WO2022092080A1 - Polymerizable composition, cured product, and method for producing cured product - Google Patents

Abstract

The purpose of the present invention is to provide a polymerizable composition from which a cured product, that is a thick film having excellent positional precision, can be obtained in a short time.　The present invention is a polymerizable composition which contains a cationic photopolymerization initiator, a cationic thermal polymerization initiator and a cationic polymerizable compound. The content of the cationic thermal polymerization initiator is 50-1000 parts by mass relative to 100 parts by mass of the cationic photopolymerization initiator. The cationic photopolymerization initiator preferably contains an aromatic sulfonium salt, and the cationic thermal polymerization initiator preferably contains a benzylphenyl sulfonium salt.

Description

Method for producing polymerizable composition, cured product and cured product

The present invention relates to a polymerizable composition containing a photocationic polymerization initiator, a thermal cationic polymerization initiator and a cationically polymerizable compound.

Cathodic curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like. Various reports have been made on the improvement of such a curable composition.

In an electronic substrate, an adhesive may be used as a method for adhering components such as semiconductors and optical components onto an insulating substrate. Due to the high integration of electronic boards in recent years, high position accuracy is required for bonding parts. Patent Documents 1 and 2 disclose a method of temporarily fixing by an ultraviolet irradiation step using an adhesive and then performing main fixing by a heating step. Further, Patent Documents 1 and 2 disclose a composition containing an epoxy resin as a main raw material as an adhesive used for adhering optical components.

Japanese Unexamined Patent Publication No. 2019-019286 Japanese Unexamined Patent Publication No. 2019-073574

Adhesives for fixing members such as electronic parts are relatively thick and are required to provide a cured product with excellent position accuracy in a short time, but conventional cationic curable compositions have poor curability. In some cases it was enough.

Therefore, an object of the present invention is to provide a polymerizable composition which is excellent in position accuracy and has a thickness of 30 μm or more (hereinafter, may be referred to as “thick film”) and can obtain a cured product in a short time. It is in.

As a result of diligent studies, the present inventors have decided to use the photocationic polymerization initiator and the thermal cation polymerization initiator in combination, and preferably to increase the amount of the thermal cation polymerization initiator used with respect to the photocationic polymerization initiator. It was found that a cured product having a thickness of 30 μm or more can be obtained only by light irradiation, and the present invention has been reached.

That is, the present invention is a polymerizable composition containing a photocationic polymerization initiator, a thermal cationic polymerization initiator and a cationically polymerizable compound, and the content of the thermal cationic polymerization initiator is 100 parts by mass of the photocationic polymerization initiator. It is a polymerizable composition having an amount of 50 to 1000 parts by mass.

Hereinafter, the polymerizable composition of the present invention will be described based on a preferred embodiment.
The polymerizable composition of the present invention contains a photocationic polymerization initiator, a thermal cationic polymerization initiator and a cationically polymerizable compound.

The photocationic polymerization initiator used in the polymerizable composition of the present invention is a compound capable of generating a cationic species or Lewis acid by light irradiation, and any compound may be used, but Lewis acid may be generated by irradiation with ultraviolet rays. An onium salt or a derivative thereof that releases the above-mentioned is preferable from the viewpoint of excellent curability. Typical examples of such compounds include salts of cations and anions represented by the general formula [A] ^{m +} [B] ^m- .

Here, it is preferable that the cation [A] ^{m +} is an onium ion from the viewpoint of excellent curability, and the structure thereof can be expressed by, for example, the general formula [ _Ga Q] ^{m +} .
In the formula, G is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a G's are independent of each other and may be the same or different. Further, it is preferable that at least one G is an organic group having an aromatic ring from the viewpoint of excellent curability. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N = N. Further, when the valence of Q is q, it is necessary that the relationship m = aq is established (however, N = N is treated as valence 0).

The anion [B] ^m- is not particularly limited, but a halide complex is preferable from the viewpoint of excellent curability, and the structure thereof is, for example, the general formula [LX _b ] ^m- . Can be represented by.
In the formula, L is a metal or metalloid that is the central atom of the halide complex, and is, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom such as fluorine, chlorine, bromine or iodine. b is an integer of 3 to 7. Further, when the valence of L is p, it is necessary that the relationship m = bp is established.

Specific examples of the anion [LX _b ] ^m- of the above general formula include perchlorate ion (ClO _4- ⁾ , tetrafluoroborate ion (BF _4- ⁾ , hexafluorophosphate ion (PF _6- ⁾ , and hexa. Inorganic ions such as fluoroantimonate (SbF _6- ⁾ , hexafluoroarsenate (AsF _6- ^{) and} hexachloroantimonate (SbCl _6- ); fluorosulphonate ion (FSO _3- ⁾ , toluene sulfonic acid anion, trinitrobenzene Sulfonic acid ions such as sulfonic acid ion, camphor sulfonic acid ion, nonafluorobutane sulfonic acid ion and hexadecafluorooctane sulfonic acid ion; borate ion such as tetraaryl borate ion and tetrakis (pentafluorophenyl) borate ion; methanecarboxylic acid Carbonate ions such as ions, ethane carboxylic acid ion, propane carboxylic acid ion, butane carboxylic acid ion, octane carboxylic acid ion, trifluoromethane carboxylic acid ion, benzene carboxylic acid ion and p-toluene carboxylic acid ion; trifluoromethyl sulfite ion (CF ₃ SO _3- ⁾ , methyl sulfate ion (CH ₃ OSO _3- ⁾ , bis (trifluoromethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion and the like can be mentioned.

In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). From these, one of them can be used alone, or two or more of them can be mixed and used.
(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryliodonium salts such as hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilucmiliodonium tetrakis (pentafluorophenyl) borate, etc. (c) With sulfonium cations represented by the following group I or group II. Sulfonium salt consisting of hexafluoroantimon ion, tetrakis (pentafluorophenyl) borate ion, etc.

In addition, as other preferable ones, (η5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron- Iron-arene complex such as hexafluorophosphate; aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum and tris (salitylaldehidato) aluminum, and silanols such as triphenylsilanol. Mixtures and the like can also be mentioned.

Among these, aromatic iodonium salts, aromatic sulfonium salts and iron-alene complexes are preferable, and aromatic sulfonium salts represented by the following general formula (1) are excellent in curability of the obtained polymerizable composition. Especially preferable.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, and carbon atoms 1 to 10. Represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are. Independently, each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, Z represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, and X ₁ ⁻ is monovalent. Represents an anion.

Among the aromatic sulfonium salts represented by the general formula (1), Z is more preferable because it is excellent in curability of the polymerizable composition which is the group represented by the following general formula (1a).

In the formula, R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or carbon. It represents an ester group having 2 to 10 atoms, and * represents a bond.

Examples of the halogen atom in the general formula (1) include fluorine, chlorine, bromine and iodine.

In the alkyl group having 1 to 10 carbon atoms in the general formula (1), the hydrogen atom in the group is replaced with a halogen atom, and the methylene group in the group is —O—, —S—, Groups substituted with -CO-, -OCO-, -COO-, -C = C-, -NHCO-, -NH- or -CONH- are also included. Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, and octyl. , Nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl , Trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tri Decafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxy Methyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxy Methyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, Acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl and 1,2-dihydroxyethyl And so on.

Examples of the alkoxy group having 1 to 10 carbon atoms in the general formula (1) include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, and t. -Amiloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy , Methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy and the like.

Examples of the ester group having 2 to 10 carbon atoms in the general formula (1) include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy and trichloroacetyl. Examples thereof include oxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy and benzoyloxy.

The hydrocarbon group having 1 to 20 carbon atoms in the general formula (1) may be a group having 1 to 20 carbon atoms including a carbon atom and a hydrogen atom, and is not particularly limited, but carbon. Alkyl group with 1 to 20 atoms, alkenyl group with 2 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, cycloalkylalkyl group with 4 to 20 carbon atoms, aryl with 6 to 20 carbon atoms Examples thereof include a group and an arylalkyl group having 7 to 20 carbon atoms. Further, in the hydrocarbon group having 1 to 20 carbon atoms in the general formula (1), the hydrogen atom in the group is replaced with a halogen atom, and the methylene group in the group is -O-,-. Groups substituted with S-, -CO-, -OCO-, -COO-, -C = C-, -NHCO-, -NH- or -CONH- are also included.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, heptyl, isoheptyl, t. -Heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and Examples thereof include linear, branched and cyclic alkyl groups such as cyclodecyl.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-Tetradecatrienylallyl and the like, linear and cyclic alkenyl groups and the like.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthrasenyl, etc. Can be mentioned.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-Cyclononylpropyl, 3-Cyclodecylpropyl, 4-Cyclobutylbutyl, 4-Cyclopentylbutyl, 4-Cyclohexylbutyl, 4-Cycloheptylbutyl, 4-Cyclooctylbutyl, 4-Cyclononylbutyl, 4-Cyclodecyl Examples thereof include butyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, trill, xylyl, ethylphenyl, biphenylyl, naphthyl, anthryl and phenanthrenyl, and the hydrogen atom in these groups is the alkyl group and the alkenyl group. Examples thereof include groups substituted with a carboxyl group or a halogen atom, such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl and 2,4,6-trimethylphenyl.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom in the alkyl group is replaced with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom in the alkyl group is substituted with an aryl group, and examples thereof include benzyl and α-methylbenzyl. , Α, α-dimethylbenzyl, phenylethyl and the like.

Examples of the _monovalent ^anion represented by X1- in the general formula (1) include a monovalent anion among the anions exemplified as the above-mentioned anion [LX _b ] ^m- .

Among the aromatic sulfonium salts represented by the general formula (1), compounds having one or more halogen atoms among R ¹ to R ²³ are preferable because the obtained polymerizable composition has high curability. In particular, a compound in which one or more of R ¹ to R ¹⁰ is a halogen atom, particularly a fluorine atom is preferable. It is preferable that R ³ or R ⁸ is a halogen atom because the stability of the compound is high and the curability of the obtained polymerizable composition is high, and both R ³ and R ⁸ are halogen atoms, especially fluorine. It is preferably an atom. Further, it is also preferable that one or more of R ¹⁵ to R ¹⁸ are halogen atoms, especially chlorine atoms.

Examples of the monovalent anion represented by X ₁ ⁻ constituting the aromatic sulfonium salt represented by the general formula (1) include perchlorate ion (ClO _4- ⁾ and tetrafluoroborate ion (BF _4- ⁾ . ), Hexafluorophosphate ion (PF _6- ⁾ , Hexafluoroantimonate (SbF _6- ⁾ , Hexafluoroarsenate (AsF _6- ^{) and} Hexachloroantimonate (SbCl _6- ); And tetrax (pentafluorophenyl) borate ion and other borate ions; tris (trifluoromethanesulfonyl) methide ion; tris (perfluoroalkyl) phosphine anion trifluoride are preferable, and the obtained polymerizable composition has good curability. In particular, hexafluorophosphate ion (PF _6- ⁾ and hexafluoroantimonate (SbF _6- ⁾ are preferable.

Commercially available products can also be used as the photocationic polymerization initiator, for example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (all manufactured by Union Carbide), Irgacure 261 and CG-. 24-61 (above, BASF), DAICATII (Daicel), UVAC1591 (Daicel Ornex), CI-2481, CI-2734, CI-2823, CI-2758 (above, Nippon Soda) , FFC509 (manufactured by 3M), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (all manufactured by Midori Chemical Co., Ltd.) ) Etc. can be mentioned.

The content of the photocationic polymerization initiator is not particularly limited, but is preferably 0.01 to 10 parts by mass and 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound. Parts are more preferable, and 0.5 to 3.0 parts by mass are particularly preferable. When the content of the photocationic polymerization initiator is within the above range, the obtained polymerizable composition is preferable because it has excellent curability. As the photocationic polymerization initiator, one type may be used alone, or two or more types may be mixed and used. When two or more kinds are mixed and used, the content refers to the total content of the plurality of photocationic polymerization initiators.

The thermal cationic polymerization initiator used in the polymerizable composition of the present invention is a compound capable of generating a cationic species or Lewis acid by heating, and any compound may be used, but the above-mentioned photocationic polymerization initiator may be used. Compounds classified as are excluded.

Examples of the thermal cation polymerization initiator include salts such as sulfonium salt, iodonium salt, diazonium salt, phosphonium salt, selenium salt, oxonium salt, ammonium salt, thiophenium salt, thiolanium salt, benzylammonium salt, pyridinium salt and hydrazinium salt; Iimide sulfonates such as imide sulfonate and phthalimide sulfonate; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and Alicyclic polyamines such as isophoronediamine; aromatic polyamines such as m-xylylene diamine, diaminodiphenylmethane and diaminodiphenylsulfone; the polyamines and phenylglycidyl ether, butylglycidyl ether, bisphenol A-diglycidyl ether and bisphenol. Polyepoxy addition-modified product produced by reacting glycidyl ethers such as F-diglycidyl ether or various epoxy resins such as glycidyl esters of carboxylic acid by a conventional method; the organic polyamines and phthalic acid and isophthal. Amidated modified products produced by reacting an acid with a carboxylic acid such as a dimeric acid by a conventional method; the polyamines, aldehydes such as formaldehyde, phenol, cresol, xylenol, tertiary butylphenol, resorcin and the like. Mannig modified product produced by reacting with a phenol having at least one aldehyde oxidation-reactive site in the nucleus by a conventional method; polyvalent carboxylic acid (succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid). , Pimelic acid, Sveric acid, Azelaic acid, Sevacinic acid, Dodecanedioic acid, 2-Methylsuccinic acid, 2-Methyladipic acid, 3-Methyladipic acid, 3-Methylpentanedioic acid, 2-Methyloctanedioic acid, 3, Aliphatic dicarboxylic acids such as 8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; cyclohexane. Acid anhydrides of alicyclic dicarboxylic acids such as dicarboxylic acids; tricarboxylic acids such as trimerics of trimellitic acid, trimesic acid and castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid; benzointosylate , P-Nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyltosylate, 2,6-dinitrobenzyltosylate and 2,4-dinitrobenzyltosylate and other sulfonic acid esters; dicyandiamide, imidazole Types, carboxylic acid esters, amineimides, halogen compounds and the like can be mentioned, and these can be used alone or in admixture of two or more.

As the thermal cationic polymerization initiator, a sulfonium salt is preferable because the obtained polymerizable composition has good curability. In particular, a monophenylsulfonium salt is preferable because it is easily available industrially, and the monophenylsulfonium salt includes a benzyl-p-hydroxyphenylmethylsulfonium salt, a p-hydroxyphenyldimethylsulfonium salt, and a p-acetoxyphenyldimethylsulfonium salt. , Benzyl-p-hydroxyphenylmethylsulfonium salt, benzylphenylsulfonium salt and the like.

Among them, the benzylphenylsulfonium salt is preferable because it is excellent in the deep curability of the obtained polymerizable composition, and the benzylphenylsulfonium salt represented by the following general formula (2) is particularly preferable.

In the formula, R ³¹ represents a hydrogen atom, an acyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, and represents R ³² , R ³³ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ . , R ³⁹ , R ⁴⁰ and R ⁴¹ are independently hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms or ester group having 2 to 10 carbon atoms. R ³² and R ³³ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , and R ⁴⁰ and R ⁴¹ are bonded to each other and have 3 to 10 carbon atoms. R ³⁴ represents an alkyl group having 1 to 10 carbon atoms or an aromatic ring-containing group having 6 to 20 carbon atoms, ^and X _2- represents a monovalent anion.

The halogen atom in the general formula (2), the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the ester group having 2 to 10 carbon atoms are in the general formula (1). It is the same as a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms.

Examples of the acyl group having 2 to 10 carbon atoms in the general formula (2) include acetyl, propionyl, isopropionyl, butyryl, isobutyryl, benzoyl, chloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, methoxyacetyl and acet. Acetyl and the like can be mentioned.

Examples of the aromatic ring-containing group having 6 to 20 carbon atoms in the general formula (2) include an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl and anthrasenyl.
Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl and the like.

A ring of 3 to 10 carbon atoms formed by bonding R ³² and R ³³ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , and R ⁴⁰ and R ⁴¹ to each other. Examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopentene ring, a cyclopentadiene ring, a cyclohexane ring, a cyclohexene ring, a benzene ring and a cyclooctane ring.

A compound in which R ³¹ in the benzylphenyl sulfonium salt represented by the general formula (2) is a hydrogen atom or an acyl group having 2 to 10 carbon atoms has a high deep curability of the obtained polymerizable composition. Therefore, a compound which is an acyl group is particularly preferable.

If R ³² and R ³³ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , and R ⁴⁰ and R ⁴¹ are not coupled to each other to form a ring, then R ³² , R ³³ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ are preferably hydrogen atoms. A compound having such a structure is preferable because it is chemically stable and has excellent deep curability of the obtained polymerizable composition.

A compound in which one or more of R ³² and R ³³ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , and R ⁴⁰ and R ⁴¹ are bonded to each other to form a benzene ring. It is preferable because the deep curability of the obtained polymerizable composition is high, and any one of R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , and R ³⁸ and R ³⁹ is bonded to each other and benzene. Compounds forming a ring are particularly preferred.

The monovalent anions represented ^by X2- _are perchlorate ion (ClO _4- ⁾ , tetrafluoroborate ion (BF _4- ⁾ , hexafluorophosphoric acid ion (PF _6- ⁾ , and hexafluoroantimonate. Inorganic ions such as (SbF _6- ⁾ , hexafluoroarsenate (AsF _6- ^{) and} hexachloroantimonate (SbCl _6- ) are preferable, and hexafluorophosphoric acid ions (hexafluorophosphoric acid ions) are particularly good because the polymerizable composition has good curability. PF _6- ⁾ and hexafluoroantimonate (SbF _6- ⁾ are preferred.

Examples of the monophenylsulfonium salt represented by the general formula (2) include benzyl-p-hydroxyphenylmethylsulfonium salt, benzyl-p-acetoxyphenylmethylsulfonium salt, benzyl-p-hydroxyphenylmethylsulfonium salt and 1-naphthyl. Examples thereof include methyl-p-hydroxyphenylmethylsulfonium salt.

Commercially available products can also be used as the thermal cationic polymerization initiator, for example, CI-2064, CI-2624, CI-2739, CI-2855, CI-2920, CI-2921, CI-2946, CI-3128 (or more). , Made by Nippon Soda Corporation), SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110L, SI-145, SI-150 , SI-160, SI-180, SI-180L (above, manufactured by Sanshin Chemical Co., Ltd.), TA-90, TA-100, TA-120, TA-160, IK-1, IK-2 (above, manufactured by Sun Appro). , Adeka Opton CP-66, Adeka Opton CP-77 (above, manufactured by ADEKA), FC-520 (manufactured by 3M) and the like.

The content of the thermal cationic polymerization initiator is 50 to 1000 parts by mass with respect to 100 parts by mass of the photocationic polymerization initiator. It is preferably 100 to 500 parts by mass, and particularly preferably 150 to 500 parts by mass. When the content of the thermal cationic polymerization initiator is within the above range, it is preferable because the obtained polymerizable composition is excellent in deep curability. As the thermal cationic polymerization initiator, one type may be used alone, or two or more types may be mixed and used. When two or more kinds are mixed and used, the content refers to the total content of the plurality of thermal cationic polymerization initiators.

The cationically polymerizable compound used in the polymerizable composition of the present invention is a compound that undergoes a polymerization or cross-linking reaction with a cationic species or Lewis acid generated from the above-mentioned photocationic polymerization initiator or thermal cationic polymerization initiator. However, examples thereof include an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro-orthoester compound and a vinyl compound.

As the cationically polymerizable compound, a polyfunctional cationically polymerizable compound having a plurality of groups causing a polymerization or cross-linking reaction in the molecule is preferable because it has excellent deep curability.

Among these compounds, epoxy compounds and oxetane compounds are preferable because they are easy to obtain and have good curability.

Examples of the epoxy compound include an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound and the like, and among them, an alicyclic epoxy compound and an aromatic epoxy compound are preferable. When the cationically polymerizable compound is the above-mentioned compound, the obtained polymerizable composition has excellent curability.
The epoxy compound includes all compounds containing an epoxy group. For example, a compound containing both an epoxy group and an oxetanyl group shall be included in the epoxy compound.

Specific examples of the alicyclic epoxy compound include polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, and a cycloalkene structure-containing compound such as a cyclohexene structure or a cyclopentene structure to be epoxidized with an oxidizing agent. Examples thereof include cycloalkene oxide structure-containing compounds obtained by. Examples of the alicyclic epoxy compound include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-1-methylcyclohexyl-3,4. -Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4 -Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro) -3,4-Epoxy) Cyclohexane-Metadioxane, Bis (3,4-Epoxycyclohexylmethyl) adipate, 3,4-Epoxy-6-methylcyclohexylcarboxylate, Methylenebis (3,4-Epoxycyclohexane), Dicyclopentadiene Diepoxyside, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2- Examples thereof include epoxy-2-epoxyethylcyclohexane, 3,4-epoxycyclohexylmethylacrylate and 3,4-epoxycyclohexylmethylmethacrylate.
An epoxy compound having both an aliphatic ring and an aromatic ring is considered to correspond to an alicyclic epoxy compound.

Commercially available products that can be suitably used as the alicyclic epoxy compound include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (all manufactured by Union Carbide), seroxide 2021, and seroxide 2021P. Selokiside 2081, Selokiside 2083, Selokiside 2085, Selokiside 2000, Selokiside 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolyde HD300, EHPE- 3150, EHPE-3150CE (above, manufactured by Daicel), KRM-2110, KRM-2199 (above, manufactured by ADEKA) and the like can be mentioned.
Among the alicyclic epoxy compounds, an epoxy resin having a cyclohexene oxide structure is preferable because the obtained polymerizable composition has excellent curability.

Specific examples of the aromatic epoxy compound include polyhydric phenol having at least one aromatic ring or polyglycidyl ether of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F, and further alkylene oxide. Examples thereof include glycidyl ether, which is a compound to which the above is added, and epoxy novolak resin.
The aromatic epoxy compound is an epoxy compound having an aromatic ring and no aliphatic ring.
The aromatic epoxy compound is preferable because the obtained polymerizable composition has excellent deep curability.

Specific examples of the aliphatic epoxy compound include polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, polyglycidyl ester of an aliphatic long-chain polybasic acid, glycidyl acrylate or homo synthesized by vinyl polymerization of glycidyl methacrylate. Examples thereof include polymers synthesized by vinyl polymerization of polymers, glycidyl acrylate or glycidyl methacrylate and other vinyl monomers, and typical compounds include 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether. , Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol and diglycidyl ether of polyhydric alcohols such as diglycidyl ether of polypropylene glycol. Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylol propane and glycerin; diglycidyl ester of aliphatic long chain dibasic acid etc. Can be mentioned. Further, monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol, or alkylene oxide to these; glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxide stearers. Examples thereof include octyl acid, butyl epoxide stearate, epoxidized soybean oil and epoxidized polybutadiene.
The aliphatic epoxy compound is an epoxy compound having no aromatic ring and cyclohexene oxide structure.

Commercially available products that can be suitably used as the aromatic epoxy compound and the aliphatic epoxy compound include jERYX-4000, jERYX-8000, jER871, jER872, jER157S70, jER806, jER1001, jER152, and jER604 (all manufactured by Mitsubishi Chemical Corporation) PY. -306, 0163, DY-022 (above, manufactured by Ciba Geigy), KRM-2720, EP-4100, EP-4000, EP-4080, EP-4088, EP-4900, ED-505, ED-506 (above, ED-506) ADEKA), Epolite M-1230, Epolite EHDG-L, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 100MF , Epolite 3002, Epolite FR-1500 (above, manufactured by Kyoeisha Chemical Co., Ltd.), Santoto ST0000, YD-716, YH-300, PG-202, PG-207, YD-172, YDPN638 (above, manufactured by Nippon Steel Chemical Co., Ltd.) ) Denacol EX321, Denacol EX313, Denacol 314, Denacol EX-411, EM-150 (all manufactured by Nagase ChemteX Corporation), EPPN-201, EPPN-502H, NC-3000, NC-7300L, XD-1000, NC- 2000-L, NC-7000L, CER-3000-L, EOCN-104S, EOCN-1020, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

Specific examples of the oxetane compound include, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-. Fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-) Oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether ) Ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl Oxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-) Ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3) -Ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3) -Oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, Bornil (3-ethyl-3-oxetanylmethyl) ether, 3, 7-Bis (3-oxetanyl) -5-oxa-nonane, 3,3'-(1,3- (2-methyrenyl) propandiylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-) Oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl) -3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecandyldimethylene (3-ethyl) -3-oxetanylmethyl) ether, trimethylolpropanthris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl) -3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ) Ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ) Ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, ditrimethylol propanetetrax (3-ethyl-) 3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A-bis (3) -Ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like can be mentioned.

Commercially available products that can be suitably used as the oxetane compound include Aron Oxetane OXT-101, OXT-121, OXT-221, OXT-212, OXT-221 (all manufactured by Toagosei Corporation), Ethanacole EHO, OXBP, and OXTP. OXMA (above, manufactured by Ube Kosan Co., Ltd.) and the like can be mentioned.

A polymerizable composition containing an oxetane compound as a cationically polymerizable compound is preferable because it has excellent deep curability. As the oxetane compound, an oxetane compound having two or more oxetane groups in the same molecule is more preferable, and an oxetane compound having two oxetane group is particularly preferable.

The content of the oxetane compound is not particularly limited, but is preferably 5 to 90 parts by mass, more preferably 20 to 80 parts by mass, and 30 to 70 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound. Part is particularly preferable. When the content of the cationic compound is within the above range, the obtained polymerizable composition is preferable because it has excellent curability.

Other cationically polymerizable compounds include oxorane compounds such as tetrahydrofuran and 2,3-dimethyltetraxyl; cyclic acetal compounds such as trioxane, 1,3-dioxolane and 1,3,6-trioxanecyclooctane; β-propiolactone. And Cyclic lactone compounds such as ε-caprolactone; Thiylan compounds such as ethylene sulfide and thioepicrolhydrin; Thietan compounds such as 1,3-propine sulfide and 3,3-dimethylthietan; Cyclic thioether compounds such as tetrahydrothiophene derivatives; Ethylene Vinyl ether compounds such as glycol divinyl ether, alkyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether and propenyl ether of propylene glycol; epoxy. Spiro-orthoester compounds obtained by the reaction of compounds with lactones; ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene and polybutadiene, derivatives of these compounds and the like can be mentioned.

The polymerizable composition of the present invention may contain a sensitizer.
A polymerizable composition containing a sensitizer is preferable because it has excellent deep curability. The sensitizer means a substance that does not have polymerizability and promotes cationic polymerization when used in combination with the photocationic polymerization initiator, and is classified into the photocationic polymerization initiator or the thermal cationic polymerization initiator. Compounds that are used are excluded.

Examples of the sensitizer include anthracene-based sensitizers, naphthalene-based sensitizers, benzocarbazole-based initiators, and the like, and benzocarbazole-based sensitizers are particularly preferable because they have excellent reactivity. Two or more of these sensitizers can be used in combination. The structure of the preferred sensitizer is illustrated below.

In the formula, R represents an alkyl group having 1 to 10 carbon atoms.

The content of the sensitizer is not particularly limited, but is preferably 1 to 1000 mol, more preferably 5 to 500 mol, and 10 to 200 mol with respect to 1 mol of the photocationic polymerization initiator. Is particularly preferred. When the content of the sensitizer is within the above range, the obtained polymerizable composition is preferable because it has excellent curability.

The polymerizable composition of the present invention may contain a sulfate.
A polymerizable composition containing a sulfate is preferable because it has good thermal stability and excellent deep curability. Among the sulfates, alkyl sulfates are particularly preferable. Examples of the anion ion of the alkyl sulfate include methyl sulfate ion, ethyl sulfate ion and propyl sulfate ion.

As the cation ion of the sulfate, sulfonium ion is preferable because the polymerizable composition has good thermal stability and high deep curability, and sulfonium ion represented by the following general formula (3) is particularly preferable.

In the formula, R ⁵¹ represents a hydrogen atom, an acyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, and R ⁵² , R ⁵³ , R ⁵⁶ and R ⁵⁷ are independent of each other. Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and R ⁵² and R ⁵³ and R ⁵⁶ and R ⁵⁷ represent. , May be bonded to each other to form a ring having 3 to 10 carbon atoms, and R ⁵⁴ and R ⁵⁵ represent a hydrocarbon group having 1 to 20 carbon atoms.

The halogen atom in the general formula (3), an acyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms. The ring having 3 to 10 carbon atoms is a halogen atom in the general formula (2), an acyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an alkoxy having 1 to 10 carbon atoms. It is the same as a group, an ester group having 2 to 10 carbon atoms, and a ring having 3 to 10 carbon atoms. Further, the hydrocarbon group having 1 to 20 carbon atoms in the general formula (3) is the same as the hydrocarbon group having 1 to 20 carbon atoms in the general formula (1).

Among the cation ions represented by the general formula (3), those in which R ⁵¹ is a hydrogen atom are preferable because they have good thermal stability and excellent deep curability of the obtained polymerizable composition.

Among the cation ions represented by the general formula (3), those in which R ⁵² , R ⁵³ , R ⁵⁶ and R ⁵⁷ are hydrogen atoms have good thermal stability of the obtained polymerizable composition and have good thermal stability. It is preferable because it has excellent deep curability.

Examples of the sulfate used in the present invention include aromatic sulfonium alkyl sulphate, and specific examples thereof include 4-hydroxyphenyl (dimethyl) sulfonium methyl sulphate.

The content of the sulfate is not particularly limited, but is preferably 0.01 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the thermal cationic polymerization initiator. Especially preferable. When the content of the sulfate is within the above range, the obtained polymerizable composition has good thermal stability and excellent curability, which is preferable.

The polymerizable composition of the present invention usually contains a solvent (a compound that exists as a liquid at 25 ° C. under atmospheric pressure and does not belong to each of the above-mentioned components) capable of dissolving or dispersing the above-mentioned components as needed, for example. Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol and the like can be added. In the polymerizable composition of the present invention, the content of the solvent is appropriately selected depending on the intended use of the polymerizable composition and is not particularly limited, but usually, the solid content of the polymerizable composition (total of all components other than the solvent). When the solvent is contained so that the content) is 5 to 90% by mass, handling such as when forming a coating film becomes easy.

Further, as long as the effects of the present invention are not impaired, benzotriazole-based, triazine-based and benzoate-based ultraviolet absorbers; phenol-based, phosphorus-based and sulfur-based antioxidants; cationic surfactants, anions, as necessary. Antistatic agents such as based surfactants, nonionic surfactants and amphoteric surfactants; halogen-based compounds, phosphate ester-based compounds, phosphate amide-based compounds, melamine-based compounds, fluororesins or metal oxides, (poly). ) Flame-retardant agents such as melamine phosphate and (poly) piperazine phosphate; hydrocarbon-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based and metal soap-based lubricants; pigments and carbon black, etc. Colorants; fumed silica, fine particle silica, silicate, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, cericite, kaolinite, flint, spleen powder, sardine, attapargit, talc, mica, minesotite, pyro Silica-based inorganic additives such as philite and silica; fillers such as glass fibers and calcium carbonate; crystallization agents such as nucleating agents and crystallization accelerators; rubber elasticity-imparting agents such as silane coupling agents and flexible polymers Add various additives such as other monomers, defoaming agents, thickeners, leveling agents, plasticizers, polymerization inhibitors, antistatic agents, flow regulators, coupling agents and adhesion promoters. Can be done. The total amount of these various additives used is 50% by mass or less in the polymerizable composition of the present invention.

The polymerizable composition of the present invention can be cured by irradiating it with active energy rays such as ultraviolet rays, and usually cures to a dry touch or a solvent-insoluble state 0.1 seconds to several minutes after irradiation. be able to. Suitable active energy rays may be any as long as they induce the decomposition of the photoacid generator, but are preferably ultrahigh pressure, high pressure, medium pressure and low pressure mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, fluorescence. 200nm obtained from lamps, tungsten lamps, excimer lamps, sterilization lamps, excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, YAG lasers, light emitting diodes, CRT light sources, etc. Electromagnetic energy having a wavelength of 700 nm and high active energy rays such as electron beam, X-ray and radiation are used.

The irradiation time of the active energy ray depends on the intensity of the active energy ray, the coating thickness and the cationically polymerizable organic compound, but usually about 0.1 to 10 seconds is sufficient. However, for a relatively thick coating film, it is preferable to set the irradiation time longer. After 0.1 seconds to several minutes after irradiation with active energy rays, most of the compositions are touch-dried by cationic polymerization, but in some cases, thermal energy from heating or a thermal head may be used in combination to promote cationic polymerization. Is preferable.

Further, the polymerizable composition of the present invention can be cured by heating with a hot plate such as a hot plate, an atmospheric oven, an inert gas oven, a vacuum oven, a hot air circulation oven or the like.

The heating temperature at the time of thermosetting is not particularly limited, but is preferably 70 to 200 ° C., more preferably 90 to 150 ° C. from the viewpoint of promoting the polymerization of the cationically polymerizable compound. The curing time is not particularly limited, but is preferably 1 to 60 minutes, more preferably 1 to 30 minutes from the viewpoint of improving productivity.

Furthermore, the polymerizable composition of the present invention can be cured by using irradiation with active energy rays and heating in combination. In this case, the polymerizable composition may be heated after being irradiated with the active energy rays, or the polymerizable composition may be heated and then irradiated with the active energy rays. From the viewpoint of improving the position accuracy when used as a member fixing adhesive, it is preferable to heat the composition after irradiating it with active energy rays.

When irradiation and heating of an active energy ray are used in combination for curing the polymerizable composition of the present invention, the above-mentioned active energy rays and a heating device can be used without particular limitation, but the deep curability can be achieved. Since it is excellent, it is preferable to use ultraviolet rays as the active energy ray.

Specific uses of the polymerizable composition of the present invention include optical filters; paints; coating agents; lining agents; adhesives; printing plates; insulating varnishes; insulating sheets; laminated plates; printed substrates; semiconductor devices, LED packages. Sealants for printing, liquid crystal injection ports, organic EL, optical elements, electrical insulation, electronic parts, separation films, etc .; molding materials; putty; glass fiber impregnating agents; sealing agents; semiconductors and the sun Passion film for batteries, etc .; Interlayer insulation film; Protective film; Print substrate; Color filter for color TVs, PC monitors, mobile information terminals and CCD image sensors; Electrode material for plasma display panels; Printing ink; Dental composition; It can be used for various purposes such as optotyping resin; liquid and dry film; micromechanical parts; glass fiber cable coating; holography recording material, and the use is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples and the like.

[Examples 1 to 32 and Comparative Examples 1 to 10]
Each component and a solvent (propylene carbonate) were mixed with the formulations shown in Tables 1 to 4 and stirred until the insoluble matter disappeared to obtain a polymerizable composition of each Example and Comparative Example.
Cationic polymerizable compounds A-1 to A-4, photocationic polymerization initiators B-1 to B-2, thermal cationic polymerization initiators C-1 to C-3, sensitizers D-1 to D-4, stable. The agent E-1, the radically polymerizable compounds F-1 to F-2, and the photoradical polymerization initiator G-1 are compounds having the following structures, respectively.

(Storage stability)
After preparing the polymerizable composition, the rate of change in viscosity after storage at 25 ° C. for 1 week was evaluated. The results are summarized in Tables 1 to 4. A with a viscosity change rate of less than 10%, B with a viscosity change rate of 10% or more and less than 25%, C with a viscosity change rate of 25% or more and less than 50%, and a viscosity change rate of 50% or more. The thing was designated as D. The smaller the change in viscosity, the better the storage stability, which is preferable.

(Deep curability)
A polymerizable composition was applied to a release film (Lumilar T60: manufactured by Toray Industries, Inc.) with a bar coater so as to have a specified film thickness (100 μm, 50 μm, and 30 μm), and an LED light source (100 mW / cm ² ) having a wavelength of 365 nm was applied. After ² exposures at 500 mJ / cm, the film was allowed to stand at room temperature for 2 hours. After that, the release film was peeled off and the condition of the peeled surface was confirmed. When the tack was not confirmed on the peeled surface, it was judged that the cured product was obtained, and when the tack was confirmed, it was judged that the cured product was not obtained. A cured product having a larger film thickness can be obtained, which is preferable as an adhesive for members. The results are summarized in Tables 1 to 4.
A: A cured product having a film thickness of 100 μm was obtained.
B: A cured product having a film thickness of 100 μm was not obtained, but a cured product having a film thickness of 50 μm was obtained.
C: A cured product having a film thickness of 50 μm was not obtained, but a cured product having a film thickness of 30 μm was obtained.
D: A cured product having a film thickness of 30 μm could not be obtained.

(Curing shrinkage rate)
A polymerizable composition was applied to a release film (Lumilar T60: manufactured by Toray Industries, Inc.) with a bar coater so as to have a film thickness of 30 μm, and exposed to 500 mJ / cm ² using an LED light source (100 mW / cm ² ) having a wavelength of 365 nm. After that, it was allowed to stand at room temperature for 2 hours. Then, the release film was peeled off to obtain a sample. The densities of the obtained sample and the pre-cured sample were measured using a gas pycnometer (JIS Z8837). After that, the curing shrinkage rate was calculated from the rate of density change before and after curing. The smaller the curing shrinkage rate, the higher the position accuracy, which is preferable as an adhesive for members. The results are summarized in Tables 1 to 4.
A: Curing shrinkage rate is less than 4%.
B: Curing shrinkage rate 4% or more and less than 7%.
C: Curing shrinkage rate 7% or more.

From Tables 1 to 4, it is clear that the polymerizable composition of the present invention is excellent in storage stability, sensitivity, deep curability and position accuracy. The use of the polymerizable composition of the present invention is not limited, but it is particularly useful as a member fixing adhesive typified by electronic parts, wiring, in-vehicle materials, and the like.

The polymerization composition of the present invention can obtain a cured product of a thick film having excellent position accuracy in a short time by irradiating it with active energy rays, and a cured product of a thick film is required because of its high productivity. It is useful as a polymerizable composition used for applications.

Claims (8)

1. A polymerizable composition containing a photocationic polymerization initiator, a thermal cationic polymerization initiator, and a cationically polymerizable compound.
   A polymerizable composition in which the content of the thermal cationic polymerization initiator is 50 to 1000 parts by mass with respect to 100 parts by mass of the photocationic polymerization initiator.
2. The polymerizable composition according to claim 1, wherein the photocationic polymerization initiator contains an aromatic sulfonium salt.
3. The polymerizable composition according to claim 1 or 2, wherein the thermal cationic polymerization initiator contains a benzylphenyl sulfonium salt.
4. The polymerizable composition according to any one of claims 1 to 3, wherein the cationically polymerizable compound contains an oxetane compound.
5. The polymerizable composition according to any one of claims 1 to 4, which contains a sensitizer.
6. The polymerizable composition according to any one of claims 1 to 5, which contains an alkyl sulfate.
7. The cured product of the polymerizable composition according to any one of claims 1 to 6.
8. A method for producing a cured product, which comprises a step of irradiating the polymerizable composition according to any one of claims 1 to 6 with light.