one type of hydrophilic functional group or structure in the same molecule, or may have two or more types. Similarly, the radical polymerizable group may have only one type of radical polymerizable group in the same molecule, or may have two or more types. Furthermore, the radical polymerizable group may have only one type of radical polymerizable group in the same molecule, or may have two or more types.

[0048] Examples of hydrophilic functional groups or structures include a hydroxyl group, a polyoxyethylene structure, an amino group, an amide group, a carboxy group, a sulfonic acid group, a phosphate group, a quaternary ammonium salt structure, a betaine structure, a cyano group, an imide group, a silanol group, a lactone structure, and a cyclic ether structure, and preferred examples thereof include a hydroxyl group, a polyoxyethylene structure, an amino group, an amide group, a carboxy group, a sulfonic acid group, a phosphate group, a quaternary ammonium salt structure, and a betaine structure.

[0049] The radical polymerizable group is preferably a carbon-carbon double bond adjacent to a functional group that activates the carbon-carbon double bond, and preferred examples of the functional group that activates the carbon-carbon double bond include a carbonyl group, an amide group, a cyano group, an aromatic ring, an alkoxy group, an acyloxy group, a carbon-carbon double bond, and a halogen atom. Only one functional group may be adjacent to the carbon-carbon double bond, or two or more groups may be adjacent to the carbon-carbon double bond. Preferred examples of compounds having such radical polymerizable groups include compounds having a (meth)acryloyl group, N-vinyl amides, aromatic vinyls, vinyl ethers, and vinyl esters.

[0050] Specific examples of the radically polymerizable compound having a hydroxyl group include monofunctional (meth)acrylates having only one radically polymerizable group in the same molecule, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol mono(meth)acrylate; polyfunctional (meth)acrylates of polyhydric alcohols, such as glycerol di(meth)acrylate and pentaerythritol tri(meth)acrylate; and epoxy (meth)acrylates obtained by adding (meth)acrylic acid to an epoxy resin.

[0051] Specific examples of the radically polymerizable compound having a polyoxyethylene structure include mono- or di(meth)acrylates of polyalkylene glycols having an oxyethylene structure as a repeating unit, such as polyethylene glycol mono(meth)acrylate, polyethylene glycol di(meth)acrylate, (methoxy)polyethylene glycol (meth)acrylate, and poly(ethylene glycol-propylene glycol) mono(meth)acrylate; and ethylene oxide-modified polyfunctional (meth)acrylates obtained by adding (meth)acrylic acid to a compound obtained by adding ethylene oxide to a polyhydric alcohol such as trimethylolpropane, dipentaerythritol, polyglycerin, or bisphenol A.

[0052] Specific examples of radically polymerizable compounds having an amino group include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate hydrochloride, diallylamine, diallylamine hydrochloride, N-[3-(dimethylamino)propyl]acrylamide, etc. The amino group may form an amine salt structure with an inorganic or organic acid, as exemplified above.

[0053] Specific examples of the radically polymerizable compound having an amide group include (meth)acrylamide, N,N-dimethylacrylamide, N-(2-hydroxyethyl)acrylamide, acryloylmorpholine, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, and 1,3,5-tri(meth)acryloylhexahydro-1,3,5-triazine.

[0054] Specific examples of the radically polymerizable compound having a carboxy group include (meth)acrylic acid, terminally carboxylated (meth)acrylic acid esters (2-carboxyethyl acrylate, 2-(meth)acryloyloxyethyl succinate, etc.), 2-(meth)allyloxymethyl acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. The carboxy group may form a carboxylate structure with an inorganic or organic base other than an amine, such as sodium acrylate or zinc 2-(meth)allyloxymethyl acrylate (excluding the radically polymerizable carboxylic acid amine salt compound (A)), or may form a carboxylic acid anhydride structure, such as maleic anhydride.

[0055] Specific examples of radically polymerizable compounds having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, 2-sulfoethyl(meth)acrylate, sodium p-styrenesulfonate, potassium 3-sulfopropyl(meth)acrylate, etc. The sulfonic acid group may form a sulfonate structure with an inorganic or organic base.

[0056] Specific examples of radical polymerizable compounds having a phosphoric acid group include 2-(meth)acryloyloxyethyl acid phosphate, vinylphosphonic acid, etc. The phosphoric acid group may form a phosphate structure with an inorganic or organic base.

[0057] Specific examples of the radical polymerizable compound having a quaternary ammonium salt structure include [2-((meth)acryloyloxy)ethyl]trimethylammonium chloride, [2-((meth)acryloyloxy)ethyl]dimethylbenzylammonium chloride, and (3-acrylamidopropyl)trimethylammonium chloride.

[0058] Specific examples of the radical polymerizable compound having a betaine structure include 2-[[2-((meth)acryloyloxy)ethyl]dimethylammonio]acetic acid, 2-(meth)acryloyloxyethyl phosphorylcholine, 3-[[2-((meth)acryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid, 3-[(3-(meth)acrylamidopropyl)dimethylammonio]propane-1-sulfonic acid, and bis[2-(methacryloyloxy)ethyl](methyl)ammoniopropane-1-sulfonic acid.

[0059] The curable composition (1) may contain one or more radical polymerizable compounds having the hydrophilic functional group or structure. The curable composition (1) does not have to contain the radical polymerizable compound having the hydrophilic functional group or structure. When the curable composition (1) contains the radical polymerizable compound, the content thereof is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, and even more preferably 5 to 40 mass%, relative to 100 mass% of the curable composition.

[0060] (Polyfunctional radically polymerizable compound) The curable composition (1) further contains a polyfunctional radically polymerizable compound, which can introduce covalent crosslinks into the cured product, thereby further improving the water resistance of the cured product and improving mechanical properties such as hardness.

[0061] The polyfunctional radical polymerizable compound may have two or more radical polymerizable groups in the same molecule, and may have only one type or two or more types in the same molecule. The structure of the radical polymerizable group is preferably a carbon-carbon double bond adjacent to a functional group that activates the carbon-carbon double bond.

[0062] Preferred examples of the functional group that activates the carbon-carbon double bond include a carbonyl group, an amide group, a cyano group, an aromatic ring, an alkoxy group, an acyloxy group, a carbon-carbon double bond, and a halogen atom. Only one functional group may be adjacent to the carbon-carbon double bond, or two or more types of functional groups may be adjacent to the carbon-carbon double bond.

[0063] Preferred examples of the compound having a radical polymerizable group include compounds having a (meth)acryloyl group, N-vinylamides, aromatic vinyls, vinyl ethers, and vinyl esters.

[0064] Examples of the polyfunctional radically polymerizable compound include polyfunctional (meth)acrylic compounds such as polyfunctional (meth)acrylic esters, vinyl ether group-containing (meth)acrylic esters, allyl group-containing (meth)acrylic esters, polyfunctional (meth)acryloyl group-containing isocyanurates, and polyfunctional urethane (meth)acrylates; polyfunctional 2-(meth)allyloxymethyl acrylic esters; polyfunctional maleimide compounds; polyfunctional vinyl ethers; polyfunctional allyl compounds; and polyfunctional aromatic vinyls.

[0065] Examples of polyfunctional (meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F. Examples of the polyfunctional (meth)acrylic acid esters include those described in JP-A-2014-40585, such as alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide-added trimethylolpropane tri(meth)acrylate.

[0066] Examples of vinyl ether group-containing (meth)acrylic acid esters include the vinyl ether group-containing (meth)acrylic acid esters described in JP-A-2014-40585, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, and 4-vinyloxycyclohexyl (meth)acrylate.

[0067] Examples of the allyl group-containing (meth)acrylic acid ester include allyl (meth)acrylate.

[0068] Examples of polyfunctional (meth)acryloyl group-containing isocyanurates include tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate.

[0069] Examples of the polyfunctional urethane (meth)acrylate include polyfunctional urethane (meth)acrylates obtained by reacting a polyfunctional isocyanate such as tolylene diisocyanate, isophorone diisocyanate, or xylylene diisocyanate with a hydroxyl group-containing (meth)acrylic acid ester such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

[0070] Examples of polyfunctional 2-(meth)allyloxymethyl acrylates include the polyfunctional 2-(meth)allyloxymethyl acrylates described in Japanese Patent No. 5,689,628.

[0071] Examples of polyfunctional maleimide compounds include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and phenylmethane maleimide oligomer.

[0072] Examples of polyfunctional vinyl ethers include polyfunctional vinyl ethers described in JP-A-2014-40585, such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, and trimethylolpropane trivinyl ether.

[0073] Examples of polyfunctional allyl compounds include polyfunctional allyl compounds described in JP 2014-40585 A, such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, and trimethylolpropane triallyl ether.

[0074] Examples of polyfunctional aromatic vinyls include divinylbenzene.

[0075] The polyfunctional radical polymerizable compound may be an oligomer or polymer having a skeleton portion other than the radical polymerizable group that is a repeating unit based on a monomer. Generally, a polyfunctional radical polymerizable compound having a molecular weight of less than 1000 can be classified as an oligomer, and a polyfunctional radical polymerizable compound having a molecular weight of 1000 or more can be classified as a polymer.

[0076] Examples of the backbone of the oligomer or polymer of the polyfunctional radical polymerizable compound include a polyester backbone, a polyether backbone, a polyurethane backbone, a conjugated diene polymer backbone such as polybutadiene or polyisoprene, a poly(meth)acrylate backbone, a phenolic resin backbone, an aniline resin backbone, a polyolefin backbone, a polyamide backbone, a cycloolefin polymer backbone, and a polysiloxane backbone. Among these backbones, a polyester backbone, a polyether backbone, a polyurethane backbone, a conjugated diene polymer backbone, a poly(meth)acrylate backbone, a phenolic resin backbone, and an aniline resin backbone are preferred. The backbone portion and the radical polymerizable group may be bonded by a covalent bond, but are preferably bonded via an ester bond and / or a urethane bond.

[0077] Examples of oligomers or polymers of polyfunctional radical polymerizable compounds include urethane(meth)acrylate-based polymerizable oligomers in which a (meth)acryloyl group is bonded to a skeleton portion via a urethane bond, urethane(meth)acrylate-based polymers in which a (meth)acryloyl group is bonded to a skeleton portion via a urethane bond, epoxy(meth)acrylate-based polymerizable oligomers having a structure in which (meth)acrylic acid is added to an epoxy resin (oligomer or polymer having an epoxy group), and epoxy(meth)acrylate-based polymers having a structure in which (meth)acrylic acid is added to an epoxy resin (oligomer or polymer having an epoxy group). polyester (meth)acrylate polymerizable oligomers in which a (meth)acryloyl group is bonded to a polyester skeleton via an ester bond; phenylmethane (meth)acrylate polymerizable oligomers in which a (meth)acryloyl group is bonded to a phenol resin skeleton via an ester bond; phenylmethane (meth)acrylate polymers in which a (meth)acryloyl group is bonded to a phenol resin skeleton via an ester bond; phenylmethane maleimide polymerizable oligomers in which a maleimide group is bonded directly to an aniline resin skeleton; and phenylmethane maleimide polymers in which a maleimide group is bonded directly to an aniline resin skeleton.

[0078] The curable composition (1) may contain one or more of the polyfunctional radical polymerizable compounds. The curable composition (1) does not necessarily contain the polyfunctional radical polymerizable compound, but when it does contain the polyfunctional radical polymerizable compound, the content thereof is preferably 3 to 50 mass%, more preferably 5 to 45 mass%, and even more preferably 7 to 40 mass%, relative to 100 mass% of the curable composition.

[0079] (Low-Viscosity Radically Polymerizable Compound) The curable composition (1) contains a low-viscosity radically polymerizable compound, which can reduce the viscosity of the curable composition to improve reaction efficiency, or can adjust the content of a high-viscosity substance to improve water resistance.

[0080] The low-viscosity radically polymerizable compound preferably has a viscosity at 23° C. of 180 mPa·s or less, more preferably 140 mPa·s or less, and even more preferably 100 mPa·s or less.

[0081] The low-viscosity radical polymerizable compound may have only one type of radical polymerizable group in the same molecule, or may have two or more types. Also, the same molecule may have only one type of radical polymerizable group, or may have two or more types. Examples of the radical polymerizable group include the same radical polymerizable groups as those in the radical polymerizable compound having the above-mentioned hydrophilic functional group or structure.

[0082] As the low-viscosity radically polymerizable compound, from the viewpoints of availability, radical polymerizability, dilutability, etc., particularly preferred examples include monofunctional (meth)acrylic acid esters and monofunctional 2-(meth)allyloxymethylacrylic acid esters.

[0083] Examples of monofunctional (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, sec-amyl (meth)acrylate, tert-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and silyl (meth)acrylate. Examples thereof include cyclohexyl, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate.

[0084] Examples of monofunctional 2-(meth)allyloxymethyl acrylate esters include methyl 2-(meth)allyloxymethyl acrylate, ethyl 2-(meth)allyloxymethyl acrylate, n-propyl 2-(meth)allyloxymethyl acrylate, isopropyl 2-(meth)allyloxymethyl acrylate, n-butyl 2-(meth)allyloxymethyl acrylate, sec-butyl 2-(meth)allyloxymethyl acrylate, tert-butyl 2-(meth)allyloxymethyl acrylate, n-amyl 2-(meth)allyloxymethyl acrylate, sec-amyl 2-(meth)allyloxymethyl acrylate, tert-amyl 2-(meth)allyloxymethyl acrylate, n-hexyl 2-(meth)allyloxymethyl acrylate, 2-ethylhexyl 2-(meth)allyloxymethyl acrylate, p) cyclohexyl allyloxymethylacrylate, cyclohexylmethyl 2-(meth)allyloxymethylacrylate, octyl 2-(meth)allyloxymethylacrylate, lauryl 2-(meth)allyloxymethylacrylate, benzyl 2-(meth)allyloxymethylacrylate, isobornyl 2-(meth)allyloxymethylacrylate, tricyclodecanyl 2-(meth)allyloxymethylacrylate, 2-methoxyethyl 2-(meth)allyloxymethylacrylate, 2-ethoxyethyl 2-(meth)allyloxymethylacrylate, phenoxyethyl 2-(meth)allyloxymethylacrylate, tetrahydrofurfuryl 2-(meth)allyloxymethylacrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl 2-(meth)allyloxymethylacrylate.

[0085] The curable composition (1) may contain one or more of the low-viscosity radically polymerizable compounds. The curable composition (1) does not have to contain the low-viscosity radically polymerizable compound, but when it does contain the low-viscosity radically polymerizable compound, the content thereof is preferably 3 to 40 mass%, more preferably 5 to 35 mass%, and even more preferably 7 to 30 mass%, relative to 100 mass% of the curable composition.

[0086] (Compound that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group) The curable composition (1) further contains a compound that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group, other than the epoxy compound (B) and the silane coupling compound (C), thereby introducing covalent crosslinks into the cured product, and improving the water resistance and mechanical properties such as hardness of the cured product.

[0087] The functional group possessed by the compound that undergoes a thermal addition reaction or thermal condensation reaction with the active hydrogen group may be any functional group that undergoes a thermal addition reaction or thermal condensation reaction with the active hydrogen group, and may have only one type or two or more types in the same molecule.

[0088] Examples of functional groups that undergo a thermal addition reaction or a thermal condensation reaction with an active hydrogen group include an oxetanyl group, a carbodiimide group, an oxazoline group, an isocyanate group, a hydroxymethyl group or an alkoxymethyl group bonded to a nitrogen atom, etc. Furthermore, a compound having a functional group that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group may be a low molecular weight compound, an oligomer, or a high molecular weight compound.

[0089] Examples of compounds having an oxetanyl group include low molecular weight compounds such as (3-ethyl-3-oxetanyl)methyl(meth)acrylate, 3-allyloxymethyl-3-ethyloxetane, 2-ethylhexylmethyl-3-ethyloxetane, bis(3-ethyl-3-oxetanylmethyl)ether, bis[(3-ethyl-3-oxetanyl)methyl]isophthalate, and 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl; and radical (co)polymers of compounds having an oxetanyl group and a radical polymerizable group such as (3-ethyl-3-oxetanyl)methyl(meth)acrylate.

[0090] Examples of compounds having a carbodiimide group include N,N'-diisopropylcarbodiimide, N,N'-di-tert-butylcarbodiimide, N,N'-dicyclohexylcarbodiimide, bis(2,6-diisopropylphenyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and Carbodista (product name, Teijin Limited).

[0091] Examples of compounds having an oxazoline group include EPOCROS WS-300 (product name, Nippon Shokubai Co., Ltd.), EPOCROS WS-500 (product name, Nippon Shokubai Co., Ltd.), EPOCROS WS-700 (product name, Nippon Shokubai Co., Ltd.), and EPOCROS RPS-1005 (product name, Nippon Shokubai Co., Ltd.).

[0092] Examples of compounds having an isocyanate group include low molecular weight compounds such as 2-isocyanatoethyl (meth)acrylate, tolylene diisocyanate, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate (monomeric MDI); polymeric compounds such as radical (co)polymers of compounds having a radical polymerizable group and an isocyanate group, such as polymeric MDI and 2-isocyanatoethyl (meth)acrylate; and isocyanate-terminated prepolymers obtained by reacting a polyol with an excess of polyisocyanate. The isocyanate group may be masked with a blocking agent such as phenol, ε-caprolactam, methyl ethyl ketone oxime, diethyl malonate, ethyl acetoacetate, or dimethylpyrazole.

[0093] Examples of compounds having a hydroxymethyl group or alkoxymethyl group bonded to a nitrogen atom include hydroxymethylated (meth)acrylamide compounds such as N-(hydroxymethyl)(meth)acrylamide, N-(methoxymethyl)(meth)acrylamide, and radical (co)polymers of N-(hydroxymethyl)(meth)acrylamide and N-(methoxymethyl)(meth)acrylamide; melamine resins such as hexamethylol melamine, partially or completely methyl etherified products of hexamethylol melamine, partially methylolated melamine, and methyl etherified products of partially methylolated melamine; benzoguanamine resins such as tetramethylolbenzoguanamine and methyl etherified products of tetramethylolbenzoguanamine; and urea resins such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril, dimethylol dihydroxyethylene urea, and methyl etherified products of dimethylol dihydroxyethylene urea.

[0094] The curable composition (1) may contain one or more compounds that undergo a thermal addition reaction or a thermal condensation reaction with the active hydrogen group. The curable composition (1) does not need to contain a compound having a functional group that undergoes a thermal addition reaction or a thermal condensation reaction with the active hydrogen group. When the curable composition (1) contains a compound having a functional group that undergoes a thermal addition reaction or a thermal condensation reaction with the active hydrogen group, the content of the compound is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 7 to 30% by mass, relative to 100% by mass of the curable composition.

[0095] (Resin Having Hydrophilic Functional Group or Structure) The curable composition (1) further contains a resin having a hydrophilic functional group or structure, which can cause intermolecular interactions with ions contained in the curable composition or, in the case where a compound that undergoes a thermal addition reaction or a thermal condensation reaction with an active hydrogen group is used, can react with such a compound, thereby further improving the water resistance of the cured product.

[0096] Preferred examples of the hydrophilic functional group or structure include a hydroxyl group, a polyoxyethylene structure, an amino group (which may be an amine salt structure with an inorganic or organic acid), an amide group, a carboxyl group (which may be a carboxylate structure with an inorganic or organic base), a sulfonic acid group (which may be a sulfonate structure with an inorganic or organic base), a phosphoric acid group (which may be a phosphate structure with an inorganic or organic base), a quaternary ammonium salt structure, and a betaine structure. These functional groups and structures include the same as those described in the radical polymerizable compound having the above-mentioned hydrophilic functional group or structure.

[0097] Specific examples of the resin having the hydrophilic functional group or structure include polyvinyl alcohol, 2-hydroxyethyl acrylate (co)polymer, polyethylene glycol, poly(ethylene glycol-propylene glycol) copolymer, polyethylene ion, poly(diallyldimethylammonium chloride), polyvinylpyrrolidone, sodium polyacrylate, etc.

[0098] The curable composition (1) may contain one or more resins having the hydrophilic functional group or structure. When the curable composition (1) contains the resin having the hydrophilic functional group or structure, the content thereof is preferably 3 to 30 mass%, more preferably 4 to 25 mass%, and even more preferably 5 to 20 mass%, relative to 100 mass% of the curable composition.

[0099] (Surfactant) The curable composition contains one or more surfactants, which can improve the hydrophilicity of the cured product and the leveling property of the curable composition. The surfactant is not particularly limited as long as it is a compound having a hydrophilic portion and a lipophilic portion in the same molecule and is a commonly known compound as a surfactant, and examples thereof include known anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

[0100] Specific 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; alkylbenzenesulfonates and alkylnaphthalenesulfonates, such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate; polyoxyethylene sulfate salts, such as naphthalenesulfonate-formalin 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.

[0101] Specific 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 fluorine-containing cationic surfactants such as perfluoroalkyltrimethylammonium salts and perfluoroalkenyltrimethylammonium salts.

[0102] Specific examples of nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol; polyoxyethylene sorbitan fatty acid esters such as polypropylene glycol ethylene oxide adduct, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate; phosphate esters such as alkyl phosphate esters and polyoxyethylene alkyl ether phosphate esters; sugar esters, cellulose ethers; perfluoroalkylamine oxynitride; fluorine-containing nonionic surfactants such as perfluoroalkenylamine oxide, perfluoroalkylethylene oxide adducts, perfluoroalkenylethylene oxide adducts, oligomers having a perfluoroalkyl group and a hydrophilic group, oligomers having a perfluoroalkenyl group and a hydrophilic group, oligomers having a perfluoroalkyl group and a lipophilic group, oligomers having a perfluoroalkenyl group and a lipophilic group, oligomers having a perfluoroalkyl group, a hydrophilic group and a lipophilic group, and oligomers having a perfluoroalkenyl group, a hydrophilic group and a lipophilic group; modified silicone-based nonionic surfactants such as polyester-modified silicone and polyether-modified silicone.

[0103] Specific examples of amphoteric surfactants 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; and alkyl glycine.

[0104] The surfactant may have a radical polymerizable group or a functional group that undergoes a thermal addition reaction or thermal condensation reaction with an active hydrogen group. From the viewpoint of polymerizability, the type of radical polymerizable group is preferably a carbon-carbon double bond adjacent to the aforementioned functional group that activates the carbon-carbon double bond. However, considering availability as a surfactant, surfactants having a (meth)acryloyl group, surfactants having an allyloxy structure, and surfactants having an aromatic vinyl structure are preferred. Examples of functional groups that undergo a thermal addition reaction or thermal condensation reaction with an active hydrogen group include the aforementioned epoxy group, oxetanyl group, carbodiimide group, aziridine group, isocyanate group, alkoxysilyl group, and hydroxymethyl or alkoxymethyl group bonded to a nitrogen atom. However, considering availability as a surfactant, surfactants having an epoxy group and surfactants having an alkoxysilyl group are preferred.

[0105] The content of the surfactant may be adjusted depending on the application or purpose, and it does not have to be included; however, when a surfactant is used, the content is preferably 0.001 to 20 mass%, more preferably 0.003 to 15 mass%, and even more preferably 0.005 to 10 mass%, relative to 100 mass% of the curable composition.

[0106] (Inorganic Fine Particles) The curable composition (1) contains one or more types of inorganic fine particles, which can improve the hydrophilicity and hardness of the cured product.

[0107] Examples of inorganic fine particles include fine particles of silica, alumina, zinc oxide, tin oxide, iron oxide, titanium oxide, indium oxide, zirconium oxide, vanadium oxide, cerium oxide, antimony oxide, indium-doped tin oxide, etc. Among these inorganic fine particles, silica, alumina, zinc oxide, titanium oxide, and zirconium oxide are more preferred from the viewpoint of maintaining high transparency.

[0108] The inorganic fine particles may be surface-modified, for example, may have lipophilic alkyl groups or radical polymerizable groups on the surface.

[0109] From the viewpoint of transparency, the particle size of the inorganic fine particles is preferably from 1 to 100 nm, more preferably from 1 to 50 nm, and even more preferably from 1 to 30 nm.

[0110] The content of inorganic fine particles may be adjusted depending on the application or purpose, and they do not necessarily have to be included. However, when inorganic fine particles are used, their content is preferably 0.1 to 90 mass%, more preferably 0.5 to 70 mass%, and even more preferably 1 to 60 mass%, relative to 100 mass% of the curable composition.

[0111] (Radical Polymerization Initiator) The curable composition (1) can improve radical polymerizability by containing one or more radical polymerization initiators. Radical polymerization initiators can be classified into photoradical initiators that generate radicals upon irradiation with active energy rays and thermal radical initiators that generate radicals upon heating. They can be selected according to the application and purpose, and a photoradical initiator and a thermal radical initiator may be used in combination.

[0112] Examples of photoradical initiators include alkylphenone compounds, benzophenone compounds, benzoin compounds, ketal compounds, anthraquinone compounds, phosphine oxide compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, titanocene compounds, benzoic acid ester compounds, and acridine compounds, but the present disclosure is not limited to these examples. These photoradical initiators may be used alone or in combination of two or more.

[0113] Specific examples include acetophenone, 1,1-dichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzene}- alkylphenone compounds such as {4-methyl-1-(4-methylthiophenyl)phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone, 4-benzoyl-4'-methyldiphenyl benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; ketal compounds such as acetophenone dimethyl ketal and benzil dimethyl ketal; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl) ... phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride;Halomethylated triazine compounds such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, and 2-(4-ethoxycarboxynylnaphthyl)-4,6-bis(trichloromethyl)-sec-triazine; 2-trichloromethyl-5-[β-(2'-benzofuryl) halomethylated oxadiazole compounds such as 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; halomethylated oxadiazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2 biimidazole compounds such as 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1-[4-(phenylthio)-,2-(O-benzoyloxime)]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime)ethanone; bis(η5-2,4-cyclopentadiene-1 titanocene compounds such as bis(2,4,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine.

[0114] Suitable thermal radical initiators are organic peroxide initiators and azo initiators. For example, organic peroxide initiators such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetyl acetate peroxide; azo initiators such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobisisobutyronitrile; and the organic peroxide initiators and azo initiators described in JP-A-2020-122053 are exemplified.

[0115] The content of the radical polymerization initiator may be adjusted depending on the application or purpose, and it does not have to be contained; however, when used, the content is preferably 0.01 to 10 mass%, more preferably 0.05 to 8 mass%, and even more preferably 0.01 to 7 mass%, relative to 100 mass% of the curable composition of the present invention.

[0116] (Radical Polymerization Inhibitor) The curable composition (1) contains one or more radical polymerization inhibitors, which can inhibit undesired radical polymerization during storage, transportation, and various operations in preparing and processing the composition.

[0117] As the radical polymerization inhibitor, a primary antioxidant having a radical chain inhibitory property and / or a secondary antioxidant having a peroxide decomposing property can be used.

[0118] Examples of primary antioxidants include hydroquinones, benzoquinones, phenols, aromatic amines, phenothiazines, dithiocarbamic acid metal salts, and nitroso compounds. Examples of secondary antioxidants include phosphorus-based compounds such as phosphine and phosphites, and sulfur-based compounds such as thioethers, mercaptobenzimidazole, and thiourea. The primary antioxidants and secondary antioxidants may be used alone, but are more preferably used in combination. Among primary antioxidants, phenols are preferred from the viewpoint of inhibiting coloration, and among secondary antioxidants, thioethers are preferred from the viewpoint of acid resistance and hydrolysis resistance.

[0119] Examples of phenols include monoetherified hydroquinones, hindered phenols and their polymers (including dimers) or derivatives of the polymers, and semi-hindered phenols and their polymers (including dimers) or derivatives of the polymers.

[0120] Examples of monoetherified hydroquinones include hydroquinone monomethyl ether, hydroquinone mono-n-butyl ether, and the monoetherified hydroquinones described in JP-A-2014-40585.

[0121] Examples of hindered phenols include those described in JP-A-2014-40585, such as 2,6-bis(tert-butyl)-4-methylphenol, octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, and isooctyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate. Examples of oligomers or derivatives of oligomers of hindered phenols include the compounds described in JP-A-2014-40585.

[0122] Examples of semi-hindered phenols include those described in JP-A-2014-40585, such as 6-tert-butyl-o-cresol and 6-tert-butyl-2,4-xylenol. Examples of polymerized products or derivatives of polymerized products of semi-hindered phenols include the compounds described in JP-A-2014-40585.

[0123] Examples of phosphines include triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, and the phosphines described in JP-A-2014-40585.

[0124] Examples of the phosphites include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, and the phosphites described in JP-A-2014-40585.

[0125] Examples of thioethers include 2,2'-thiodiglycolic acid, (ethylenedithio)diacetic acid, 2,2'-(ethylenedithio)diethanol, 3,3'-thiodipropionic acid, dimethyl 3,3'-thiodipropionate, and 3-laurylthiopropionic acid, as well as thioethers described in JP-A-2014-40585.

[0126] The content of the radical polymerization inhibitor may be adjusted depending on the application or purpose, and it does not have to be included; however, when used, the content is preferably 0.0005 to 10 mass%, more preferably 0.001 to 5 mass%, and even more preferably 0.002 to 3 mass%, relative to 100 mass% of the curable composition of the present invention.

[0127] (Solvent) The curable composition (1) contains one or more solvents, which makes it easier to adjust the viscosity and the thickness of the coating film.

[0128] As the solvent, from the viewpoint of compatibility with the radical polymerizable carboxylic acid amine salt compound (A), the epoxy compound (B), and the silane coupling compound (C), a polar organic solvent containing at least one structure selected from the group consisting of a hydroxyl group, an ether structure, an ester structure, a ketone structure, and an amide structure is preferred.

[0129] Specific examples of the polar organic solvent include monoalcohols such as methanol, ethanol, and isopropanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether; Examples of the alkyl ester include esters of glycol monoethers such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0130] The content of the solvent may be adjusted depending on the application or purpose, and may not be included, but when used, the content is preferably 1 to 500 parts by mass, more preferably 2 to 400 parts by mass, and even more preferably 3 to 300 parts by mass, relative to 100 parts by mass of the total nonvolatile content of the curable composition of the present invention. Note that the "total nonvolatile content" refers to the total amount of components that form a cured product in the curable composition (excluding solvents and the like that volatilize during the formation of a cured product).

[0131] The curable composition (1) may further contain components other than those described above depending on the intended use, application, etc., and examples of such components include light stabilizers, ultraviolet absorbers, antistatic agents, antibacterial agents, antifungal agents, deodorizers, thixotropic agents, organic fine particles, dyes, pigments, dispersants, matting agents, anti-settling agents, defoamers, flame retardants, and mold release agents. These may be appropriately selected from known compounds. The content of these compounds may also be appropriately selected from known methods.

[0132] <Curable composition (2)> The curable composition of the second invention is characterized by comprising a polymer (x1) having a structural unit derived from a radically polymerizable carboxylic acid compound (a1), a neutralized polymer (X) of an amine compound (x2), and an epoxy compound (B) and / or a silane coupling compound (C). It is preferable that the composition further comprises a polar organic solvent. Such a curable composition of the second invention is hereinafter also referred to as "curable composition (2)." The curable composition (2) can also provide a cured product having excellent hydrophilicity and water resistance. Each component contained in the curable composition (2) will be described.

[0133] [Neutralized Polymer (X)] The neutralized polymer (X) in the present invention is a neutralized product of a polymer (x1) having a structural unit derived from a radically polymerizable carboxylic acid compound (a1) and an amine compound (x2). All of the carboxylic acid groups may be neutralized, or only a portion of the groups may be neutralized. The base used for neutralization includes at least an amine compound (x2), but may include two or more types, or may include other bases.

[0134] As a method for obtaining the neutralized polymer (X), there can be mentioned two types: a method in which a monomer component containing a radical polymerizable carboxylic acid compound (a1) is polymerized and then neutralized with a base containing an amine compound (x2) (post-neutralization method); and a method in which a monomer component containing a monomer obtained by previously neutralizing a radical polymerizable carboxylic acid compound (a1) with a base containing an amine compound (x2) is polymerized (pre-neutralization method). Either or both may be used, but it is preferable to use at least the post-neutralization method.

[0135] (Polymer (x1)) The polymer (x1) having a structural unit derived from the radical polymerizable carboxylic acid compound (a1) can be obtained, for example, by polymerizing a monomer component containing the radical polymerizable carboxylic acid compound (a1). Examples of the radical polymerizable carboxylic acid compound (a1) used in the curable composition (2) include the same compounds as the radical polymerizable carboxylic acid compound (a1) used in the curable composition (A) described above. From the viewpoint of polymerization activity, the radical polymerizable carboxylic acid compound (a1) preferably contains a compound having a (meth)acryloyl group and / or a 2-(meth)allyloxymethylacryloyl group, and from the viewpoint of improving the solvent solubility of the polymer and the compatibility with the epoxy compound (B) and / or the silane coupling compound (C), it is more preferable that the radical polymerizable carboxylic acid compound (a1) contains a compound having a 2-(meth)allyloxymethylacryloyl group.

[0136] From the viewpoints of improving the solvent solubility of the polymer and the compatibility with the epoxy compound (B) and / or the silane coupling compound (C), and adjusting the balance between the hydrophilicity and water resistance of the cured product, the polymer (x1) preferably has, in addition to the structural unit derived from the radically polymerizable carboxylic acid compound (a1), one or more structural units derived from other radically polymerizable monomers.

[0137] As the other radical polymerizable monomer, the radical polymerizable compound having the hydrophilic functional group or structure described above, or the low-viscosity radical polymerizable compound is preferable. Also, a surfactant having a radical polymerizable group is preferable. Furthermore, these are preferably monofunctional radical polymerizable monomers.

[0138] In the polymer (x1), the content of the structural units derived from the radically polymerizable carboxylic acid compound (a1) is preferably 20 to 80 mass%, more preferably 25 to 75 mass%, and even more preferably 30 to 70 mass%, relative to 100 mass% of all structural units in the polymer (x1).

[0139] The weight-average molecular weight of the polymer (x1) is preferably 5,000 to 300,000, more preferably 7,000 to 200,000, and even more preferably 9,000 to 150,000, from the viewpoint of balancing the viscosity that allows easy application when formed into a curable composition and the water resistance of the cured product. The weight-average molecular weight is determined by measurement using SEC (size exclusion chromatography).

[0140] The polymer (x1) can be obtained by polymerizing the radical polymerizable carboxylic acid compound (a1) and a monomer component containing a compound capable of introducing a structural unit derived from the other radical polymerizable monomer. The polymerization method will be described later in the method for producing the curable composition (2).

[0141] (Amine Compound (x2)) Examples of the amine compound (x2) include compounds similar to the amine compound (a2) in the curable composition (A) described above. Among these, from the viewpoint of improving the hydrophilicity and water resistance of the cured product, the amine compound (x2) preferably includes an amine compound having a hydroxyl group, such as trishydroxymethylaminomethane, 2-amino-2-methyl-1,3-propanediol, triethanolamine, or diethanolamine. Furthermore, from the viewpoint of promoting the reaction in which an epoxy group or an alkoxysilyl group forms a covalent bond with an active hydrogen group, the amine compound (x2) preferably further includes an amine having an amidine structure or an amine having a bicyclocyclic tertiary amine structure, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, diazabicycloundecene, diazabicyclononene, or diazabicyclooctane.

[0142] The content of the amine compound (x2) in the neutralized polymer (X) is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 15 to 45 mass%, relative to 100 mass% of the neutralized polymer (X).

[0143] The content of the neutralized polymer (X) in the curable composition (2) is preferably 4 to 40 mass%, more preferably 5 to 35 mass%, and even more preferably 6 to 30 mass%, relative to 100 mass% of the curable composition.

[0144] [Epoxy compound (B)] Examples of the epoxy compound (B) in the curable composition (2) include the same compounds as the epoxy compound (B) in the curable composition (1). The content of the epoxy compound (B) in the curable composition (2) is preferably 4 to 40 mass%, more preferably 5 to 35 mass%, and even more preferably 6 to 30 mass%, relative to 100 mass% of the curable composition.

[0145] [Silane coupling compound (C)] Examples of the silane coupling compound (C) in the curable composition (2) include the same compounds as the silane coupling compound (C) in the curable composition (1). The content of the silane coupling compound (C) in the curable composition (2) is preferably 4 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 6 to 30% by mass, relative to 100% by mass of the curable composition.

[0146] [Polar Organic Solvent] In order to liquefy the neutralized polymer (X) and to make it compatible with the epoxy compound (B) and / or the silane coupling compound (C), the curable composition (2) preferably contains a polar organic solvent. Examples of the polar organic solvent include polar organic solvents containing at least one of the above-mentioned hydroxyl groups, ether structures, ester structures, ketone structures, and amide structures. Among them, preferred polar organic solvents having a hydroxyl group include monoalcohols such as methanol, ethanol, and isopropanol; glycols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; and glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

[0147] The content of the polar organic solvent in the curable composition (2) is preferably 40 to 95 mass%, more preferably 50 to 90 mass%, and even more preferably 55 to 85 mass%, relative to 100 mass% of the curable composition.

[0148] The curable composition (2) may contain other components in addition to the neutralized polymer (X), the epoxy compound (B), the silane coupling compound (C), and the polar organic solvent. Examples of the other components include the same components as those described in the curable composition (1).

[0149] The method for producing the curable composition (2) is not particularly limited, but preferably includes the following steps (1) and (2) from the viewpoint of reducing the viscosity of the reaction solution during polymerization and facilitating temperature control, and preferably includes the following steps (3) and (4) from the viewpoint of stabilizing the performance of the cured product: (1) a step of polymerizing a monomer component containing the radically polymerizable carboxylic acid compound (a1) to obtain a solution containing a polymer (x); (2) a step of adding the amine compound (x2) to the polymer (x) and neutralizing the polymer to obtain a solution containing the neutralized polymer (X); (3) a step of preparing a solution containing an epoxy compound (B) and / or a silane coupling compound (C); and (4) a step of mixing the solution containing the neutralized polymer (X) with the solution containing the epoxy compound (B) and / or the silane coupling compound (C).

[0150] Step (1) is a step of polymerizing a monomer component containing the radically polymerizable carboxylic acid compound (a1) to obtain a solution containing a polymer (x) as a base polymer. In addition to the radically polymerizable carboxylic acid compound (a1), the monomer component preferably contains a compound capable of introducing a structural unit derived from the other radically polymerizable monomer, such as a radically polymerizable compound having the hydrophilic functional group or structure described above, a low-viscosity radically polymerizable compound, or a surfactant having a radically polymerizable group. The monomer component may also contain a monomer in which the radically polymerizable carboxylic acid compound (a1) is neutralized with the amine compound (x2). The amounts of the various monomers may be appropriately adjusted so that the desired structural unit content in the polymer (x) is achieved.

[0151] In the step (1), the method for polymerizing the monomer components is not particularly limited, but a method of thermally polymerizing the monomer components in a solvent is preferred. Examples of the solvent include the polar organic solvents containing at least one of the above-mentioned hydroxyl groups, ether structures, ester structures, ketone structures, and amide structures. Examples of the polymerization initiator include thermal radical initiators such as the above-mentioned organic peroxide initiators and azo initiators. It is also preferred to use a chain transfer agent in combination, as described in JP-A-2010-168539.

[0152] In step (2), the amine compound (x2) is added to a solution containing the polymer (x1) obtained in step (1) and neutralized to obtain a solution containing the neutralized polymer (X). The neutralization reaction may be carried out by mixing and stirring the polymer (x1) and the amine compound (x2) in the presence of the above-mentioned polar organic solvent, preferably a polar organic solvent having a hydroxyl group. The reaction temperature is not particularly limited and is, for example, 10 to 90°C, preferably 20 to 80°C.

[0153] The amount of the amine compound (x2) added to the polymer (x1) may be appropriately adjusted so that the desired content of the amine compound (x2) in the neutralized polymer (X) is achieved.

[0154] In step (3), a solution containing the epoxy compound (B) and / or the silane coupling compound (C) is prepared. The solution can be prepared by mixing the epoxy compound (B) and / or the silane coupling compound (C) in a solvent. The solvent used is not particularly limited, but preferably contains the polar organic solvent described above.

[0155] In step (4), the solution containing the neutralized polymer (X) is mixed with the solution containing the epoxy compound (B) and / or the silane coupling compound (C). The components are mixed appropriately so that the desired content ratios of the components in the curable composition are obtained. The mixing may be carried out by known mixing or dispersion techniques.

[0156] <Cured Product> The cured product of the present invention is obtained by curing the above-mentioned curable composition (the above-mentioned curable compositions (1) and (2)). The cured product of the present invention is a cured product of the above-mentioned curable composition, and has excellent hydrophilicity and water resistance. Even if the cured product is hydrophilic, if it is water-soluble it will be easily removed on contact with water or moisture and will have no practical use, so the cured product must be water-insoluble. Here, water-insolubility is determined by whether or not the cured product maintains its original shape without dissolving or dispersing in water when immersed in pure water at 23°C for 1 hour. Whether or not the cured product maintains its original shape is determined visually.

[0157] There are various indices for determining hydrophilicity, such as breath anti-fogging property, warm water or hot steam anti-fogging property, water contact angle, surface tension, and surface free energy. However, breath anti-fogging property and water contact angle are preferred from the viewpoint of simplicity and reproducibility. The water-insoluble cured product of the present invention preferably satisfies at least one of the following indices of hydrophilicity: Indicator (I) Exhibits breath anti-fogging property. Indicator (II) Water contact angle is 50° or less.

[0158] Index (I) The determination of whether or not a product exhibits anti-fogging properties against breath is made by the following method. That is, in an environment of 23°C temperature and 50% humidity, breath is blown onto the surface of a cured product from a position 5 cm away in a direction perpendicular to the surface for 3 seconds, and the surface of the cured product is then visually observed. If no fogging occurs, the product is deemed to have anti-fogging properties, and if fogging occurs, the product is deemed not to have anti-fogging properties. Whether or not fogging occurs is determined by visual observation.

[0159] Index (II) The water contact angle of a cured product is measured by determining whether or not the contact angle becomes 50° or less within 3 minutes after a water droplet (2 μL) is deposited on the surface of the cured product. For applications requiring antifouling properties, the water contact angle is preferably 40° or less, more preferably 30° or less, and particularly for applications classified as superhydrophilic, it is even more preferably 20° or less. The water contact angle is measured using a contact angle meter capable of measuring by the sessile drop method, in an environment at a temperature of 23°C and a humidity of 50%, and the static contact angle is calculated by the θ / 2 method based on an image of the droplet after deposition.

[0160] When the occurrence of cloudiness can be easily visually confirmed, it is preferable to judge by index (I), and when the cloudiness is difficult to visually confirm, such as when the cured product is colored or matte, it is preferable to judge by index (II). The cured product may satisfy either index (I) or index (II) or both, depending on the application.

[0161] The method for curing the curable composition (1) includes a step of radically polymerizing the radically polymerizable carboxylic acid amine salt compound (A) (hereinafter, sometimes referred to as the "radical polymerization step"), and a step of reacting the epoxy compound (B) and / or the silane coupling compound (C) with active hydrogen groups in the curable composition by heating (hereinafter, sometimes referred to as the "thermal addition / condensation step"). The order of the radical polymerization step and the thermal addition / condensation step does not matter, and either may be performed first, or they may be performed simultaneously. They may also be performed repeatedly. The method for curing the curable composition (2) includes the thermal addition / condensation step.

[0162] Examples of a method for radically polymerizing the curable composition (1) include a method of heating the curable composition (1), a method of irradiating the curable composition (1) with active energy rays, or a combination thereof. Heating or irradiation with active energy rays may be performed in one step, or may be performed in two separate steps. When both heating and irradiation with active energy rays are performed, these may be performed simultaneously or separately. When heating or irradiation with active energy rays is performed, the curable composition (1) preferably contains a radical polymerization initiator.

[0163] The heating temperature in the radical polymerization step may be appropriately selected depending on the presence or absence, type, content, and application of a radical polymerization initiator. When a thermal radical initiator is used, the heating temperature is preferably 40 to 160°C, more preferably 50 to 150°C, and even more preferably 60 to 140°C.

[0164] As the active energy ray, those that are commonly used can be used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle rays such as electron beams, neutron beams, and proton beams.Among these, in terms of energy intensity, energy ray generator, etc., gamma rays, X-rays, ultraviolet rays, visible light, and electron beams are preferred, ultraviolet rays, visible light, and electron beams are more preferred, and ultraviolet rays are most preferred.When a photoradical initiator is not used, it is preferable to use active energy rays with high energy such as gamma rays, X-rays, and electron beams, and when a photoradical initiator is used, it is preferable to use active energy rays that have relatively low energy but are easy to generate and economical, such as ultraviolet rays and visible light.

[0165] The radical polymerization of the curable composition (1) is preferably carried out under a low oxygen concentration in order to suppress inhibition of radical polymerization by oxygen. To achieve a low oxygen concentration, methods such as blowing an inert gas such as nitrogen or argon over the surface of the curable composition, placing the curable composition in a sealed container filled with an inert gas, placing the curable composition in a sealed container capable of reducing the pressure and reducing the pressure, or adhering a cover film that can be released after curing to the surface of the curable composition can be mentioned.

[0166] The heating temperature in the thermal addition / condensation step of the curable composition (1) may be appropriately selected depending on the type, content, and application of the radically polymerizable carboxylic acid amine salt compound (A), the epoxy compound (B), and the silane coupling compound (C), but is 40 to 170° C., more preferably 70 to 160° C., and even more preferably 90 to 150° C. The heating time may be selected depending on the heating temperature and is not particularly limited, but is preferably 30 seconds to 120 minutes, more preferably 1 minute to 90 minutes, and even more preferably 3 minutes to 60 minutes.

[0167] The heating temperature in the thermal addition / condensation step of the curable composition (2) may be appropriately selected depending on the type and content of the neutralized polymer (X), the epoxy compound (B), the silane coupling compound (C), and the polar organic solvent, and the intended use, but is 40 to 170° C., more preferably 70 to 160° C., and even more preferably 90 to 150° C. The heating time may be selected depending on the heating temperature and is not particularly limited, but is preferably 30 seconds to 120 minutes, more preferably 1 minute to 90 minutes, and even more preferably 3 minutes to 60 minutes.

[0168] <Article Having Cured Product> The present invention also relates to an article having the above-described cured product on its surface. By applying the curable composition for obtaining the above-described cured product to the surface of a substrate and obtaining the cured product by the above-described method, an article having a cured film with excellent hydrophilicity and water resistance can be obtained.

[0169] The type and shape of the substrate are not particularly limited and may be appropriately selected depending on the application and purpose. Specific examples of the type of substrate include inorganic substrates such as glass, iron, stainless steel, and aluminum; and organic substrates such as silicone resins, acrylic resins, methacrylic resins, fluororesins, alkyd resins, aminoalkyd resins, vinyl resins, polyester resins, styrene-butadiene resins, polyolefin resins, polystyrene resins, polyketone resins, polyamide resins, polycarbonate resins, polyacetal resins, polyether ether ketone resins, polyphenylene oxide resins, polysulfone resins, polyphenylene sulfone resins, polyether resins, polyvinyl chloride resins, polyvinylidene chloride resins, urea resins, phenolic resins, melamine resins, epoxy resins, urethane resins, silicone-acrylic resins, cellulose-based resins, isoprene-based resins such as natural rubber, and protein-based resins such as casein.

[0170] The surface of the substrate to which the curable composition is applied may be provided with a functional layer such as an adhesion-improving primer, a colored coating, an antireflection layer, a gas barrier layer, or a transparent conductive layer, or may be subjected to a surface treatment such as a corona discharge treatment, a flame treatment, or a plasma treatment.

[0171] The method for applying the curable composition is not particularly limited and may be appropriately selected depending on the type and shape of the substrate. Specific examples include spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, and flexographic printing.

[0172] After the curable composition is applied, drying or the like is carried out as necessary, and then the curing method described above is carried out, whereby a hydrophilic cured film can be satisfactorily formed on the substrate.

[0173] The film thickness of the cured product in the above-mentioned article is not particularly limited and may be appropriately selected depending on the purpose or application. In order to form a smooth and uniform coating film using a general-purpose device, the film thickness is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and even more preferably 2 to 15 μm.

[0174] <Applications> The curable composition, cured product, and article of the present invention can be used in a variety of fields, including everyday items such as eyeglasses, helmets, bathroom mirrors, automobile lamps, air conditioner heat exchangers, camera lenses, and endoscopes, as well as building materials, transportation equipment, home appliances, precision electronic devices, and medical equipment. Furthermore, by taking advantage of the various durability improvements achieved by the reaction of the epoxy compound and / or silane coupling compound with the active hydrogen group, the composition can be applied to a variety of applications, including various coatings other than hydrophilic coatings (such as anti-crack coatings for brittle films, protective coatings for decorative films, and phase difference adjustment coatings), primers, sealants, adhesives, encapsulants, pressure-sensitive adhesives, various methods of three-dimensional modeling (inkjet, SLA, DLP), thermoplastic molding, thermosetting molding, hot-melt adhesives, optical films, lenses, electronic components, prepregs, dental materials, paints, printing inks, fiber treatment agents, and resist materials for microfabrication.

[0175] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0176] The measurement and evaluation methods used in this example are as follows. <Quantitative Determination of 2-Allyloxymethylacrylic Acid> 2-Allyloxymethylacrylic acid with a purity of 96.5% was prepared, containing 0.04% (based on the total liquid volume) of hydroquinone monomethyl ether and 0.06% (based on the total liquid volume) of 2,2'-(ethylenedithio)diethanol as radical polymerization inhibitors. The purity was measured using the following capillary electrophoresis system. - Measurement Device - Capillary Electrophoresis System: Agilent 7100 (Agilent Technologies, Inc.) - Measurement Conditions - Measurement was performed by indirect absorption using a background absorbent. Capillary: Bubble self-fused silica capillary (inner diameter 75 μm x total length 80.5 cm) Running solution: Running solution for anion analysis (pH = 8.2) Applied voltage: -20 kV - Quantification method - Quantification was performed using the internal standard method based on the area ratio (internal standard substance: sodium propionate). Preparation of standard sample: Sodium propionate and the substance to be quantified (sodium salt of carboxylate ion) were dissolved in heavy water. １ After determining the molar ratio by H-NMR, the solution was further diluted with ultrapure water to prepare a standard sample for preparing a calibration curve. Preparation of measurement samples: The aqueous sodium propionate solution and the test sample were weighed and diluted with 0.1 N aqueous sodium hydroxide solution and ultrapure water to prepare a measurement sample.

[0177] <Water Resistance> (Preparation of Laminate) In Examples 1 to 9, the curable composition was applied to a 100 μm-thick PET film (Lumirror Film T60, Toray Industries, Inc.) using a bar coater No. 4 to obtain an uncured coating film with a dry film thickness of 8 to 9 μm. The coating was applied using a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 150 mW / cm ２ , under a nitrogen atmosphere) to apply a cumulative light dose of 1000 mJ / cm ２The film was fixed to a glass plate with clips and heated in an oven at 130°C for 30 minutes, then removed from the oven and the clips were removed to obtain a laminate in which a cured layer was formed on a PET film. For Examples 10 and 11, laminates were obtained in the same manner as in Examples 1 to 9, except that the curable composition was applied using bar coater No. 3 to give an uncured coating film with a dry film thickness of 5 to 6 μm. For Comparative Examples 1 to 5, the curable composition was applied to a 100 μm-thick PET film (Lumirror Film T60, Toray Industries, Inc.) using bar coater No. 4, and dried on a hot plate heated to 70°C for 1 minute to obtain an uncured coating film with a dry film thickness of approximately 5 μm. Next, the curable composition was applied to a belt conveyor-type UV irradiation device (high-pressure mercury lamp, illuminance 150 mW / cm ２ , under a nitrogen atmosphere) to apply a cumulative light dose of 1000 mJ / cm ２ Thus, a laminate in which a cured layer was formed on the PET film was obtained.

[0178] (Water Resistance Evaluation) The laminate obtained above was used as a test article. The test article was immersed in ion-exchanged water at 23°C for 24 hours, and then removed. Pure water was poured onto the surface using a wash bottle containing ion-exchanged water, and the test article was then air-dried at room temperature. The surface after air-drying was visually observed, and a mark indicating no change in the appearance of the surface (cured product) was given as "○", while a mark indicating that the original shape was not maintained, such as that the surface had dissolved and disappeared, or that partial swelling or peeling was observed, or that the original shape was maintained but the surface had turned white was given as "×".

[0179] <Anti-fogging properties due to breath after water resistance test> For the test articles that had undergone the above-mentioned water resistance test, breath was sprayed onto the surface of the test article for 3 seconds from a position 5 cm away from the surface of the test article in an environment of a temperature of 23°C and a humidity of 50%, and those that did not produce fogging were marked with "○", and those that did produce fogging were marked with "×".

[0180] <Water Contact Angle After Water Resistance Test> For the test article that underwent the water resistance test, the contact angle was measured 30 seconds and 3 minutes after a water droplet landed on the surface of the test article using an MSA Flex (manufactured by KRUESS) contact angle meter under the following conditions: Measurement temperature: 23°C, humidity: 50% Amount of pure water dropped: 2 μL Calculation of measurement value: The static contact angle was measured at three arbitrary locations on the surface of the test article using the θ / 2 method, and the average value was taken as the water contact angle.

[0181] <Pencil Hardness After Water Resistance Test> The pencil hardness of the test article that had been subjected to the water resistance test was measured using an electric pencil hardness tester under a load of 750 g.

[0182] Example 1: 0.009 g of a fluorochemical surfactant (Ftergent 215M, Neos Corporation), 0.2 g of methanol, 1.04 g of 2-allyloxymethylacrylic acid, and 0.52 g of N,N'-bis(2-hydroxyethyl)ethylenediamine were weighed into a screw tube containing a stirrer and stirred until the mixture was transparent while heating to 50°C. Then, 1.38 g of methoxypolyethylene glycol acrylate (NK Ester AM-230G, Shin-Nakamura Chemical Co., Ltd.) was added and stirred until homogenous. After returning the mixture to room temperature, 0.85 g of 3-(trimethoxysilyl)propyl acrylate and 0.85 g of polyethylene glycol diglycidyl ether (Denacol EX-850, Nagase ChemteX Corporation) with an average repeating number of polyethylene glycol chains of 2 were added and stirred until homogenous. Finally, 0.15 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a coating liquid (curable composition) having an active ingredient content of more than 90 mass % at a weight ratio as shown in Table 1. The substances represented by the abbreviations shown in Table 1 are as shown in Table 2. Test articles were produced using the prepared curable compositions as described above, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0183] Example 2 0.007 g of a fluorochemical surfactant (Ftergent 215M, Neos Corporation), 0.2 g of methanol, 1.04 g of 2-allyloxymethylacrylic acid, and 0.10 g of zinc oxide were weighed into a screw tube containing a stirrer and stirred until the mixture became transparent while heating to 50°C. Then, 0.34 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and stirred until the mixture became homogeneous. After returning the mixture to room temperature, 0.82 g of 3-(trimethoxysilyl)propyl acrylate and 1.32 g of polyethylene glycol diglycidyl ether (Denacol EX-830, Nagase ChemteX Corporation) with an average repeating number of polyethylene glycol chains of 9 were added and stirred until homogenous. Finally, 0.09 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0184] Example 3 0.007 g of a fluorochemical surfactant (Ftergent 215M, Neos Corporation), 0.2 g of methanol, 1.04 g of 2-allyloxymethylacrylic acid, and 0.10 g of zinc oxide were weighed into a screw tube containing a stirrer and stirred until the mixture was transparent while heating to 50°C. Then, 0.34 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and stirred until the mixture was homogenous. After returning to room temperature, 0.82 g of 3-(trimethoxysilyl)propyl acrylate, 0.60 g of polyethylene glycol diglycidyl ether having an average repeat number of 2 polyethylene glycol chains (Denacol EX-850, Nagase ChemteX Corporation), and 0.71 g of polyethylene glycol diglycidyl ether having an average repeat number of 13 polyethylene glycol chains (Denacol EX-841, Nagase ChemteX Corporation) were added and stirred until homogenous. Finally, 0.09 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0185] Example 4 0.007 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.2 g of methanol, 1.04 g of 2-allyloxymethylacrylic acid, and 0.11 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred until transparent while heating to 50°C. Then, 0.31 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and stirred until homogenous. After returning the mixture to room temperature, 0.82 g of 3-(trimethoxysilyl)propyl acrylate, 0.33 g of 3-glycidyloxypropyltrimethoxysilane, 0.26 g of trimethylolpropane polyglycidyl ether (Denacol EX-321, Nagase ChemteX Corporation), 0.33 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 9 (Denacol EX-830, Nagase ChemteX Corporation), and 0.13 g of lauryloxy polyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation) were added and stirred to homogenize. Finally, 0.09 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0186] Example 5 0.007 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.2 g of methanol, 1.04 g of 2-allyloxymethylacrylic acid, and 0.11 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred until transparent while heating to 50°C. Then, 0.31 g of N,N'-bis(2-hydroxyethyl)ethylenediamine was added and stirred until homogenous. After returning the mixture to room temperature, 0.14 g of 2-ethylhexyl acrylate, 0.77 g of 3-(trimethoxysilyl)propyl acrylate, 0.35 g of 3-glycidyloxypropyltrimethoxysilane, 0.18 g of glycerol polyglycidyl ether (Denacol EX-313, Nagase ChemteX Corporation), 0.18 g of hydrogenated bisphenol A epoxy resin (jER YX8000, Mitsubishi Chemical Corporation), 0.35 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 9 (Denacol EX-830, Nagase ChemteX Corporation), and 0.14 g of lauryloxy polyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation) were added and stirred to homogenize. Finally, 0.09 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0187] Example 6 0.004 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.2 g of methanol, 0.85 g of 2-allyloxymethylacrylic acid, 0.18 g of acrylic acid, and 0.13 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred while heating to 50°C until the mixture became transparent. Then, 0.48 g of diallylamine was added and stirred while cooling in an ice bath. After returning the mixture to room temperature, 0.40 g of 4-hydroxybutyl acrylate, 0.79 g of 3-(trimethoxysilyl)propyl acrylate, 0.32 g of 3-glycidyloxypropyltrimethoxysilane, 0.32 g of hydrogenated bisphenol A epoxy resin (jER YX8000, Mitsubishi Chemical Corporation), 0.40 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 9 (Denacol EX-830, Nagase ChemteX Corporation), and 0.16 g of lauryloxypolyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation) were added and stirred to make a homogenous mixture. Finally, 0.11 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0188] Example 7 0.004 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.2 g of methanol, 0.85 g of 2-allyloxymethylacrylic acid, 0.18 g of acrylic acid, and 0.13 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred while heating to 50°C until the mixture became transparent. Then, 0.48 g of diallylamine was added and stirred while cooling in an ice bath. After returning the mixture to room temperature, 0.40 g of 4-hydroxybutyl acrylate, 0.79 g of 3-(trimethoxysilyl)propyl methacrylate, 0.32 g of 3-glycidyloxypropyltrimethoxysilane, 0.32 g of hydrogenated bisphenol A epoxy resin (jER YX8000, Mitsubishi Chemical Corporation), 0.40 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 9 (Denacol EX-830, Nagase ChemteX Corporation), and 0.16 g of lauryloxypolyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation) were added and stirred to make a homogenous mixture. Finally, 0.11 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0189] Example 8 0.004 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.2 g of methanol, 0.69 g of 2-allyloxymethylacrylic acid, 0.34 g of acrylic acid, and 0.19 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred while heating to 50°C until the mixture became transparent. Then, 0.46 g of diallylamine was added and stirred while cooling in an ice bath. After returning the mixture to room temperature, 0.37 g of 4-hydroxybutyl acrylate, 0.64 g of 3-(trimethoxysilyl)propyl acrylate, 0.30 g of 3-glycidyloxypropyltrimethoxysilane, 0.30 g of hydrogenated bisphenol A epoxy resin (jER YX8000, Mitsubishi Chemical Corporation), 0.37 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 9 (Denacol EX-830, Nagase ChemteX Corporation), and 0.15 g of lauryloxypolyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation) were added and stirred to make a homogenous mixture. Finally, 0.10 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0190] Example 9 0.004 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.2 g of methanol, 0.69 g of 2-allyloxymethylacrylic acid, 0.34 g of acrylic acid, and 0.19 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred while heating to 50°C until the mixture became transparent. Then, 0.46 g of diallylamine was added and stirred while cooling in an ice bath. After returning the mixture to room temperature, 0.37 g of 4-hydroxybutyl acrylate, 0.64 g of 3-(trimethoxysilyl)propyl methacrylate, 0.30 g of 3-glycidyloxypropyltrimethoxysilane, 0.30 g of hydrogenated bisphenol A epoxy resin (jER YX8000, Mitsubishi Chemical Corporation), 0.37 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 9 (Denacol EX-830, Nagase ChemteX Corporation), and 0.15 g of lauryloxypolyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation) were added and stirred to make a homogenous mixture. Finally, 0.10 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of more than 90 mass % at the weight ratio of the active ingredient shown in Table 1. Test articles were prepared in the same manner as in Example 1, and the water resistance, breath anti-fogging property, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0191] Example 10 0.003 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.20 g of trishydroxymethylaminomethane, 0.49 g of 2-allyloxymethylacrylic acid, and 0.6 g of methanol were weighed into a screw tube containing a stirrer, and the mixture was stirred while heating to 50°C until the solid was completely dissolved. After the mixture was returned to room temperature, 0.30 g of 3-aminopropyltrimethoxysilane was added and stirred. Next, 0.81 g of 4-hydroxybutyl acrylate, 0.65 g of 3-glycidyloxypropyltrimethoxysilane, 0.65 g of hydrolysis / polycondensation oligomer of tetramethoxysilane (MKC Silicate MS51, Mitsubishi Chemical Corporation), 0.16 g of lauryloxy polyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation), and 0.06 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) were added and stirred to homogenize. Separately, 0.20 g of 2-allyloxymethylacrylic acid, 0.21 g of diazabicycloundecene, and 0.40 g of ethyl acetate were weighed into a screw tube and shaken to homogenize. Then, 0.38 g of the mixture was taken and added to the screw tube containing the previously prepared curable composition and stirred. The mixture was filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of approximately 80% by mass, with the weight ratio of the active ingredient being as shown in Table 1. Test articles were prepared using the prepared curable composition as described above, and the breath anti-fogging properties, water contact angle, and pencil hardness after the water resistance test were evaluated. The results are shown in Table 1.

[0192] Example 11 0.003 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 0.37 g of trishydroxymethylaminomethane, 0.45 g of 2-allyloxymethylacrylic acid, and 0.6 g of methanol were weighed into a screw tube containing a stirrer, and the mixture was stirred while being heated to 50°C until the solid was completely dissolved, and then the mixture was returned to room temperature. Next, 0.48 g of 4-hydroxybutyl acrylate, 0.32 g of glycerol monomethacrylate, 0.58 g of 3-glycidyloxypropyltrimethoxysilane, 0.77 g of hydrolysis / polycondensation oligomer of tetramethoxysilane (MKC Silicate MS51, Mitsubishi Chemical Corporation), 0.13 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 13 (Denacol EX-841, Nagase ChemteX Corporation), 0.13 g of lauryloxy polyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation), and 0.06 g of 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, IGM Resins) were added, and the mixture was stirred to be homogenized. Separately, 0.20 g of 2-allyloxymethylacrylic acid, 0.21 g of diazabicycloundecene, and 0.40 g of ethyl acetate were weighed into a screw tube and shaken to homogenize. Then, 0.38 g of the mixture was taken and added to the screw tube containing the previously prepared curable composition, followed by stirring. The mixture was filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient content of approximately 80% by mass, with the active ingredient being in the weight ratio shown in Table 1. Test articles were prepared in the same manner as in Example 10, and the breath anti-fogging properties after the water resistance test, the water contact angle after the water resistance test, and the pencil hardness after the water resistance test were evaluated. The results are shown in Table 1.

[0193] Comparative Example 1 0.004 g of a fluorine-based surfactant (Ftergent 215M, Neos Corporation), 1.5 g of ultrapure water, 1.03 g of 2-allyloxymethylacrylic acid, 0.50 g of acrylic acid, and 0.57 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred until transparent while heating to 50° C. After returning to room temperature, 0.064 g of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Omnirad 2959, IGM Resins) was added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient weight ratio as shown in Table 1 and a solvent (water) content of approximately 45% by mass. Test articles were prepared using the prepared curable compositions as described above, and the breath anti-fogging properties, water contact angle, and pencil hardness after the water resistance test were evaluated. The results are shown in Table 1.

[0194] (Comparative Example 2) 0.004 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 1.55 g of ultrapure water, 0.62 g of 2-allyloxymethylacrylic acid, 0.91 g of acrylic acid, and 0.69 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred at 50 ° C until transparent. After returning to room temperature, 0.061 g of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Omnirad 2959, IGM Resins) was added, stirred until the powder dissolved, and then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient weight ratio as shown in Table 1 and a solvent (water) content of approximately 45% by mass. Test articles were prepared in the same manner as in Comparative Example 1, and water resistance, breath anti-fogging properties, water contact angle, and pencil hardness were evaluated. The results are shown in Table 1.

[0195] (Comparative Example 3) 0.003 g of a fluorine-based surfactant (Ftergent 215M, Neos Co., Ltd.), 1.1 g of ultrapure water, 0.62 g of 2-allyloxymethylacrylic acid, 0.91 g of acrylic acid, and 0.49 g of magnesium hydroxide were weighed into a screw tube containing a stirrer, and the mixture was stirred until transparent while heating to 50 ° C. After returning to room temperature, 0.051 g of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Omnirad 2959, IGM Resins) was added, stirred until the powder dissolved, and then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient weight ratio as shown in Table 1 and a solvent (water) content of approximately 45% by mass. A test article was prepared in the same manner as in Comparative Example 1, and water resistance evaluation was performed. However, the water resistance was not good, so other evaluations could not be performed.

[0196] (Comparative Example 4) 0.005 g of a fluorochemical surfactant (Ftergent 215M, Neos Co., Ltd.), 1.9 g of ultrapure water, 0.62 g of 2-allyloxymethylacrylic acid, 0.91 g of acrylic acid, and polyethyleneimine (K-85, Nippon Shokubai Co., Ltd.) were weighed into a screw tube containing a stirrer and stirred at room temperature until the mixture became transparent. Then, 0.058 g of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Omnirad 2959, IGM Resins) was added, stirred until the powder dissolved, and then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient weight ratio as shown in Table 1 and a solvent (water) content of approximately 45% by mass. A test article was prepared in the same manner as in Comparative Example 1, and water resistance evaluation was performed. However, the water resistance was poor, so other evaluations could not be performed.

[0197] Comparative Example 5: 0.005 g of a fluorine-based surfactant (Ftergent 215M, Neos Co., Ltd.), 2.0 g of ultrapure water, 0.44 g of 2-allyloxymethylacrylic acid, 1.08 g of acrylic acid, and 0.73 g of zinc oxide were weighed into a screw tube containing a stirrer, and the mixture was stirred until transparent while heating to 50°C. After returning to room temperature, 0.52 g of glycerol monomethacrylate and 0.078 g of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Omnirad 2959, IGM Resins) were added, and the mixture was stirred until the powder was dissolved. The mixture was then filtered through a membrane filter with a pore size of 0.45 μm to obtain a curable composition having an active ingredient weight ratio as shown in Table 1 and a solvent (water) content of approximately 45% by mass. A test article was prepared in the same manner as in Comparative Example 1 and subjected to a water resistance evaluation. However, the water resistance was not good, so other evaluations could not be performed.

[0198]

[0199]

[0200] It was confirmed from Tables 1 and 2 that the coating liquids (compositions) of the Examples were capable of forming cured films with excellent water resistance and hydrophilicity. Furthermore, the cured films obtained using the coating liquids of the Examples also had excellent hardness.

[0201] Example 12 (Production Process 1) Synthesis of Base Polymer A 100 mL reaction vessel equipped with a stirring blade, a condenser, a thermometer, and a nitrogen inlet tube was charged with 6.21 g of 2-allyloxymethylacrylic acid, 3.20 g of 4-hydroxybutyl acrylate, 2.56 g of acryloylmorpholine, 7.30 g of propylene glycol monomethyl ether, and 3.92 g of methanol. The mixture was stirred at room temperature for 30 minutes while flowing nitrogen at 0.5 mL / min. The reaction vessel was heated in an oil bath, and after confirming that reflux had commenced and the internal temperature had reached 87°C, 0.43 g of a 30% solution of pentaerythritol tetrakis(3-mercaptobutyrate) (solvent: propylene glycol monomethyl ether) and 0.26 g of a 10% solution of t-butylperoxy-2-ethylhexanoate (solvent: propylene glycol monomethyl ether) were added to the reaction vessel in this order to initiate polymerization. While adjusting the heating so that the internal temperature remained at 90°C ± 3°C, 6.0 g of propylene glycol monomethyl ether was added dropwise over 60 minutes. Sixty minutes after the start of polymerization, 1.09 g of 2-allyloxymethylacrylic acid and 12.0 g of propylene glycol monomethyl ether were added. After the internal temperature returned to 87°C, 0.51 g of a 10% solution of t-butylperoxy-2-ethylhexanoate (solvent: propylene glycol monomethyl ether) was added, and heating was continued for 90 minutes, followed by cooling to room temperature. The weight of the reaction vessel containing the contents was measured, yielding a base polymer solution with an active ingredient concentration of 30.2% (the proportion of the total amount of 2-allyloxymethylacrylic acid, 4-hydroxybutyl acrylate, acryloylmorpholine, and pentaerythritol tetrakis(3-mercaptobutyrate) charged to the total weight of the contents).

[0202] (Production process 2-1) Preparation of solution A 1.50 g of the base polymer solution, 1.14 g of propylene glycol monomethyl ether, 1.34 g of propylene glycol, 0.084 g of diazabicycloundecene, and 0.134 g of trishydroxymethylaminomethane were weighed into a screw tube containing a stirrer, and the mixture was stirred at 60°C until homogenous. The mixture was then returned to room temperature to obtain solution A.

[0203] (Production Process 2-2) Preparation of Solution B Into a screw tube containing a stirrer were weighed 0.11 g of 3-glycidyloxypropyltrimethoxysilane, 0.11 g of hydrolysis / polycondensation oligomer of tetramethoxysilane (MKC Silicate MS56, Mitsubishi Chemical Corporation), 0.022 g of polyethylene glycol diglycidyl ether having an average repeating number of polyethylene glycol chains of 4 (Denacol EX-821, Nagase ChemteX Corporation), 0.022 g of lauryloxypolyethylene glycol glycidyl ether (Denacol EX-171, Nagase ChemteX Corporation), and 0.48 g of a mixed solution of propylene glycol monomethyl ether / propylene glycol = 2 / 1 (weight ratio), and the mixture was stirred at room temperature until homogenous to obtain Solution B.

[0204] (Production Step 3) 0.88 g of Solution A and 0.61 g of Solution B were weighed into a screw tube containing a stirrer and stirred for 3 minutes to obtain a curable composition with an active ingredient concentration of 18.2%.

[0205] Thirty minutes after the start of stirring, the curable composition obtained above (a mixture of liquids A and B) was applied to a 125 μm-thick PET film (Lumirror Film T60, Toray Industries, Inc.) using a bar coater No. 8, and then heated on a hot plate at 120° C. for 30 minutes, thereby obtaining a laminate (test article) in which a cured layer having a thickness of approximately 3 μm was formed on the PET film.

[0206] (Evaluation before immersion in water) Antifouling property: A mark (x) was made on the cured layer of the test article with a black ink marker. Pure water was placed on the mark, and after 3 minutes, it was wiped with a paper wiper. If the mark could be erased, it was evaluated as O; if not, it was evaluated as X.

[0207] (Evaluation after immersion in water) The change in appearance (water resistance), breath anti-fogging property, water contact angle, and pencil hardness were evaluated one day after immersion in water in the same manner as in Example 1. The results of each of the above evaluations are shown in Table 3 together with the mass ratios of the components of the curable composition. The structures or substances represented by the abbreviations shown in Table 3 are as shown in Table 4.

[0208] (Examples 13 to 16) Test articles were prepared and evaluated in the same manner as in Example 12, except that the type and amount of each component in (Production process 2-2) and the amounts of Liquid A and Liquid B in (Production process 3) were changed so as to obtain a curable composition with the mass ratio of the constituent components and an active ingredient concentration of 18.2% as shown in Table 3. The results are shown in Table 3.

[0209]

[0210]

[0211] From Tables 3 and 4, it was confirmed that the cured films formed from the curable compositions of Examples 12 to 16 also had excellent water resistance and hydrophilicity, as well as excellent antifouling properties.

Claims

1. A curable composition comprising a radically polymerizable carboxylic acid amine salt compound (A) which is a neutralization product of a radically polymerizable carboxylic acid compound (a1) and an amine compound (a2), and an epoxy compound (B) and / or a silane coupling compound (C), wherein at least one of the radically polymerizable carboxylic acid compound (a1) and the amine compound (a2) has 5 or more carbon atoms.

2. The curable composition according to claim 1, wherein the radical polymerizable group of the radical polymerizable carboxylic acid amine salt compound (A) is a (meth)acryloyl group and / or a 2-(meth)allyloxymethylacryloyl group.

3. A curable composition comprising a neutralized polymer (X) of a polymer (x1) having a structural unit derived from a radically polymerizable carboxylic acid compound (a1) and an amine compound (x2), and an epoxy compound (B) and / or a silane coupling compound (C).

4. The curable composition according to claim 3, characterized in that the radically polymerizable carboxylic acid compound (a1) is a compound having a (meth)acryloyl group and / or a 2-(meth)allyloxymethylacryloyl group.

5. The curable composition according to claim 3, characterized in that the amine compound (x2) includes an amine compound having a hydroxyl group.

6. A cured product of the curable composition according to any one of claims 1 to 5.

7. An article having the cured product according to claim 6 on its surface.

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