Silica particle-containing composition and cured product thereof

Abstract

To provide a silica particle-containing composition, the cured body of which has improved excoriation resistance and heat resistance.SOLUTION: A composition contains a silica particle, and a specific diene-based carboxylate represented by a formula (1). Alternatively, a composition contains a silica particle, and at least one selected from the group consisting of a specific diene-based carboxylic acid or ester represented by a formula (2) and a specific diene-based carboxylic acid anion represented by a formula (3). The contents of the components are in specific ranges. Preferably, the silica particles have an average primary particle size of 100 nm or less, and the silica particles have a coefficient of variation in particle size of 25% or less. There is also provided a cured product of the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a silica particle-containing composition and a cured product thereof. [Background technology]

[0002] Conventional curable compositions composed solely of organic monomers have the problem of low heat resistance and scratch resistance after curing. To address this problem, a technique has been proposed in which inorganic fillers are added to the composition to improve heat resistance and scratch resistance. For example, Patent Document 1 discloses that adding silica particles that meet specific parameters to a photocurable coating composition can achieve high scratch resistance. It is also generally known that adding silica to a photocurable composition increases the inorganic component content in the composition, improving heat resistance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-12078 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, in the case of a photocurable composition, adding an inorganic filler to the composition makes it difficult to ensure curability at a predetermined light intensity, and also impairs transparency, limiting its applications. Therefore, an object of the present invention is to provide a silica particle-containing composition that can ensure predetermined curability and transparency while satisfying heat resistance and scratch resistance. [Means for solving the problem]

[0005] As a result of investigations, the present inventors have found that by forming a composition containing [Component A] silica particles and [Component B] at least one of a diene carboxylic acid, a diene carboxylic acid anion, and a diene carboxylic acid ester, it is possible to impart heat resistance and scratch resistance to the resulting cured product, and further to achieve the curability and transparency required for the composition, thereby completing the present invention.

[0006] The present invention is configured as follows. [1] [Component A-1] Silica particles and [Component B-1] A composition containing a diene carboxylic acid ester represented by the following formula (1):

[0007] [ka] In the above formula (1), R 1 is an organic group having 5 to 15 carbon atoms, R 2 is a hydrogen atom or a methyl group, X 1 , Y 1 , and Z 1 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 1 , Y 1 and Z 1 At least one of the is an oxygen atom. [2] [Component A-2] Silica particles, A composition comprising [Component B-2] at least one selected from the group consisting of diene carboxylic acids and esters represented by the following formula (2), and [Component B-3] diene carboxylate anions represented by the following formula (3), A composition in which [Component A-2] is 15% by mass or more based on 100% by mass of the solid components of the composition, and the total amount of [Component B-2] and [Component B-3] is 5% by mass or more based on 100% by mass of the solid components of the composition.

[0008] [ka] In the above formula (2), R 3 is a hydrogen atom or an organic group having 1 to 4 carbon atoms, R 4 is a hydrogen atom or a methyl group, X 2 , Y 2 , and Z 2 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 2 , Y 2 and Z 2 At least one of the is an oxygen atom.

[0009] [ka] In the above formula (3), R 5 is a hydrogen atom or a methyl group, X 3 , Y 3 , and Z 3 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 3 , Y 3 , and Z 3 At least one of the oxygen atoms is an oxygen atom, and the oxygen-carbon-oxygen bond represented by the dotted line and the solid line indicates that the two carbon-oxygen bonds contained within this bond are equivalent, and the entire oxygen-carbon-oxygen bond forms a monovalent anion. [3] The composition according to [1] or [2], wherein the average primary particle diameter of the silica particles is 100 nm or less. [4] The composition according to any one of [1] to [3], wherein the coefficient of variation of the particle diameter of the silica particles is 25% or less. [5] A cured product of the composition according to any one of [1] to [4]. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a composition that is imparted with heat resistance and scratch resistance while ensuring curability and transparency. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention is a composition comprising [Component A] silica particles and [Component B] at least one of a diene carboxylic acid, a diene carboxylic acid anion, and a diene carboxylic acid ester having a predetermined structure.

[0012] [Components A-1 and A-2] Silica particles The average primary particle diameter of the silica particles of the present invention is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 50 nm or less, and preferably 5 nm or more, more preferably 10 nm or more. When the average primary particle diameter of the silica particles is within the above range, the transparency of the silica particle-containing composition is easily improved. As shown in the examples described below, the average primary particle diameter can be calculated by observing the particles with a scanning electron microscope (SEM), measuring the major axis of each of 50 particles from images taken at a measurement magnification set so that 50 to 100 particles are included in a single field of view, and calculating the arithmetic average value of these.

[0013] The coefficient of variation (CV value) of the primary particle diameter of the silica particles is preferably 25% or less, more preferably 20% or less, even more preferably 18% or less, and even more preferably 15% or less. The lower limit of the CV value is not particularly limited, but may be, for example, 5% or more. The coefficient of variation of the primary particle diameter is a value expressed as a percentage by dividing the standard deviation of the primary particle diameter by the average value of the primary particle diameter.

[0014] The average sphericity ratio of the silica particles is preferably 1.2 or less, more preferably 1.1 or less, even more preferably 1.05 or less, and preferably at least 1. The average sphericity ratio can be determined by observing the silica particles under a transmission electron microscope (magnification: 200,000 times), measuring the major axis and minor axis of each silica particle to calculate the sphericity ratio (major axis / minor axis), and averaging the sphericity ratios measured for 50 silica particles.

[0015] The silica particles may be surface-treated with a surface treatment agent, which preferably contains at least one of an organosilicon compound, an organic acid, and a titanium coupling agent, and more preferably contains at least an organosilicon compound.

[0016] The organosilicon compound is preferably a silane coupling agent or a silazane compound.

[0017] The silane coupling agent refers to a compound in which a hydrolyzable group (a group that can form a silanol group by hydrolysis) and an organic group are bonded to a central silicon atom.

[0018] Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Triethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, p-styryltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamino N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane Alkoxysilane compounds such as acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane; chlorosilane compounds such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, methylvinyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and methyldiphenylchlorosilane;Examples of suitable silane compounds include acyloxysilane compounds such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, and trimethylacetoxysilane; and silanol compounds such as dimethylsilanediol, diphenylsilanediol, and trimethylsilanol.

[0019] The silazane compound refers to a compound having an Si-N-Si bond in the molecule. Examples of the silazane compound include 1,1,1,3,3,3-hexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis(chloromethyl)tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, lithium hexamethyldisilazane, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.

[0020] The content of the organosilicon compound is preferably 1% by mass or more, more preferably 10% by mass or more, and preferably 100% by mass or less, based on 100% by mass of the surface treatment agent. The content of the silazane compound is preferably 1% by mass or more, more preferably 10% by mass or more, and preferably 100% by mass or less, based on 100% by mass of the total of the silazane compound and the silane coupling agent.

[0021] The organic acid is preferably a compound having a carboxy group (hereinafter, sometimes referred to as a "carboxylic acid compound"), and the carboxylic acid compound may form a salt with a cation (e.g., a metal cation such as an alkali metal cation or an alkaline earth metal cation; or a molecular cation such as an ammonium ion).

[0022] The carboxylic acid compound that is preferably used is (meth)acrylic acid; a carboxylic acid having one or more substituents selected from the group consisting of an ester group, an ether group, an amide group, a thioester group, a thioether group, a carbonate group, a urethane group, and a urea group; or a compound having 4 to 20 carbon atoms and having one or more (preferably one) carboxy groups selected from a linear carboxylic acid (a linear aliphatic carboxylic acid, preferably a linear saturated aliphatic carboxylic acid, etc.), a branched carboxylic acid (a branched aliphatic carboxylic acid, preferably a branched saturated aliphatic carboxylic acid, etc.), a cyclic carboxylic acid (an alicyclic carboxylic acid, preferably an alicyclic carboxylic acid having no unsaturated double bond, etc.), and an aromatic carboxylic acid.

[0023] Specific examples of the carboxylic acid compound include (meth)acrylic acids (e.g., acrylic acid, methacrylic acid, and (meth)acryloxy C such as 3-acryloxypropionic acid). 1-6 Alkyl carboxylic acid, etc.); C 3-9 (Meth)acryloxy C of aliphatic dicarboxylic acids 1-6 Half esters with alkyl alcohols (e.g., 2-acryloxyethyl succinate, 2-methacryloxyethyl succinate, etc.), C 5-10 (Meth)acryloxy C of alicyclic dicarboxylic acids 1-6 Half esters with alkyl alcohol (e.g., 2-acryloxyethylhexahydrophthalic acid, 2-methacryloxyethylhexahydrophthalic acid, 2-acryloxyethylphthalic acid, 2-methacryloxyethylphthalic acid, etc.), C 8-14 (Meth)acryloxy group of aromatic dicarboxylic acids C 1-6Examples of suitable carboxylic acids include carboxylic acids having an ester group, such as half esters with alkyl alcohols (e.g., 2-acryloxyethyl phthalate, 2-methacryloxyethyl phthalate, etc.); linear carboxylic acids such as butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, and stearic acid; branched carboxylic acids such as pivalic acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,2-dimethylvaleric acid, 2,2-diethylbutyric acid, 3,3-diethylbutyric acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 3-methylhexanoic acid, 3-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, and neodecanoic acid; and cyclic carboxylic acids such as naphthenic acid and cyclohexanedicarboxylic acid.

[0024] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri(dodecyl)benzenesulfonyl titanate, neopentyl(diallyl)oxy-tri(dioctyl)phosphate titanate, and neopentyl(diallyl)oxy-trineododecanoyl titanate.

[0025] The surface treatment agent preferably contains an organosilicon compound having an organic group with 12 or less carbon atoms, more preferably contains an organosilicon compound having an organic group with 9 or less carbon atoms, and even more preferably contains a silane coupling agent having an aromatic ring and 9 or less carbon atoms, and a silazane compound having an organic group with 6 or less carbon atoms.

[0026] Preferred examples of the silane coupling agent include phenyltrimethoxysilane and phenyltriethoxysilane, and preferred examples of the silazane compound include 1,1,1,3,3,3-hexamethyldisilazane.

[0027] The amount of the surface treatment agent, in terms of the charged amount, is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the silica particles, and is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 100 parts by mass or less.

[0028] [Component B-1] Diene carboxylic acid ester The diene carboxylic acid ester (B-1 component) in the composition of the present invention is represented by the following formula (1).

[0029] [ka] In the above formula (1), R 1 is an organic group having 5 to 15 carbon atoms, R 2 is a hydrogen atom or a methyl group, X 1 , Y 1 , and Z 1 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 1 , Y 1 and Z 1 At least one of the is an oxygen atom.

[0030] The diene carboxylic acid and ester represented by the above formula (1) have low viscosity, high dissolving power and excellent dilution properties.

[0031] In formula (1), R 1When is an organic group having 5 to 15 carbon atoms, the organic group is preferably composed of a hydrocarbon group, and the hydrocarbon group may have an ether group, and the hydrogen atoms of the hydrocarbon group may be substituted. The organic group may be linear or branched, and may also have a cyclic structure. Examples of the hydrocarbon group include a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Of these, a chain saturated hydrocarbon group having 5 to 15 carbon atoms, a chain unsaturated hydrocarbon group having 5 to 15 carbon atoms, an alicyclic hydrocarbon group having 5 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 15 carbon atoms are preferred. Examples of substituents that may substitute for the hydrogen atoms of the hydrocarbon group include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, a cyano group, and a trimethylsilyl group, but the present invention is not limited to these examples.

[0032] Examples of the chain saturated hydrocarbon group include an n-amyl group, a sec-amyl group, a tert-amyl group, a neopentyl group, an n-hexyl group, a sec-hexyl group, an n-heptyl group, an n-octyl group, a sec-octyl group, a tert-octyl group, a 2-ethylhexyl group, a capryl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, a tridecyl group, a myristyl group, and a pentadecyl group, but the present invention is not limited to these examples.

[0033] Examples of the chain unsaturated hydrocarbon group include a 1,1-dimethyl-2-propenyl group, a 2-methyl-butenyl group, a 3-methyl-2-butenyl group, a 3-methyl-3-butenyl group, and a 2-methyl-3-butenyl group, but the present invention is not limited to these examples.

[0034] Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a 4-methylcyclohexyl group, a 4-tert-butylcyclohexyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group, a dicyclopentanyl group, and a dicyclopentenyl group, but the present invention is not limited to these examples.

[0035] Examples of the aromatic hydrocarbon group include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a 4-tert-butylphenyl group, a benzyl group, a diphenylmethyl group, a diphenylethyl group, a cinnamyl group, a naphthyl group, and an anthranyl group, but the present invention is not limited to these examples.

[0036] Examples of hydrocarbon groups having an ether bond include chain ether groups such as a methoxyethoxyethoxyethyl group, a 3-methoxybutyl group, and an ethoxyethoxyethyl group; groups having both an alicyclic hydrocarbon group and a chain ether group, such as a cyclopentoxyethyl group, a cyclohexyloxyethyl group, a cyclopentoxyethoxyethyl group, a cyclohexyloxyethoxyethyl group, and a dicyclopentenyloxyethyl group; groups having both an aromatic hydrocarbon group and a chain ether group, such as a phenoxyethyl group and a phenoxyethoxyethyl group; and cyclic ether groups such as a β-ethylglycidyl group, a 3,4-epoxycyclohexylmethyl group, a 3-methyl-3-oxetanemethyl group, a 3-ethyl-3-oxetanemethyl group, a tetrahydrofurfuryl group, a tetrahydropyranyl group, a dioxazolanyl group, and a dioxanyl group, but the present invention is not limited to these examples.

[0037] R 1is preferably a chain saturated hydrocarbon group having 5 to 15 carbon atoms or an alicyclic hydrocarbon group having 5 to 15 carbon atoms, more preferably a chain saturated hydrocarbon group having 5 to 10 carbon atoms or an alicyclic hydrocarbon group having 5 to 10 carbon atoms, even more preferably a chain saturated hydrocarbon group having 5 to 8 carbon atoms or an alicyclic hydrocarbon group having 5 to 8 carbon atoms, and most preferably an alicyclic hydrocarbon group having 5 to 6 carbon atoms from the viewpoint of cure shrinkage.

[0038] In formula (1), X 1 and Z 1 are the same or different and are methylene groups or methylene groups in which a hydrogen atom is substituted with a methyl group, and Y 1 is preferably an oxygen atom, and X 1 and Z 1 is a methylene group, and Y 1 is more preferably an oxygen atom.

[0039] R 2 is preferably a hydrogen atom.

[0040] The diene carboxylic acid or ester represented by formula (1) includes n-amyl α-allyloxymethyl acrylate, sec-amyl α-allyloxymethyl acrylate, tert-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, sec-hexyl α-allyloxymethyl acrylate, n-heptyl α-allyloxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, sec-octyl α-allyloxymethyl acrylate, and α-allyloxymethyl acrylate. α-Allyloxymethylacrylate, tert-octyl α-allyloxymethylacrylate, 2-ethylhexyl α-allyloxymethylacrylate, capryl α-allyloxymethylacrylate, nonyl α-allyloxymethylacrylate, decyl α-allyloxymethylacrylate, undecyl α-allyloxymethylacrylate, lauryl α-allyloxymethylacrylate, tridecyl α-allyloxymethylacrylate, myristyl α-allyloxymethylacrylate, pentadecyl α-allyloxymethylacrylate, 1,1-dimethyl-2-propenyl α-allyloxymethylacrylate , 2-methylbutenyl α-allyloxymethylacrylate, 3-methyl-2-butenyl α-allyloxymethylacrylate, 3-methyl-3-butenyl α-allyloxymethylacrylate, 2-methyl-3-butenyl α-allyloxymethylacrylate, cyclopentyl α-allyloxymethylacrylate, cyclopentylmethyl α-allyloxymethylacrylate, cyclohexyl α-allyloxymethylacrylate, cyclohexylmethyl α-allyloxymethylacrylate, 4-methylcyclohexyl α-allyloxymethylacrylate, α-allyl 4-tert-butylcyclohexyl α-allyloxymethylacrylate, tricyclodecanyl α-allyloxymethylacrylate, isobornyl α-allyloxymethylacrylate, adamantyl α-allyloxymethylacrylate, dicyclopentanyl α-allyloxymethylacrylate, dicyclopentenyl α-allyloxymethylacrylate, phenyl α-allyloxymethylacrylate, methylphenyl α-allyloxymethylacrylate, dimethylphenyl α-allyloxymethylacrylate, trimethylphenyl α-allyloxymethylacrylate,4-tert-butylphenyl α-allyloxymethylacrylate, benzyl α-allyloxymethylacrylate, diphenylmethyl α-allyloxymethylacrylate, diphenylethyl α-allyloxymethylacrylate, cinnamyl α-allyloxymethylacrylate, naphthyl α-allyloxymethylacrylate, anthranil α-allyloxymethylacrylate, methoxyethoxyethyl α-allyloxymethylacrylate, methoxyethoxyethoxyethyl α-allyloxymethylacrylate, 3-methoxybutyl α-allyloxymethylacrylate, ethoxyethoxyethyl α-allyloxymethylacrylate, cyclopentoxyethyl α-allyloxymethylacrylate, cyclohexyloxyethyl α-allyloxymethylacrylate, α-allyloxymethylacrylate Examples of the diene-based carboxylic acid or diene-based carboxylic acid ester represented by formula (1) include cyclopentoxyethoxyethyl acrylate, cyclohexyloxyethoxyethyl α-allyloxymethylacrylate, dicyclopentenyloxyethyl α-allyloxymethylacrylate, phenoxyethyl α-allyloxymethylacrylate, phenoxyethoxyethyl α-allyloxymethylacrylate, β-ethylglycidyl α-allyloxymethylacrylate, 3,4-epoxycyclohexylmethyl α-allyloxymethylacrylate, 3-methyl-3-oxetanemethyl α-allyloxymethylacrylate, 3-ethyl-3-oxetanemethyl α-allyloxymethylacrylate, tetrahydrofurfuryl α-allyloxymethylacrylate, and tetrahydropyranyl α-allyloxymethylacrylate, but the present invention is not limited to these examples. The diene-based carboxylic acid or diene-based carboxylic acid ester represented by formula (1) may be used alone or in combination of two or more. Among these, alkyl α-allyloxymethylacrylates having an alkyl group (including both linear and alicyclic alkyl groups) with 5 to 6 carbon atoms are preferred.

[0041] [Component B-2] Diene carboxylic acid ester The diene carboxylic acid or ester (B-2 component) in the composition of the present invention is represented by the following formula (2).

[0042] [ka] In the above formula (2), R 3 is a hydrogen atom or an organic group having 1 to 4 carbon atoms, R 4 is a hydrogen atom or a methyl group, X 2 , Y 2 , and Z 2 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 2 , Y 2 and Z 2 At least one of the is an oxygen atom.

[0043] The diene carboxylic acids and esters represented by the above formula (2) are characterized by low viscosity, high dissolving power, excellent dilution properties, and particularly good curability.

[0044] In equation (2), R 3 When is an organic group having 1 to 4 carbon atoms, the organic group is preferably composed of a hydrocarbon group, and the hydrocarbon group may have an ether group, and the hydrogen atoms of the hydrocarbon group may be substituted. The organic group may be linear or branched, and may also have a cyclic structure. Examples of the hydrocarbon group include a chain saturated hydrocarbon group having 1 or more carbon atoms, a chain unsaturated hydrocarbon group having 3 or more carbon atoms, and an alicyclic hydrocarbon group having 3 or more carbon atoms. Of these, a chain saturated hydrocarbon group having 1 to 4 carbon atoms and a chain unsaturated hydrocarbon group having 3 or 4 carbon atoms are preferred. Examples of substituents that may substitute for the hydrogen atoms of the hydrocarbon group include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, a cyano group, and a trimethylsilyl group, but the present invention is not limited to these examples.

[0045] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, but the present invention is not limited to these examples.

[0046] Examples of the chain unsaturated hydrocarbon group include a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-butenyl group, and a crotyl group, but the present invention is not limited to these examples.

[0047] Examples of the alicyclic hydrocarbon group include a cyclopropyl group and a cyclobutyl group, but the present invention is not limited to these examples.

[0048] Examples of hydrocarbon groups having an ether bond include linear ether groups such as a methoxyethyl group and an ethoxyethyl group; and cyclic ether groups such as a glycidyl group, a β-methylglycidyl group, a 2-oxetanemethyl group, a tetrahydrofuranyl group, and a dioxanyl group; however, the present invention is not limited to these examples.

[0049] R 3 is preferably a chain saturated hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon group having an ether bond having 1 to 4 carbon atoms, and more preferably a chain saturated hydrocarbon group having 1 to 4 carbon atoms from the viewpoint of curability.

[0050] In formula (2), X 2 and Z 2 are the same or different and are methylene groups or methylene groups in which a hydrogen atom is substituted with a methyl group, and Y 2 is preferably an oxygen atom, and X 2 and Z 2 is a methylene group, and Y 2 is more preferably an oxygen atom.

[0051] R 4 is preferably a hydrogen atom.

[0052] Examples of the diene carboxylic acid or ester represented by formula (1) include α-allyloxymethylacrylic acid, methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, n-propyl α-allyloxymethylacrylate, isopropyl α-allyloxymethylacrylate, n-butyl α-allyloxymethylacrylate, sec-butyl α-allyloxymethylacrylate, tert-butyl α-allyloxymethylacrylate, 1-propenyl α-allyloxymethylacrylate, 2-propenyl α-allyloxymethylacrylate, 1-methyl-1-propenyl α-allyloxymethylacrylate, 1-methyl-2-propenyl α-allyloxymethylacrylate, Examples of the diaryloxymethyl acrylate include 2-methyl-1-propenyl α-allyloxymethylacrylate, 2-methyl-2-propenyl α-allyloxymethylacrylate, 1-butenyl α-allyloxymethylacrylate, crotyl α-allyloxymethylacrylate, methoxyethyl α-allyloxymethylacrylate, ethoxyethyl α-allyloxymethylacrylate, glycidyl α-allyloxymethylacrylate, β-methylglycidyl α-allyloxymethylacrylate, 2-oxetanemethyl α-allyloxymethylacrylate, tetrahydrofuranyl α-allyloxymethylacrylate, and dioxanyl α-allyloxymethylacrylate, but the present invention is not limited to these examples. The diene carboxylic acid or diene carboxylic acid ester represented by formula (1) may be used alone or in combination of two or more. Of these, α-allyloxymethylacrylic acid and alkyl α-allyloxymethylacrylates having an alkyl group (including both linear and alicyclic) with 1 to 4 carbon atoms are preferred.

[0053] [Component B-3] Diene carboxylate anion The diene carboxylate anion (Component B-3) in the composition of the present invention is represented by the following formula (3).

[0054] [ka] In the above formula (3), R5 is a hydrogen atom or a methyl group, X 3 , Y 3 , and Z 3 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 3 , Y 3 , and Z 3 At least one of the oxygen atoms is an oxygen atom, and the oxygen-carbon-oxygen bond represented by the dotted line and the solid line indicates that the two carbon-oxygen bonds contained within this bond are equivalent, and the entire oxygen-carbon-oxygen bond forms a monovalent anion.

[0055] As shown in the above formula (3), the diene carboxylate anion has a structure in which the entire oxygen atom-carbon atom-oxygen atom bond forms a monovalent anion, and like ordinary carboxylate anions, when in a highly polar solvent such as water, it exists in an ionized state solvated with solvent molecules (a so-called electrolyte solution state), and when in a low-polarity solvent, a poor solvent, or substantially no solvent, it exists in the state of an ionic substance (a so-called salt) bonded to a counter cation by an ionic bond. In this specification, "substantially solvent-free" refers to a form in which no solvent is contained, or a form in which a solvent is contained but in such a small amount that the solvent effect is not exerted.

[0056] To confirm that the diene carboxylate anion of the present invention exists in the "anionic" state, it can be confirmed by a method similar to that applied to the identification of ordinary carboxylate anions, and for details, see JP 2013-231164 A.

[0057] When the diene carboxylate anion in the present invention exists in the form of the above-mentioned salt, it is an ionic substance in which an equivalent amount of anion and a counter cation are ionic-bonded to each other and are electrically neutral (electrically neutralized) as a whole, and is a diene carboxylate salt in which at least one of the anions is a diene carboxylate anion.

[0058] Like general carboxylates, the diene carboxylate salts of the present invention may have multiple different coordination structures depending on the structure and type of counter cation, solvent, sample concentration, temperature, etc., even if they have the same chemical formula (i.e., the ratio of diene carboxylate anion to counter cation is the same). Furthermore, these different coordination structures can be easily and reversibly converted into each other, and therefore it is not uncommon for them to form a mixture of multiple coordination structures, making it difficult to isolate, identify, and quantify these multiple coordination structures. This phenomenon may occur when the counter cation can have multiple coordination numbers, and is particularly likely to occur when the counter cation is a metal atom or an atomic group consisting of metal atoms.

[0059] It is well known that carboxylate anions generally exhibit multiple coordination forms as ligands, such as unidentate, bidentate, and bridging ligands.

[0060] The term "diene carboxylate" as used herein does not refer to a single coordination structure, but rather to a salt having a plurality of different coordination structures as long as it is expressed by the same chemical formula (i.e., the ratio of the diene carboxylate anion to the counter cation is the same). In other words, the term "diene carboxylate salt" refers to a salt having the same chemical formula but different coordination structures (whether it is a single coordination structure or a mixture of multiple coordination structures) that are treated as the same salt.

[0061] Furthermore, in the diene carboxylate salt of the present invention, at least one of the valences of the counter cation may be occupied by the diene carboxylate anion of the present invention, and the remaining valences may be occupied by anions (anionic ligands) other than the diene carboxylate anion. In addition to the diene carboxylate anion and other anions, an electron pair-donating neutral molecule (neutral molecule-type ligand) may also be coordinated to the counter cation. Examples of such anions (anionic ligands) include oxide ions (O2 -), halogen ions, hydroxide ions, alkoxide ions, carboxylate anions other than diene carboxylate anions, acetylacetonate ions, carbonate ions, bicarbonate ions, nitrate ions, nitrite ions, sulfate ions, sulfite ions, hydrogen sulfite ions, phosphate ions, silicate ions, borate ions, etc. Examples of neutral molecular ligands include water, alcohols, ammonia, amines, phosphines, β-ketoesters, cyclopentadienes, etc. In addition, a great many other anions (anionic ligands) and neutral molecular ligands are known. The diene carboxylate salt of the present invention can contain only one type of such anionic ligand or neutral molecular ligand, or can contain multiple types or multiple units of different types, depending on the valence of the counter cation and the possible coordination number.

[0062] From the above, the diene carboxylate salt in the present invention is represented by a chemical formula consisting of at least a chemical formula representing a diene carboxylate anion and a chemical formula representing a counter cation. In some cases, it is represented by a chemical formula including a chemical formula representing an anion (anionic ligand) other than the diene carboxylate anion and a neutral molecular ligand. The ratio of these diene carboxylate anions, counter cations, anions (anionic ligands) other than the diene carboxylate anions, and neutral molecular ligands is represented by the smallest integer ratio. If the diene carboxylate anion is RCOO, the anion (anionic ligand) other than the diene carboxylate anion is X, the neutral molecular ligand is L, and the counter cation is M, the diene carboxylic acid in the present invention is represented by "(RCOO) a (X) b (L) c (M) d (a, b, c, d are the smallest integer ratios, a and d are integers greater than or equal to 1, b and c are integers greater than or equal to 0). However, for neutral molecular ligands L, it can be difficult to distinguish between a salt with L attached and a mixture of L and salt as an impurity.

[0063] The diene carboxylate anion of the present invention has extremely excellent polymerization and curing properties, and these properties are exhibited both in a state in which it is solvated with solvent molecules and ionized, such as in a highly polar solvent such as water (a so-called electrolyte solution state), and in a state in which it is ionic bonded to a counter cation through an ionic bond, such as in a low-polarity solvent, a poor solvent, or substantially in the absence of a solvent (a so-called salt state).

[0064] Among these, X is the most preferred from the viewpoint of polymerization activity. 3 ,Z 3 are the same or different, a methylene group or a methylene group in which a hydrogen atom is substituted with a methyl group, Y 3 = oxygen atom, and further X 3 =Z 3 = methylene group, Y 3 It is more preferable that the anion is an oxygen atom, that is, the diene carboxylate anion is an anion of α-(meth)allyloxymethylacrylic acid.

[0065] The diene carboxylate salts of the present invention exhibit excellent solubility and compatibility in a variety of common organic solvents, reactive diluents, and resins, ranging from low polarity to high polarity, and in some cases even become liquid at room temperature, because the diene carboxylate anions contain many organic groups and an ether structure.

[0066] The counter cation influences the solubility, film-forming properties, curing properties, and physical properties of the cured product of the diene carboxylate, and may be selected appropriately depending on the purpose and application.

[0067] The counter cations can be classified into cations that are metal elements (metal atoms) or atomic groups containing metal atoms, and cations that are atomic groups consisting of non-metal atoms. Examples of the former include alkali metal ions such as sodium ions and potassium ions, and examples of the latter include cations (also called onium ions) of typical non-metal elements, such as quaternized ions of Group 15 elements (ammonium ions, phosphonium ions, etc.).

[0068] In particular, when the counter cation is a cation that is a metal atom or an atomic group containing a metal atom, not only the properties derived from the ionic bond but also the properties derived from the metal itself can be imparted to a polymerized and cured product of a composition containing a diene carboxylate, making it highly useful. That is, the diene carboxylate of the present invention is more preferably a diene carboxylate whose counter cation is a cation that is a metal atom or an atomic group containing a metal atom (hereinafter sometimes simply referred to as a diene carboxylate metal salt).

[0069] The metal atoms (metal elements) are either typical metal elements or transition metal elements. Typical metals generally refer to alkali metals (metals consisting of elements from Group 1 of the periodic table excluding hydrogen), alkaline earth metals (metals consisting of elements from Group 2 of the periodic table), metals from Group 12 of the periodic table, metals from Group 13 of the periodic table excluding boron, metals from Group 14 of the periodic table excluding carbon and silicon, metals from Group 15 of the periodic table excluding nitrogen, phosphorus, and arsenic, and metals from Group 16 of the periodic table excluding oxygen, sulfur, selenium, and tellurium. However, in the present invention, elements that are sometimes classified as metalloids, such as boron, silicon, arsenic, selenium, and tellurium, may also be included as metal atoms. Transition metals refer to metals consisting of elements from Groups 3 to 11 of the periodic table.

[0070] For the production method of diene carboxylate anions and salts thereof, see, for example, JP 2013-231164 A.

[0071] composition As described above, the composition of the present invention contains [Component A] silica particles and [Component B] at least one of a diene-based carboxylic acid, a diene-based carboxylic acid anion, and a diene-based carboxylic acid ester.

[0072] The content of silica particles in [Component A-1] is preferably 5 to 70% by mass based on 100% by mass of the solid components of the composition. The content of silica particles may be 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and may be 60% by mass or less, more preferably 55% by mass or less. Note that the solid components refer to components excluding the solvent, and the reactive compound is not included in the solvent.

[0073] The content of silica particles in [Component A-2] is 15% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more, based on 100% by mass of the solid components of the composition, and may be 70% by mass or less, preferably 60% by mass or less, and more preferably 55% by mass or less.

[0074] [Component B-1] The content of the diene carboxylic acid ester compound is preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 25% by mass or more, and even more preferably 35% by mass or more, based on 100% by mass of the solid components in the composition, and may be 85% by mass or less, 75% by mass or less, or 65% by mass or less.

[0075] The total content of the diene carboxylic acid and ester compound (B-2 component) and the diene carboxylic acid anion (B-3 component) is 5% by mass or more, preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more, based on 100% by mass of the solid components in the composition, and may be 85% by mass or less, 75% by mass or less, or 65% by mass or less.

[0076] The mass ratio (A-1 / B-1) of the silica particles (A-1 component) to the diene carboxylic acid ester compound (B-1 component) in the composition is preferably 15 / 85 or more, more preferably 30 / 70 or more, and even more preferably 40 / 60 or more, and is preferably 85 / 15 or less, more preferably 70 / 30 or less, and even more preferably 60 / 40 or less.

[0077] The mass ratio (A-2 / (B-2+B-3)) of the total amount of silica particles (A-2 component), diene carboxylic acid and ester compound (B-2 component), and diene carboxylic acid anion (B-3 component) in the composition is preferably 15 / 85 or more, more preferably 30 / 70 or more, and even more preferably 40 / 60 or more, and is preferably 85 / 15 or less, more preferably 70 / 30 or less, and even more preferably 60 / 40 or less.

[0078] [Component C] Other components The composition of the present invention may also contain other polymerizable monomers, solvents, polymers (resins), or other additives in addition to the diene carboxylic acid compound.

[0079] [Component C-1] Other polymerizable monomers The polymerizable monomer may be used alone or in combination of two or more kinds, and examples thereof include monofunctional monomers and crosslinkable monomers.

[0080] The monofunctional monomer may be any compound having one polymerizable carbon-carbon double bond, and one or more types may be used. Examples of the monofunctional monomer include (meth)acrylic acid esters; styrene-based monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, and p-chloromethylstyrene; carboxy group-containing monomers such as (meth)acrylic acid; and hydroxy group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxy-2-hydroxypropyl (meth)acrylate, and 3-phenoxy-2-hydroxypropyl (meth)acrylate.Specific examples of the (meth)acrylic acid esters include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as cyclohexyl (meth)acrylate; (Meth)acrylic acid aryl esters such as 2,4-dibromo-6-sec-butylphenyl (meth)acrylate, 2,4-dibromo-6-isopropylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, and pentabromophenyl (meth)acrylate; (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate and pentabromobenzyl (meth)acrylate; phenoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. (Meth)acrylic acid esters having an aryloxy unit such as phenoxy-2-methylethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate; (meth)acrylic acid esters having an arylthiooxy group such as phenylthioethyl (meth)acrylate, 1-naphthylthioethyl (meth)acrylate, and 2-naphthylthioethyl (meth)acrylate; alkylene glycol mono(meth)acrylates such as methoxypolyethylene glycol (meth)acrylate and phenoxypolyethylene glycol (meth)acrylate; and (meth)acrylic acid esters having a glycidyl group such as glycidyl (meth)acrylate.

[0081] The crosslinkable monomer may be any compound containing a plurality of carbon-carbon double bonds. The crosslinkable monomer may be one or more types, and examples thereof include alkylene glycol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and tetramethylene glycol di(meth)acrylate; neopentyl glycol poly(meth)acrylates such as neopentyl glycol di(meth)acrylate and dineopentyl glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, ethoxylated (3) trimethylolpropane tri(meth)acrylate, propoxylated (3) trimethylolpropane tri(meth)acrylate, and epoxidized (3) trimethylolpropane tri(meth)acrylate. Trimethylolpropane poly(meth)acrylates such as ditrimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; glyceryl poly(meth)acrylates such as glyceryl tri(meth)acrylate and ethoxylated glyceryl tri(meth)acrylate; pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol Polyfunctional (meth)acrylates such as pentaerythritol poly(meth)acrylates, such as dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; polyfunctional styrene-based monomers such as divinylbenzene; polyfunctional allyl ester-based monomers such as diallyl phthalate, diallyl isophthalate, triallyl cyanurate, and triallyl isocyanurate; 2-(2-vinyloxyethoxy)ethyl (meth)acrylate;Urethane acrylate oligomers (for example, the Shikoh (registered trademark) series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), the CN series (manufactured by Sartomer), the Unidic (registered trademark) series (manufactured by DIC Corporation), and the KAYARAD (registered trademark) UX series (manufactured by Nippon Kayaku Co., Ltd.));

[0082] [Component C-2] Solvent The solvent can be selected from water, alcohol solvents, ether solvents, ketone solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, phenol solvents such as phenol, ester solvents, and the like.

[0083] Examples of the alcohol solvent include monool solvents such as methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, isobutyl alcohol, pentanol, methylbutanol, neopentyl alcohol, isopentyl alcohol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-octanol, cyclohexanol, and methylcyclohexanol; diol solvents such as ethanediol, propanediol, butanediol, pentanediol, methylpentanediol, and ethylpentanediol; triol solvents such as glycerin and hexanetriol; methoxyethanol, ethoxyethanol, methoxymethoxyethanol, isopropoxyethanol, butoxyethanol, isopentyloxyethanol, hexyloxyethanol, phenoxyethanol, benzyloxyethanol, diethylene glycol, and diethylene glycol. Examples of suitable solvents include ether alcohol solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, polyethylene glycol, methoxypropanol (propylene glycol monomethyl ether), ethoxypropanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and polypropylene glycol; halogenated alcohol solvents such as chloroethanol, chloropropanediol, and trifluoroethanol; hydroxypropionitrile; and amino alcohol solvents such as aminoethanol, dimethylaminoethanol, diethylaminoethanol, diethanolamine, N-butyldiethanolamine, and triethanolamine.

[0084] Examples of the ether solvent include aliphatic hydrocarbon ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, and dibutyl ether; aromatic hydrocarbon ether solvents such as butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, and dibenzyl ether; cyclic ether solvents such as propylene oxide, furan, and tetrahydrofuran; and polyether solvents such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and glycerin ether.

[0085] Examples of the ketone solvent include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and acetophenone. Examples of the hydrocarbon solvent include saturated aliphatic hydrocarbon solvents such as hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, mesitylene, naphthalene, cyclohexylbenzene, and diethylbenzene; and saturated alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

[0086] Examples of the halogenated hydrocarbon solvent include chlorinated aliphatic hydrocarbon solvents such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, and ethyl chloride; and halogenated aromatic hydrocarbon solvents such as chlorobenzene, fluorobenzene, and hexafluorobenzene.

[0087] Examples of the ester solvent include formate ester solvents such as methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, and pentyl formate; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol methyl ... Examples of suitable solvents include acetate ester solvents such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, methyl acetoacetate, ethyl acetoacetate, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and trifluoroacetic acid; propionate ester solvents such as methyl propionate, ethyl propionate, butyl propionate, and isopentyl propionate; γ-butyrolactone:ethylene glycol monoacetate; ethylene diacetate; ethylene glycol esters; diethylene glycol monoacetate; carbonate esters such as diethyl carbonate, ethylene carbonate, and propylene carbonate; and lactate esters such as ethyl lactate.

[0088] [Component C-3] Polymer (resin) The polymer (resin) may be one or more types, including polyamides such as 6-nylon, 66-nylon, and 12-nylon; polyimides; polyurethanes; polyolefins such as polyethylene and polypropylene; polyesters such as PET, PBT, and PEN; polyvinyl chlorides; polyvinylidene chlorides; polyvinyl acetates; polystyrenes; (meth)acrylic resin-based polymers; ABS resins; fluororesins; phenolic resins such as phenol-formalin resins and cresol-formalin resins; epoxy resins; urea resins; melamine resins; amino resins such as guanamine resins; polyvinyl butyral-based resins; polyurethane-based resins; ethylene-vinyl acetate copolymer-based resins; and soft and hard resins such as ethylene-(meth)acrylic acid ester copolymer-based resins. Among the above, polyimides, polyurethanes, polyesters, (meth)acrylic resin-based polymers, phenolic resins, amino resins, and epoxy resins are more preferred.

[0089] [C-4 ingredient] Other ingredients Examples of the other components include photopolymerization initiators and thermal polymerization initiators, which may be used alone or in combination. Some photopolymerization initiators act as thermal polymerization initiators, and some thermal polymerization initiators act as photopolymerization initiators. Those having both properties can cure the active energy ray-curable aqueous resin composition by light irradiation or heating. Among the polymerization initiators, photopolymerization initiators are preferred because they do not impart thermal history to the formed coating film or the substrate to which the active energy ray-curable aqueous resin composition is applied.

[0090] Examples of thermal polymerization initiators include oil-soluble initiators such as 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4'-dimethylvaleronitrile), benzoyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and tert-butylperoxy-2-ethylhexanoate; persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; water-soluble peroxides such as hydrogen peroxide; and water-soluble azo compounds such as 2,2'-azobis(2-amidinopropane) dihydrochloride, but the present invention is not limited to these examples. These thermal polymerization initiators may be used alone or in combination of two or more.

[0091] Examples of the photopolymerization initiator include benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oxyphenyl-acetic acid 2-[2-oxo-2-phenylacetoxyethoxy]-ethyl ester, oxyphenyl-acetic acid 2-[2-hydroxyethoxy]-ethyl ester, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of photopolymerization initiators include, but are not limited to, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinopropan-1-one, 2-morpholinopropan-1-one, iodonium, sulfonium salts, diazonium salts, (4-methylphenyl[4-(2-methylpropyl)phenyl])-hexafluorophosphate, diethylthioxanthone, and isopropylthioxanthone. These photopolymerization initiators may be used alone or in combination of two or more.

[0092] In 100% by mass of the composition of the present invention, the content of components other than the silica particles, the diene carboxylic acid compound, the other polymerizable monomers described above, and the solvent is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 0 to 30% by mass.

[0093] cured product The present invention also includes a cured product of a composition containing silica particles and a diene carboxylic acid compound. The composition of the present invention has good curability, i.e., it can be cured with small irradiation energy, and the obtained cured product also has excellent thermal stability. The shape of the cured product is not particularly limited, and the thickness is also not particularly limited, but examples include plate-like, sheet-like, film-like, and fibrous shapes. In particular, the thickness when the cured product is in the shape of a plate, sheet, or film, and the diameter when the cured product is in the shape of a fiber, are The thickness is preferably 2 μm to 1 mm, more preferably 5 to 500 μm, and even more preferably 10 to 100 μm.

[0094] When the composition of the present invention is applied to a thickness of 20 μm, the radiation energy is 3500 mJ / cm 2 The composition can be cured with an ultraviolet irradiation dose of 2000 mJ / cm or less. 2 or less, and more preferably 1500 mJ / cm 2 The lower limit is not particularly limited, but for example, 500 mJ / cm 2 is.

[0095] The heat resistance of the cured product is preferably 230° C. or higher, more preferably 240° C. or higher, and even more preferably 250° C. or higher. The heat resistance of the cured product can be evaluated by the measurement method described below.

[0096] The haze of the cured coating film is preferably 5% or less, more preferably 3% or less, and even more preferably 2% or less. The haze of the cured coating film can be measured using a turbidity meter (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the provisions of JIS K7361:2000.

[0097] The scratch resistance of the cured coating film is evaluated by comparing the haze values ​​in the scratch resistance evaluations of the examples, and the smaller the difference (ΔHaze), the better the scratch resistance. In the cured product of the present invention, ΔHaze is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.

[0098] Expected uses The composition of the present invention has good curability and is therefore desirably used in, for example, offset ink, gravure ink, inkjet ink, photoresist ink, adhesives, 3D printing resins, and the like. [Example]

[0099] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and can of course be practiced with appropriate modifications within the scope of the above and below-described aims, and all such modifications are within the technical scope of the present invention.

[0100] The examples and comparative examples were measured and evaluated by the following methods.

[0101] (1) Curability evaluation The composition was applied to a polyethylene terephthalate film (Cosmoshine A4300#100 manufactured by Toyobo) using a bar coater to a thickness of 20 μm, and then irradiated with a metal halide lamp at a single irradiation energy of 500 mJ / cm 2 The point at which the composition became tack-free was judged to be cured, and the integrated amount of irradiation energy until the composition was cured was measured.

[0102] (2) Transparency assessment Using a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.), the haze value of the coating composition prepared in (1) Curability Evaluation was recorded.

[0103] (3) Scratch resistance evaluation The cured coating film placed on a 2 mm thick glass plate was fixed to an abrasion resistance tester (Model 154A, manufactured by Imoto Machinery Co., Ltd.), and #0000 steel wool was run back and forth 10 times under a load of 500 g. The transparency evaluation (2) above was then performed, and the difference in haze value before and after the test was recorded.

[0104] (4) Heat resistance evaluation 10 mg of the particle-containing composition was placed in a deep aluminum pan for thermal analysis and irradiated with a UV irradiator manufactured by Iwasaki Electric Co., Ltd. at 10,000 mJ / cm 2 After irradiating with ultraviolet light, the sample was heated at 120°C for 30 minutes to prepare a sample. Using a simultaneous differential thermal and thermogravimetric analyzer (Hitachi High-Technologies STA7200RV), the sample was heated from room temperature to 500°C at a rate of 10°C / min in a nitrogen atmosphere, and the temperature at which the weight (mass) loss rate reached 5% was recorded as the decomposition temperature to evaluate heat resistance.

[0105] (5) Average primary particle size and coefficient of variation (CV value) The surface-treated silica particles were photographed using a JEOL JSM-7600F scanning electron microscope, and the diameters of 50 randomly selected particles from the SEM image were measured with a vernier caliper. The arithmetic mean value of the 50 diameters was taken as the average primary particle diameter. The magnification of the scanning electron microscope was set so that 50 to 100 particles were measured within the field of view of a single photograph. The coefficient of variation (CV value) of the primary particle diameters of the 50 measured particles was calculated using the following formula: CV value (%) = standard deviation of primary particle size / average primary particle size × 100

[0106] [Production Example 1: Synthesis of cyclohexyl 2-(allyloxymethyl)acrylate (AOMA-CH)] A reactor equipped with a stirrer, temperature sensor, gas inlet tube, T-shaped tube, condenser, and distillate receiver was charged with 24.04 parts of cyclohexanol (CHOH), 74.6 parts of 2-(allyloxymethyl)methyl acrylate (manufactured by Nippon Shokubai Co., Ltd., hereafter referred to as AOMA), 6.0 parts of dibutyltin(IV) oxide (DBTO), and 1.5 parts of p-methoxyphenol (MEHQ). While stirring, an oxygen / nitrogen mixed gas (oxygen concentration 8%) was introduced, and the pressure inside the reactor was gradually reduced to 27 kPa. After reaching 27 kPa, the temperature was increased and adjusted to 100 °C. The reaction was continued for 6.5 hours while distilling off the methanol produced by the transesterification reaction. After completion of the reaction, analysis by gas chromatography revealed that the area ratio of AOMA-CH, AOMA, and CHOH was 39:45:12. Thereafter, the mixture was cooled once, and the pressure was reduced to 800 Pa, after which CHOH and AOMA were distilled off until the internal temperature reached 100° C. Thereafter, the mixture was cooled and the pressure was released. The reaction mixture was diluted with n-hexane, and 4% aqueous NaOH was added to precipitate DBTO, which was then removed by filtration. The filtrate was separated into oil and water, and the resulting oil layer was washed with 15% aqueous NaOH to separate the oil and water. This procedure was repeated five times to remove the remaining AOMA and MEHQ. To the resulting organic phase, 5.0 parts of an alkaline adsorbent (Kyoward 700SL, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, stirred for 1 hour at room temperature, and then filtered. The filtrate was placed in a reactor equipped with a stirrer, temperature sensor, gas inlet tube, T-shaped tube, condenser, and distillate receiver. While stirring, an oxygen / nitrogen mixed gas (oxygen concentration 8%) was passed through, and the internal temperature was heated to 25-30°C. The pressure was slowly reduced to 800 Pa to remove n-hexane. After reaching 800 Pa, the pressure was maintained for 20 minutes and then released, yielding 26.4 parts of the target compound, AOMA-CH. 0.008 parts of MEHQ was added to the resulting AOMA-CH to adjust the MEHQ concentration to 300 ppm.

[0107] [Production Example 2: Production of silica particle solvent dispersion] [Step a] A 50 L stainless steel vessel equipped with a stirrer, a dropping port, and a thermometer was charged with 16,500 g of methanol, 3,200 g of water, and 1,300 g of 25% aqueous ammonia, and stirred for 30 minutes to obtain a homogeneous mixed solution. The temperature of the mixed solution was adjusted to 49-51°C, and while stirring, 5,700 g of tetramethyl orthosilicate (TMOS) was added dropwise through the dropping port over 90 minutes. After the dropwise addition, the mixture was continued to be stirred for 30 minutes while maintaining the temperature, yielding an alcoholic solution suspension (1) of silica particles. The resulting suspension (1) was again heated to 50°C while stirring, and 656 g of phenyltrimethoxysilane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 120 minutes while maintaining the liquid temperature and stirring. Next, 267 g of hexamethyldisilazane (SZ-31, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise from the dropping port over 50 minutes. After the addition was completed, stirring was continued for 15 hours while maintaining the liquid temperature, yielding an alcoholic solution suspension (2) of silica particles having phenyl and methyl groups on the particle surface.

[0108] [B process] The suspension (2) obtained in [Step a] was concentrated at room temperature using a commercially available ultrafiltration membrane equipped with a ceramic tubular ultrafiltration membrane with a molecular weight cutoff of approximately 10,000, with the addition of methanol as needed, to an SiO2 concentration of 11%, yielding a silica particle methanol dispersion (3). The average primary particle diameter was 25 nm, the CV value was 13.7%, and the sphericity ratio was 1.03.

[0109] [C process] The silica particle methanol dispersion (3) obtained in [Step b] was passed through a column packed with a hydrogen-type strongly acidic cation exchange resin, Amberlite IR-120B (manufactured by Organo), at room temperature and at a space velocity of 3 per hour, to obtain a silica particle methanol dispersion (4).

[0110] [Production Example 3: Production of AOMA-CH dispersion of silica particles] [d-1 process] 1800 g of the dispersion (4) obtained in [Step c] was weighed, and the solvent was concentrated by vacuum distillation in a rotary evaporator at a reduced pressure of 30 to 300 hPa and 40°C while the AOMA-CH obtained in Production Example 1 was gradually added to replace the dispersion medium. The mixture was concentrated until the SiO2 concentration reached 50%, thereby obtaining a silica particle AOMA-CH dispersion (5).

[0111] [Production Example 4: Production of Silica Particle Cyclohexyl Acrylate Dispersion] [d-2 process] 1800 g of the dispersion (4) obtained in [Step c] was weighed out, and the solvent was concentrated by vacuum distillation in a rotary evaporator at a reduced pressure of 30 to 300 hPa and 40°C, while cyclohexyl acrylate (hereinafter referred to as CHA) was gradually added to replace the dispersion medium. The mixture was concentrated to an SiO2 concentration of 50%, thereby obtaining a silica particle CHA dispersion (6).

[0112] [Production Example 5: Production of silica particle cyclohexyl methacrylate dispersion] [d-3 process] 1800 g of the dispersion (4) obtained in [Step c] was weighed out, and the solvent was concentrated by vacuum distillation in a rotary evaporator at a reduced pressure of 30 to 300 hPa and 40°C while cyclohexyl methacrylate (hereinafter referred to as CHMA) was gradually added to replace the dispersion medium. The mixture was concentrated to an SiO2 concentration of 50%, thereby obtaining silica particle CHMA dispersion (7).

[0113] [Production Example 6: Production of silica particle-containing composition] For the silica particle AOMA-CH dispersion (5) obtained in Production Example 3, 5 g of the solution was placed in a transparent glass bottle and 0.2 g of Omnirad184 (a photoradical polymerization initiator, manufactured by IGM Resins) was added, and the mixture was stirred until homogenous using a stirring / defoaming apparatus (ARE-310, manufactured by Thinky Corporation), to obtain a silica particle-containing composition (8).

[0114] [Production Example 7: Preparation of silica particle-containing composition] For the silica particle CHA dispersion (6) obtained in Production Example 4, 5 g of the solution was placed in a transparent glass bottle and 0.2 g of Omnirad184 (a photoradical polymerization initiator, manufactured by IGM Resins) was added, and the mixture was stirred until homogenous using a stirring / defoaming apparatus (ARE-310, manufactured by Thinky Corporation), to obtain a silica particle-containing composition (9).

[0115] [Production Example 8: Production of silica particle-containing composition] For the silica particle CHMA dispersion (7) obtained in Production Example 5, 5 g of the solution was placed in a transparent glass bottle and 0.2 g of Omnirad184 (a photoradical polymerization initiator, manufactured by IGM Resins) was added, and the mixture was stirred until homogenous using a stirring / defoaming apparatus (ARE-310, manufactured by Thinky Corporation), to obtain a silica particle-containing composition (10).

[0116] The silica particle-containing compositions (8) to (10) obtained in Production Examples 6 to 8, and the silica-free AOMA-CH were evaluated for (1) curability, (2) transparency, (3) scratch resistance, and (4) heat resistance of the cured product. The results are shown in Table 1.

[0117] [Table 1]

[0118] According to Table 1, Example 1 is superior in terms of curability to Comparative Example 1, which whitened when irradiated with UV light, and it is clear that the amount of energy required for curing is lower than that of Comparative Example 2. Furthermore, it is clear that Example 1 has superior thermal stability to Comparative Examples 1 and 2 in the cured product. It can also be seen that the appearance of the obtained cured body is good in terms of transparency from Comparative Example 1, and good results are obtained in terms of scratch resistance from Comparative Examples 2 and 3. [Industrial Applicability]

[0119] The composition of the present invention can be suitably used for, for example, offset ink, gravure ink, inkjet ink, photoresist ink, adhesive, 3D printing resin, etc.

Claims

1. [Component A-1] silica particles having an average primary particle size of 5 nm or more and 100 nm or less and a particle size variation coefficient (by number) of 25% or less; [Component B-1] A composition containing a diene carboxylic acid ester represented by the following formula (1): 【Chemistry 1】 In the above formula (1), R 1 is an organic group having 5 to 15 carbon atoms, R 2 is a hydrogen atom or a methyl group, X 1 , Y 1 , and Z 1 are the same or different and are a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, or an oxygen atom; X 1 , Y 1 and Z 1 At least one of the is an oxygen atom.

2. The composition of claim 1, In the formula (1), A composition wherein R 1 is an alicyclic hydrocarbon group having 5 to 15 carbon atoms.

3. A cured product of the composition according to claim 1 or 2.

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