Curable composition and cured product

Abstract

To provide a curable composition having excellent curability by heating and a cured product of the same.SOLUTION: A curable composition contains a polymerizable monomer, an aluminum chelate compound, a silanol compound, and a quaternary boron onium salt. The polymerizable monomer is preferably a radical-polymerizable monomer having a carbon-carbon double bond in the molecule, and the aluminum chelate compound is preferably held by a porous particle.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition and a cured product. [Background technology]

[0002] BACKGROUND ART Curable compositions containing polymerizable monomers have been widely used in applications such as coatings and adhesives, and the resulting cured products have excellent properties such as abrasion resistance, adhesion, and weather resistance. As such a curable composition, for example, a thermosetting composition containing a cationic curing component, a specific ammonium salt, and a radical generator has been proposed. This proposal discloses that an acid is generated by an organic peroxide as the radical generator, and the acid cures the cationic curing component such as an epoxy resin (see, for example, Patent Document 1).

[0003] Also, an adhesive composition containing a cationically polymerizable compound, an aluminum chelate-silanol curing catalyst, and an episulfide compound has been proposed, and this proposal discloses that the aluminum chelate-silanol curing catalyst causes cationic polymerization of the cationically polymerizable compound by the cooperation of cationic and anionic species as active species (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-166306 [Patent Document 2] Patent Publication No. 2021-4363 Summary of the Invention [Problem to be solved by the invention]

[0005] However, neither Patent Document 1 nor Patent Document 2 contains a radical polymerizable monomer or a quaternary boron onium salt, and the curable composition is not prepared in such a manner that, when the curable composition is heated, an aluminum chelate compound reacts with a silanol compound to generate an acid, the generated acid reacts with a quaternary boron onium salt to generate radicals, and the radicals polymerize the radical polymerizable monomer. Furthermore, when curable compositions containing radically polymerizable monomers are subjected to ultraviolet (UV) curing in applications such as bonding optical components, there is a problem that the light irradiation does not reach the composition, resulting in poor curing or difficulty in curing.

[0006] The present invention aims to solve the above-mentioned problems in the prior art and to achieve the following objects: That is, the present invention relates to a curable composition that has excellent heat curing properties and a cured product using the same. [Means for solving the problem]

[0007] The means for solving the above problems are as follows: <1> The curable composition is characterized by containing a polymerizable monomer, an aluminum chelate compound, a silanol compound, and a quaternary boron onium salt. <2> the polymerizable monomer is a radical polymerizable monomer having a carbon-carbon double bond in the molecule; <1> The curable composition according to claim 1, <3> the polymerizable monomer is a (meth)acrylate, <1> from <2> The curable composition according to any one of the above items. <4> The aluminum chelate compound is held in porous particles. <1> from <3> The curable composition according to any one of the above items. <5> The porous particles are made of a polyurea resin. <4> The curable composition according to claim 1, <6> The quaternary boron onium salt is represented by the following general formula (1): <1> from <5> The curable composition according to any one of the above items. [ka] However, in the general formula (1), R 1 From R 4 At least one of X is an optionally substituted phenyl group or naphthyl group, and the rest are optionally substituted alkyl groups, or optionally substituted phenyl groups or naphthyl groups. + represents an ammonium cation, a sulfonium cation, a pyridinium cation, a phosphonium cation, an oxonium cation, or an iodonium cation. <7> The silanol compound is an arylsilanol compound represented by the following general formula (6): <1> from <6> The curable composition according to any one of the above items. [ka] In the general formula (6), m is 2 or 3, and the sum of m and n is 4. Ar is an aryl group which may have a substituent. <8> The content of the polymerizable monomer is 80% by mass or more and 97% by mass or less. <1> from <7> The curable composition according to any one of the above items. <9> The content of the aluminum chelate compound is 0.1% by mass or more and 10% by mass or less. <1> from <8> The curable composition according to any one of the above items. <10> The content of the silanol compound is 0.1% by mass or more and 10% by mass or less. <1> from <9> The curable composition according to any one of the above items. <11> The content of the quaternary boron onium salt is 0.1% by mass or more and 5% by mass or less. <1> from <10> The curable composition according to any one of the above items. <12> The aforementioned <1> from <11> The curable composition according to any one of the above items is cured by heating. [Effects of the Invention]

[0008] According to the present invention, the above-mentioned problems in the prior art can be solved, the above-mentioned objects can be achieved, and a curable composition having excellent heat curing properties and a cured product using the same can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] (Curable composition) The curable composition of the present invention contains a polymerizable monomer, an aluminum chelate compound, a silanol compound, and a quaternary boron onium salt, and may further contain other components as required.

[0010] In the present invention, the aluminum chelate compound and the silanol compound are reacted with each other by heating to generate an acid. The generated acid reacts with the quaternary boron onium salt to form the B + The phenyl or naphthyl group bonded to the compound is released, generating a radical. This radical polymerizes the polymerizable monomer to produce a polymer, improving curing properties when heated. This solves the problem of insufficient light irradiation, resulting in poor curing or difficulty in curing when ultraviolet (UV) curing is performed in applications such as bonding optical components. Furthermore, by using porous particles holding an aluminum chelate compound instead of an aluminum chelate compound, the curable composition does not react instantly, and a good pot life can be maintained.

[0011] <Polymerizable monomer> The polymerizable monomer is not particularly limited and can be appropriately selected depending on the purpose, but a radical polymerizable monomer having a carbon-carbon double bond in the molecule is preferred. The radical polymerizable monomer may be a monofunctional radical polymerizable monomer, a polyfunctional radical polymerizable monomer, or a combination thereof. Examples of such radical polymerizable monomers include (meth)acrylates, styrene-based monomers, vinyl ethers, vinyl amides, maleimide-based monomers, etc. Among these, (meth)acrylates are particularly preferred.

[0012] -(Meth)acrylate- As the (meth)acrylate, a monofunctional (meth)acrylic monomer or a polyfunctional (meth)acrylic monomer is used. Examples of the monofunctional (meth)acrylic monomer include (meth)acrylic acid and (meth)acrylic monomers having one (meth)acrylic group, such as phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, methyl ... Diethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, methoxydixylethyl (meth)acrylate, ethyl diglycol (meth)acrylate, cyclic trimethylolpropane formal mono(meth)acrylate, imide (meth)acrylate, isoamyl (meth)acrylate, ethoxylated cocoa Cinic acid (meth)acrylate, trifluoroethyl (meth)acrylate, ω-carboxypolycaprolactone mono(meth)acrylate, N-vinylformamide, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, tribromophenyl (meth)acrylate, ethoxylated tribromophenyl (meth)acrylate, 2-Phenoxyethyl (meth)acrylate, (meth)acryloylmorpholine, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, stearyl (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, 3,3,Examples of suitable acrylates include 5-trimethylcyclohexanol (meth)acrylate, isooctyl (meth)acrylate, octyl / decyl (meth)acrylate, tridecyl (meth)acrylate, caprolactone (meth)acrylate, ethoxylated (4) nonylphenol (meth)acrylate, methoxypolyethylene glycol (350) mono(meth)acrylate, methoxypolyethylene glycol (550) mono(meth)acrylate, stearyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. These may be used alone or in combination of two or more.

[0013] Examples of polyfunctional (meth)acrylic monomers include (meth)acrylic monomers having two (meth)acrylic groups and tri- or higher functional (meth)acrylic monomers. Examples of the di(meth)acrylic monomer having two (meth)acrylic groups include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, ethoxylated (3) bisphenol A di(meth)acrylate, dipropylene glycol di(meth)acrylate, alkoxylated hexanediol di(meth)acrylate, ethoxylated (4) bisphenol A di(meth)acrylate, ethoxylated (10) bisphenol A di(meth)acrylate, polyethylene glycol ( 600) di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, ethoxylated tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, and the like. These may be used alone or in combination of two or more.

[0014] Examples of the trifunctional or higher (meth)acrylic monomer include trimethylolpropane tri(meth)acrylate, hydroxypivalic acid trimethylolpropane tri(meth)acrylate, ethoxylated phosphate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetramethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, propoxylated glyceryl tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, neopentyl glycol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, hydroxypivalic acid neopentyl glycol acrylic acid adduct, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-ethyl-2(hydroxymethyl)-1,3-propanediol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, etc. These may be used alone or in combination of two or more.

[0015] -Styrene-based monomers- As the styrene-based monomer, a monofunctional styrene-based monomer or a polyfunctional styrene-based monomer is used. Examples of the monofunctional styrene-based monomer include styrene derivatives substituted with a group that does not participate in a radical reaction, such as styrene; α-alkylstyrenes such as α-methylstyrene (the number of carbon atoms in the alkyl is preferably 1 to 4); halogen-substituted styrenes such as p-chlorostyrene and p-bromostyrene; alkyl-substituted styrenes such as 4-methylstyrene and 4-ethylstyrene; alkoxy-substituted styrenes such as p-methoxystyrene (the number of carbon atoms in the alkyl and alkoxy is preferably 1 to 12, more preferably 1 to 4); styrene-polyoxyalkylene adducts such as vinylbenzyl-ω-methylpolyoxyethylene oxide; and hydroxyl-substituted styrenes such as hydroxystyrene. These may be used alone or in combination of two or more.

[0016] Examples of the polyfunctional styrene-based monomer include vinyl-substituted styrenes such as 1,3-divinylbenzene and 1,4-divinylbenzene.

[0017] -Vinyl ether- As the vinyl ether, a monofunctional vinyl ether or a polyfunctional vinyl ether is used. Examples of the monofunctional vinyl ether include chain vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, trifluoroethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-methoxyethyl vinyl ether, and diethylene glycol ethyl vinyl ether; aliphatic ring-containing vinyl ethers such as cyclohexyl vinyl ether and 2-(vinyloxy)tetrahydropyran; and aromatic ring-containing vinyl ethers such as phenyl vinyl ether, benzyl vinyl ether, and 4-methoxybenzyl vinyl ether. These may be used alone or in combination of two or more.

[0018] Examples of the polyfunctional vinyl ether include linear vinyl ethers such as diethylene glycol divinyl ether, divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, triethylene glycol divinyl ether, and bis(vinyloxybutyl)succinate; aliphatic ring-containing vinyl ethers such as 1,4-cyclohexanedimethanol divinyl ether; and aromatic ring-containing vinyl ethers such as bis[4-(vinyloxy)butyl]terephthalate. These may be used alone or in combination of two or more.

[0019] -Vinylamide- Examples of monofunctional vinylamides, which are monofunctional radically polymerizable monomers, include chain vinylamides such as N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, and N-methyl-N-vinylacetamide; and aliphatic ring-containing vinylamides such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and 5-methyl-3-vinyloxazolidin-2-one. These may be used alone or in combination of two or more.

[0020] -Maleimide monomer- As the maleimide-based monomer, a monofunctional maleimide-based monomer having one maleimide group or a polyfunctional maleimide-based monomer having two or more maleimide groups is used. Examples of the monofunctional maleimide monomer include maleimide; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; aromatic ring-containing maleimides such as phenylmaleimide; etc. These may be used alone or in combination of two or more.

[0021] Examples of the polyfunctional maleimide monomer include aliphatic hydrocarbon group-containing maleimides such as 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, and 2,2'-(ethylenedioxy)bis(ethylmaleimide), and aromatic ring-containing maleimides such as N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, and 1,1'-(methylenedi-4,4'-phenylene) bismaleimide. These may be used alone or in combination of two or more.

[0022] -Other polymerizable monomers- Other polymerizable monomers include, for example, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; monoalkyl esters and dialkyl esters such as maleic anhydride, maleic acid, and monoalkyl esters and dialkyl esters of maleic acid; fumaric acid and monoalkyl esters and dialkyl esters of fumaric acid; nitrile-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide-containing vinyl monomers such as vinyl esters, for example, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or in combination of two or more.

[0023] The content of the polymerizable monomer is preferably 80% by mass or more and 97% by mass or less, and more preferably 85% by mass or more and 95% by mass or less, based on the total amount of the curable composition.

[0024] <Quaternary boron onium salts> The quaternary boron onium salt is composed of an organic boron anion represented by the following general formula (1) and a cation.

[0025] [ka] However, in the general formula (1), R 1 From R 4 At least one of X is an optionally substituted phenyl group or naphthyl group, and the rest are optionally substituted alkyl groups, or optionally substituted phenyl groups or naphthyl groups. + represents an ammonium cation, a sulfonium cation, a pyridinium cation, a phosphonium cation, an oxonium cation, or an iodonium cation.

[0026] The alkyl group preferably has 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a stearyl group. The alkyl group, phenyl group, or naphthyl group may be substituted with, for example, a halogen atom, a cyano group, an acyloxy group, an acyl group, an alkoxy group, or a hydroxy group.

[0027] Examples of the organic boron anion include triarylmonoalkyl boron anions. Examples of triarylmonoalkyl boron compounds include triphenylmethyl borate, triphenylethyl borate, triphenylpropyl borate, triphenylisopropyl borate, triphenylbutyl borate, triphenylisobutyl borate, triphenyl-sec-butyl borate, triphenyl-tert-butyl borate, tris(p-tolyl)butyl borate, trimesitylbutyl borate, tris(p-anisyl)butyl borate, tris(2,4,5-trifluorophenyl)butyl borate, and tris(pentafluorophenyl)butyl borate. These may be used alone or in combination of two or more.

[0028] X +represents an ammonium cation, sulfonium cation, pyridinium cation, phosphonium cation, oxonium cation, or iodonium cation. The substituent of the cation is not structurally specified, and examples thereof include an alkyl group, an alkoxy group, and a phenyl group. The ammonium cation, sulfonium cation, pyridinium cation, phosphonium cation, oxonium cation, and iodonium cation may each have a substituent, and may be linked to form a ring.

[0029] Examples of the ammonium cation include alkyl group-containing ammonium cations such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, tetrabutylammonium, tetra-sec-butylammonium, tetra-tert-butylammonium, tetrapentylammonium, tetraisopentylammonium, tetraneopentylammonium, and tetra-tert-pentylammonium; hydrogen-containing ammonium cations such as tetrahydrogenammonium, trimethylhydrogenammonium, triethylhydrogenammonium, tripropylhydrogenammonium, tripropylhydrogenammonium, tributylhydrogenammonium, and tripentylhydrogenammonium; benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium, benzyltributylammonium, benzyltripentylammonium, phenyltrimethylammonium, phenyltriethylammonium, and phenyltripropylammonium. benzyl group-containing ammonium cations such as ammonium, phenyltributylammonium, and phenyltripentylammonium; vinyl group-containing ammonium cations such as trimethylvinylammonium, triethylvinylammonium, tripropylvinylammonium, tributylvinylammonium, and tripentylvinylammonium; allyl group-containing ammonium cations such as trimethylallylammonium, triethylallylammonium, tripropylallylammonium, tributylallylammonium, tripentylallylammonium, dimethyldiallylammonium, diethyldiallylammonium, dipropyldiallylammonium, dibutyldiallylammonium, and dipentyldiallylammonium; alkoxyalkyl group-containing ammonium cations such as (2-methoxyethoxymethyl)trimethylammonium, (2-methoxyethoxymethyl)triethylammonium, (2-methoxyethoxymethyl)tripropylammonium, (2-methoxyethoxymethyl)tributylammonium, and (2-methoxyethoxymethyl)tripentylammonium;Examples of such ammonium salts include hexamethonium, decamethonium, ferrocenylmethyltrimethylammonium, ferrocenylmethyltriethylammonium, ferrocenylmethyltripropylammonium, ferrocenylmethyltributylammonium, and ferrocenylmethyltripentylammonium. These may be used alone or in combination of two or more.

[0030] Examples of the sulfonium cation include trimethylsulfonium cation, triphenylsulfonium cation, diphenyl[4-(phenylthio)phenyl]sulfonium cation, etc. These may be used alone or in combination of two or more.

[0031] Examples of pyridinium cations include methylpyridinium cations, phenylpyridinium cations, etc. These may be used alone or in combination of two or more.

[0032] Examples of the phosphonium cation include tetramethylphosphonium cation, tetraethylphosphonium cation, tetra-n-propylphosphonium cation, tetra-n-butylphosphonium cation, tetraphenylphosphonium cation, etc. These may be used alone or in combination of two or more.

[0033] Examples of oxonium cations include trimethyloxonium cation, phenyldimethyloxonium cation, etc. These may be used alone or in combination of two or more.

[0034] Examples of iodonium cations include diphenyliodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, bis(4-t-butylphenyl)iodonium cation, diphenyleneiodonium cation, etc. These may be used alone or in combination of two or more.

[0035] The quaternary boron onium salt may be appropriately synthesized or may be a commercially available product, such as P3B and N3B (both manufactured by Showa Denko K.K.), or tetraphenylphosphonium tetraphenylborate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0036] The content of the quaternary boron onium salt is preferably from 0.1% by mass to 5% by mass, more preferably from 1% by mass to 5% by mass, based on the total amount of the curable composition.

[0037] <Aluminum chelate compounds> The aluminum chelate compound may be, for example, a complex compound in which three β-ketoenolate anions are coordinated to aluminum, as represented by the following general formula (2): Here, no alkoxy group is directly bonded to the aluminum, because if it were directly bonded, it would be prone to hydrolysis and would not be suitable for emulsification.

[0038] [ka]

[0039] In the general formula (2), R 1 , R 2 and R 3 each independently represents an alkyl group or an alkoxy group. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an oleyloxy group.

[0040] Examples of the complex compound represented by the general formula (2) include aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate), and aluminum monoacetylacetonate bis(oleylacetoacetate).

[0041] The content of the aluminum chelate compound is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less, based on the total amount of the curable composition.

[0042] The aluminum chelate compound is preferably held in porous particles (porous particles holding the aluminum chelate compound) in order to maintain a good pot life. The porous particles are made of a polyurea resin. The porous particles hold the aluminum chelate compound in their pores, for example. In other words, the aluminum chelate compound is incorporated and held in the fine pores present in the porous particle matrix made of a polyurea resin.

[0043] The polyurea resin is a resin having a urea bond therein. The polyurea resin constituting the porous particles can be obtained, for example, by polymerizing a polyfunctional isocyanate compound in an emulsion. Details will be described later. The polyurea resin may contain a bond derived from an isocyanate group other than a urea bond, such as a urethane bond. When a urethane bond is contained, the resin may be referred to as a polyurea-urethane resin.

[0044] The content of the aluminum chelate compound in the porous particles is not particularly limited and can be appropriately selected depending on the purpose.

[0045] The average pore diameter of the pores of the porous particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 nm or more and 300 nm or less, and more preferably 5 nm or more and 150 nm or less.

[0046] The content of the porous particles holding the aluminum chelate compound is preferably 0.1% by mass to 10% by mass, more preferably 1% by mass to 5% by mass, based on the total amount of the curable composition.

[0047] The method for producing the porous particles holding an aluminum compound includes a porous particle producing step and a coating step, and may further include other steps as necessary.

[0048] <<Porous particle manufacturing process>> The porous particle preparation step includes at least an emulsion preparation process and a polymerization process, preferably includes an additional filling process, and further includes other processes as necessary.

[0049] -Emulsion production process- The emulsion preparation process is not particularly limited as long as it is a process in which an aluminum chelate compound, a polyfunctional isocyanate compound, and preferably an organic solvent are mixed together to obtain a liquid, and the resulting liquid is emulsified to obtain an emulsion. The process can be appropriately selected depending on the purpose, and can be carried out using, for example, a homogenizer.

[0050] The size of the oil droplets in the emulsion is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 μm or more and 100 μm or less.

[0051] The polyfunctional isocyanate compound is a compound having two or more isocyanate groups, preferably three isocyanate groups, in one molecule. More preferred examples of such trifunctional isocyanate compounds include a TMP adduct represented by the following general formula (3) obtained by reacting one mole of trimethylolpropane with three moles of a diisocyanate compound, an isocyanurate represented by the following general formula (4) obtained by self-condensing three moles of a diisocyanate compound, and a biuret represented by the following general formula (5) obtained by condensing one mole of diisocyanate with diisocyanate urea obtained from two moles of the three moles of a diisocyanate compound.

[0052] [ka]

[0053] In the general formulas (3) to (5), the substituent R is the portion of the diisocyanate compound excluding the isocyanate group. Specific examples of such diisocyanate compounds include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, hexahydro-m-xylylene diisocyanate, isophorone diisocyanate, and methylenediphenyl-4,4'-diisocyanate.

[0054] The blending ratio of the aluminum chelate compound to the polyfunctional isocyanate compound is not particularly limited and can be appropriately selected depending on the purpose, but if the blending amount of aluminum chelate is too small, the curability of the cationic curable compound to be cured will decrease, and if it is too large, the latency of the resulting latent curing agent will decrease. In this respect, the blending ratio of the aluminum chelate to 100 parts by mass of the polyfunctional isocyanate compound is preferably 10 parts by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less.

[0055] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but a volatile organic solvent is preferred. The organic solvent is preferably a good solvent for the aluminum chelate compound and the polyfunctional isocyanate compound (each having a solubility of preferably 0.1 g / ml or more in organic solvent), is substantially insoluble in water (water solubility of 0.5 g / ml or less in organic solvent), and has a boiling point of 100°C or less under atmospheric pressure. Specific examples of such volatile organic solvents include alcohols, acetates, and ketones. Among these, ethyl acetate is preferred because of its high polarity, low boiling point, and poor water solubility.

[0056] The amount of the organic solvent used is not particularly limited and can be appropriately selected depending on the purpose.

[0057] -Polymerization treatment- The polymerization treatment is not particularly limited as long as it is a treatment that polymerizes the polyfunctional isocyanate compound in the emulsion to obtain porous particles, and can be appropriately selected depending on the purpose.

[0058] In the polymerization treatment, a portion of the isocyanate groups of the polyfunctional isocyanate compound is hydrolyzed to form amino groups, and the amino groups react with the isocyanate groups of the polyfunctional isocyanate compound to form urea bonds, thereby obtaining a polyurea resin. Here, when the polyfunctional isocyanate compound has urethane bonds, the resulting polyurea resin also has urethane bonds, and in this respect, the resulting polyurea resin can also be called a polyurea-urethane resin.

[0059] The polymerization time in the polymerization treatment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 1 hour to 30 hours, more preferably from 2 hours to 10 hours. The polymerization temperature in the polymerization treatment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 30°C or higher and 90°C or lower, and more preferably 50°C or higher and 80°C or lower. The resulting porous particles holding the aluminum compound can be filtered out, washed, dried, and then crushed into primary particles using a known crushing device, if necessary.

[0060] <Silanol compounds> Examples of the silanol compound include triethylsilanol, dimethylphenylsilanol, trifluoromethylphenylsilanol, and arylsilanol compounds represented by the following general formula (6): Among these, the arylsilanol compound represented by the general formula (6) is preferred. [ka] In the general formula (6), m is 2 or 3, preferably 3, and the sum of m and n is 4. Ar is an aryl group which may have a substituent. The arylsilanol compound represented by the general formula (6) is a monool or diol.

[0061] In the general formula (6), Ar is an aryl group which may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group (e.g., a 1-naphthyl group, a 2-naphthyl group, etc.), an anthracenyl group (e.g., a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a benz[a]-9-anthracenyl group, etc.), a phenaryl group (e.g., a 3-phenaryl group, a 9-phenaryl group, etc.), a pyrenyl group (e.g., a 1-pyrenyl group, etc.), an azulenyl group, a fluorenyl group, a biphenyl group (e.g., a 2-biphenyl group, a 3-biphenyl group, a 4-biphenyl group, etc.), a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, and a pyridyl group. These may be used alone or in combination of two or more. Among these, a phenyl group is preferred from the viewpoints of availability and cost. The m Ars may be the same or different, but are preferably the same from the viewpoint of availability.

[0062] These aryl groups may have, for example, 1 to 3 substituents. Examples of the substituent include an electron-withdrawing group and an electron-donating group. Examples of the electron-withdrawing group include a halogen group (e.g., a chloro group, a bromo group, etc.), a trifluoromethyl group, a nitro group, a sulfo group, a carboxyl group, an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, etc.), and a formyl group. Examples of the electron-donating group include alkyl groups (e.g., methyl, ethyl, and propyl groups), alkoxy groups (e.g., methoxy and ethoxy groups), hydroxy groups, amino groups, monoalkylamino groups (e.g., monomethylamino groups), and dialkylamino groups (e.g., dimethylamino groups).

[0063] Specific examples of the phenyl group having a substituent include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 2,5-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2-ethylphenyl group, and a 4-ethylphenyl group.

[0064] The acidity of the hydroxyl group of the silanol group can be increased by using an electron-withdrawing group as a substituent, and the acidity of the hydroxyl group of the silanol group can be decreased by using an electron-donating group as a substituent. Here, the m Ars may have different substituents, but it is preferable that the m Ars have the same substituents from the viewpoint of availability. Alternatively, only some of the Ars may have substituents, and the other Ars may have no substituents.

[0065] Among these, triphenylsilanol and diphenylsilanediol are preferred, with triphenylsilanol being particularly preferred.

[0066] The content of the silanol compound is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less, based on the total amount of the curable composition.

[0067] <Other ingredients> The other components are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include pigments, dyes, organic or inorganic fillers, antistatic agents, antifoaming agents, viscosity modifiers, light resistance stabilizers, weather resistance stabilizers, heat resistance stabilizers, ultraviolet absorbers, antioxidants, leveling agents, pigment dispersants, and waxes.

[0068] (cured product) The cured product of the present invention is obtained by curing the curable composition of the present invention by heating. The heating conditions are not particularly limited and can be appropriately selected depending on the purpose, for example, at a temperature of 60°C to 150°C for 5 to 15 minutes in an oven or for 1 to 5 minutes on a hot plate.

[0069] The polymer (cured product) obtained by heating the curable composition of the present invention may be in any form, including a homopolymer, a copolymer that is not a block copolymer, or a block polymer, and is preferably a homopolymer or a copolymer that is not a block copolymer. Here, the term "copolymer that is not a block copolymer" includes random copolymers, alternating copolymers, and all other copolymers obtained by simultaneously polymerizing multiple types of monomers.

[0070] <Application> The curable composition of the present invention has excellent curability by heating, and therefore can be widely used in various fields, such as paints, adhesives for optical members, sealants for electronic components, hard coating agents for various plastic substrates for automobiles, home appliances, mobile phones, etc., overcoating agents for paper, etc., binders for printing inks, and solder resists. [Example]

[0071] Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

[0072] (Preparation Example 1) <Preparation of porous particles supporting aluminum chelate compounds> -Preparation of aqueous phase- 800 parts by mass of distilled water, 0.05 parts by mass of a surfactant (Newrex RT, manufactured by NOF Corporation), and 4 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant were placed in a 3-liter interfacial polymerization vessel equipped with a thermometer and mixed uniformly to prepare an aqueous phase.

[0073] -Preparation of oil phase- Next, 100 parts by mass of a 24% by mass isopropanol solution of aluminum monoacetylacetonate bis(ethylacetoacetate) (Aluminum Chelate D, manufactured by Kawaken Fine Chemicals Co., Ltd.) and 70 parts by mass of a methylenediphenyl-4,4'-diisocyanate (3 moles) to trimethylolpropane (1 mole) adduct (polyfunctional isocyanate compound, D-109, manufactured by Mitsui Chemicals, Inc.) were dissolved in 130 parts by mass of ethyl acetate to prepare an oil phase.

[0074] -Emulsification- The prepared oil phase was added to the previously prepared aqueous phase, and the mixture was mixed and emulsified using a homogenizer (10,000 rpm / 5 minutes: T-50, manufactured by IKA Japan Co., Ltd.) to obtain an emulsion.

[0075] -polymerization- The prepared emulsion was polymerized at 80°C for 6 hours while stirring at 200 rpm. After the reaction was completed, the polymerization reaction solution was allowed to cool to room temperature (25°C), and the resulting polymerized resin particles (porous particles) were filtered off, washed with distilled water, and air-dried at room temperature (25°C) to obtain agglomerated porous particles. The agglomerated porous particles were crushed into primary particles using a crusher (AO jet mill, manufactured by Seishin Enterprise Co., Ltd.) to obtain porous particles carrying the aluminum chelate compound of Preparation Example 1.

[0076] (Examples 1 to 16 and Comparative Examples 1 to 5) The compositions shown in Tables 1 to 3 were mixed to prepare curable compositions of Examples 1 to 16 and Comparative Examples 1 to 5.

[0077] Next, the "exothermic peak temperature" and "pot life" of each of the obtained curable compositions were evaluated as follows. The results are shown in Tables 1 to 3.

[0078] <Exothermic peak temperature> For each of the obtained curable compositions, a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Corporation) was used to raise the temperature at a rate of 10°C / min. Samples that showed exothermic behavior were judged to have cured, and the exothermic peak temperature of the samples that showed exothermic behavior was measured and recorded. In DSC, the reaction initiation temperature means the curing initiation temperature, the exothermic peak temperature means the temperature at which curing is most active, the reaction end temperature means the curing end temperature, and the peak area means the amount of heat generated.

[0079] <Pot life evaluation> For each of the obtained curable compositions, the initial heat release amount after adding each component shown in Tables 1 to 3, and the heat release amount after leaving each curable composition at 23°C for 72 hours were measured using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Corporation). When the heat release amount after leaving at 23°C for 72 hours was reduced by 20% or more compared to the initial heat release amount, the pot life was evaluated as poor and rated as "×". When the heat release amount was reduced by 15% or more but less than 20%, the pot life was evaluated as normal and rated as "△", and when the heat release amount was reduced by less than 15%, the pot life was evaluated as good and rated as "◯".

[0080] [Table 1]

[0081] [Table 2]

[0082] [Table 3]

[0083] Details of each component in Tables 1 to 3 are as follows. *DCP-A: Dimethyloltricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. *AT-20E: Ethoxylated trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. *IBXA: Isobornyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. *P3B: Tetrabutylammonium butyltriphenylborate, manufactured by Showa Denko K.K. *N3B: Tetrabutylammonium butyltrinaphthyl borate, manufactured by Showa Denko K.K. *4P4B: Tetraphenylphosphonium tetraphenylborate, manufactured by Tokyo Chemical Industry Co., Ltd. *TPS: Triphenylsilanol, manufactured by Tokyo Chemical Industry Co., Ltd. *AIBN: Azobisisobutyronitrile, manufactured by Tokyo Chemical Industry Co., Ltd. [Industrial Applicability]

[0084] The curable composition of the present invention has excellent curing properties due to heating, and therefore can be suitably used in various fields, such as paints, adhesives for optical members, sealants for electronic components, and hard coating agents for various plastic substrates of automobiles, home appliances, mobile phones, etc.

Claims

1. The composition contains a polymerizable monomer, an aluminum chelate compound, a silanol compound, and a quaternary boron onium salt, A curable composition, wherein the aluminum chelate compound is held in porous particles.

2. 2. The curable composition according to claim 1, wherein the polymerizable monomer is a radical polymerizable monomer having a carbon-carbon double bond in the molecule.

3. The curable composition according to claim 1 , wherein the polymerizable monomer is a (meth)acrylate.

4. The curable composition according to claim 1 , wherein the porous particles are made of a polyurea resin.

5. The curable composition according to claim 1 , wherein the quaternary boron onium salt is represented by the following general formula (1): 【Chemical 1】 However, in the general formula (1), R １ From R ４ At least one of X is an optionally substituted phenyl group or naphthyl group, and the rest are optionally substituted alkyl groups, or optionally substituted phenyl groups or naphthyl groups. ＋ represents an ammonium cation, a sulfonium cation, a pyridinium cation, a phosphonium cation, an oxonium cation, or an iodonium cation.

6. The curable composition according to claim 1 , wherein the silanol compound is an aryl silanol compound represented by the following general formula (6): 【Chemistry 2】 In the general formula (6), m is 2 or 3, and the sum of m and n is 4. Ar is an aryl group which may have a substituent.

7. The curable composition according to claim 1 , wherein the content of the polymerizable monomer is 80% by mass or more and 97% by mass or less.

8. The curable composition according to claim 1 , wherein the content of the aluminum chelate compound is 0.1% by mass or more and 10% by mass or less.

9. The curable composition according to claim 1 , wherein the content of the silanol compound is 0.1% by mass or more and 10% by mass or less.

10. The curable composition according to claim 1 , wherein the content of the quaternary boron onium salt is 0.1% by mass or more and 5% by mass or less.

11. A cured product obtained by curing the curable composition according to any one of claims 1 to 10 by heating.

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