TW202223052A - 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

Polymerizable composition, cured product, and method for producing the cured product

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

Cationic curable compositions are used in fields such as inks, paints, various coating agents, adhesives, and optical members. Various reports have been made regarding the improvement of such curable compositions.

In electronic substrates, an adhesive may be used as a method of bonding components such as semiconductors and optical components to an insulating substrate. Due to the high integration of electronic substrates in recent years, high positional accuracy is required for the attachment of components. 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. Moreover, in patent documents 1 and 2, the composition which uses an epoxy resin as a main raw material is disclosed as the adhesive agent used for the adhesion|attachment of an optical component. Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent Laid-Open No. 2019-019286 Patent Document 2: Japanese Patent Laid-Open No. 2019-073574

An adhesive for fixing components such as electronic parts is required to provide a relatively thick cured product with excellent positional accuracy in a short period of time, but the conventional cationic curable compositions have insufficient curability.

Therefore, an object of the present invention is to provide a polymerizable composition that can obtain a cured product having a thickness of 30 μm or more (hereinafter, sometimes referred to as a “thick film”), which is excellent in positional accuracy in a short period of time.

The inventors of the present invention have conducted intensive research, and as a result found that by using a cationic photopolymerization initiator and a cationic thermal polymerization initiator together, it is preferable to increase the ratio of the cationic thermal polymerization initiator to the cationic photopolymerization initiator. The amount used is such that a cured product having a thickness of 30 μm or more can be obtained only by light irradiation, thereby completing the present invention.

That is, the present invention is a polymerizable composition comprising a cationic photopolymerization initiator, a cationic thermal polymerization initiator, and a cationic polymerizable compound, and the content of the cationic thermal polymerization initiator is relative to the cationic photopolymerization initiator. 100 parts by mass of the agent is 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 cationic photopolymerization initiator, a cationic thermal polymerization initiator, and a cationic polymerizable compound.

The cationic photopolymerization initiator used in the polymerizable composition of the present invention is a compound that can generate a cationic species or a Lewis acid by light irradiation. It does not matter what kind of compound it is. In terms of excellent curability, Preferably, an onium salt of a Lewis acid or a derivative thereof is released by irradiation with ultraviolet rays. Typical examples of such compounds include salts of cations and anions represented by the general formula [A] ^m+ [B] ^m- .

Here, as the cation [A] ^m+ , an onium ion is preferable in terms of excellent curability, and its structure can be represented by, for example, the general formula [G _a Q] ^m+ . In the formula, G is an organic group having 1 to 60 carbon atoms and may contain several atoms other than carbon atoms. a is an integer of 1-5. a G is independent of each other and may be the same or different. Moreover, it is preferable that at least one G is an organic group which has an aromatic ring from the point which is excellent in hardenability. 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. Furthermore, when the valence of Q is set to q, the relationship of m=a-q must be established (wherein, N=N is regarded as 0 as the valence).

In addition, the anion [B] ^m- is not particularly limited, but is preferably a halide complex in terms of excellent curability, and its structure can be represented, for example, by the general formula [LX _b ] ^m- . In the formula, L is a metal or semi-metal (Metalloid) as the central atom of the halide complex, such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc , V, Cr, Mn, or Co, etc. X is a halogen atom such as fluorine, chlorine, bromine, or iodine. b is an integer of 3-7. Furthermore, when the valence of L is set to p, the relationship of m=b-p must be 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 ^{- )} ), hexafluoroantimonate (SbF ₆ ^- ), hexafluoroarsenate (AsF ₆ ^- ), and hexachloroantimonate (SbCl ₆ ^- ) and other inorganic ions; fluorosulfonate ion (FSO ₃ ^- ), tosylate anion , trinitrobenzenesulfonate ions, camphorsulfonate ions, nonafluorobutanesulfonate ions, and hexafluorooctanesulfonate ions and other sulfonate ions; tetraarylborate ions and tetrakis (pentafluorophenyl)borate ions Borate ions such as ions; methane carboxylate ions, ethane carboxylate ions, propane carboxylate ions, butane carboxylate ions, octane carboxylate ions, trifluoromethane carboxylate ions, benzene carboxylate ions, and p-toluene carboxylate ions Carboxylate ions such as acid ions; trifluoromethyl sulfite ions (CF ₃ SO ₃ ^- ), methyl sulfate ions (CH ₃ OSO ₃ ^- ), bis(trifluoromethanesulfonyl)imide ions, And tris (trifluoromethanesulfonyl) methide ions and so on.

In the present invention, it is particularly effective to use the aromatic onium salts (a) to (c) below among such onium salts. Among these, one kind of them may be used alone, or two or more kinds thereof may be used in combination. (a) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate (b) Diphenyl iodonium hexafluoroantimonate, bis(4-methylphenyl) iodonium hexafluorophosphate, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, tolyl cumene Diaryl iodonium salts such as tetrakis (pentafluorophenyl) borate (c) Perinium salts containing pericium cations represented by the following group I or group II, hexafluoroantimony ions, tetrakis(pentafluorophenyl)borate ions, and the like

[Chemical 1] <Group I>

[Chemical 2] <Group II>

Moreover, as other preferable ones, (η5-2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-n)-(1-methyl) ethyl)benzene]-iron-hexafluorophosphate and other iron-aromatic complexes; aluminum tris (acetone) aluminum, tris (ethyl acetone acetate) aluminum, and tris (salicylic acid) aluminum and other aluminum complexes Compounds and mixtures of silanols such as triphenylsilanol, etc.

Among these, aromatic iodonium salts, aromatic periconium salts, and iron-aromatic complexes are preferred, and in terms of the excellent sclerosing properties of the polymerizable composition obtained, those represented by the following general formula are particularly preferred (1) Aromatic permanium salts.

式中，R ¹、R ²、R ³、R ⁴、R ⁵、R ⁶、R ⁷、R ⁸、R ⁹、及R ¹⁰分別獨立地表示氫原子、鹵素原子、碳原子數為1～10之烷基、碳原子數為1～10之烷氧基、或碳原子數為2～10之酯基，R ¹¹、R ¹²、R ¹³、R ¹⁴、R ¹⁵、R ¹⁶、R ¹⁷、及R ¹⁸分別獨立地表示氫原子、鹵素原子、或碳原子數為1～10之烷基，Z表示氫原子、碳原子數為1～20之烴基，X ₁ ^-表示一價陰離子。 [hua 3]

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

Among the aromatic perylene salts represented by the above-mentioned general formula (1), it is more preferable that Z is a group represented by the following general formula (1a) from the viewpoint of excellent curability of the polymerizable composition.

式中，R ¹⁹、R ²⁰、R ²¹、R ²²、及R ²³分別獨立地表示氫原子、鹵素原子、碳原子數為1～10之烷基、碳原子數為1～10之烷氧基、或碳原子數為2～10之酯基，*表示鍵結鍵。 [hua 4]

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

As a halogen atom in the said general formula (1), fluorine, chlorine, bromine, iodine, etc. are mentioned.

The alkyl group having 1 to 10 carbon atoms in the above general formula (1) also includes a group in which the hydrogen atom in the group is substituted by a halogen atom, and the methylene group in the group is -O-, -S-, -CO-, -OCO-, -COO-, -C=C-, -NHCO-, -NH-, or -CONH- substituted group. Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl yl, isopentyl, third pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxy butyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoro Methyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl , dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl , 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tertiary butylthiomethyl , 4-pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1 -Methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, tert-butyldimethylsilyloxymethyl, 2-(trimethylsilyl) Ethoxymethyl, 3rd-butoxycarbonylmethyl, ethoxycarbonylmethyl, ethylcarbonylmethyl, 3rd-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxy Ethyl, 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, etc.

The alkoxy group having 1 to 10 carbon atoms in the general formula (1) may, for example, include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a second butoxy group. radical, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy, tetrahydrofuranoxy, tetrahydropyridine pyranoxy, 2-methoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxyethoxyethoxy, Methoxyethoxyethoxyethoxy, 3-methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy and the like.

Examples of the ester group having 2 to 10 carbon atoms in the general formula (1) include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, acetyloxy, Propionyloxy, Butyloxy, Chloroacetoxy, Dichloroacetoxy, Trichloroacetoxy, Trifluoroacetoxy, 3-butylcarbonyloxy, Methoxyacetoxy oxy, and benzyloxy, etc.

The hydrocarbon group having 1 to 20 carbon atoms in the general formula (1) is not particularly limited, as long as it is a group having 1 to 20 carbon atoms including carbon atoms and hydrogen atoms, for example: carbon atoms Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkylalkyl having 4 to 20 carbon atoms, An aryl group of 6 to 20, an aralkyl group of 7 to 20 carbon atoms, and the like. In addition, the hydrocarbon group having 1 to 20 carbon atoms in the general formula (1) also includes a group in which the hydrogen atom in the group is substituted by a halogen atom, and the methylene group in the group is replaced by -O-, -S- , -CO-, -OCO-, -COO-, -C=C-, -NHCO-, -NH-, or -CONH- substituted base.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, and pentyl. , isopentyl, third pentyl, hexyl, heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, third octyl, 2-ethylhexyl, n-nonyl, n-decyl , n-dodecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl straight chain, branched , and cyclic alkyl groups, etc.

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-decenyl Linear and cyclic alkenyl such as tetracarbatrienyl allyl, etc.

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms refers to 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, octahydrocyclopentyl Diene, bicyclo[1.1.1]pentyl, and tetradecylhydroanthracenyl, etc.

The above-mentioned cycloalkylalkyl group having 4 to 20 carbon atoms refers to a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted by 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-cyclohexylethyl Decylethyl, 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-cyclodecylbutyl, 3-3-adamantylpropyl, decalinylpropyl, etc.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and the like, and the The hydrogen atom in the base is substituted by the above-mentioned alkyl group, the above-mentioned alkenyl group, carboxyl group, or halogen atom, etc., for example: 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4- Methylphenyl, 2,4,6-trimethylphenyl, etc.

The above-mentioned aralkyl group having 7 to 20 carbon atoms refers to a group having 7 to 20 carbon atoms in which the hydrogen atom in the alkyl group is substituted by an aryl group. For example, a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a naphthylpropyl group, and the like can be mentioned. The above-mentioned aralkyl group with 7 to 10 carbon atoms refers to a group with 7 to 10 carbon atoms formed by replacing the hydrogen atom in the alkyl group with an aryl group, for example, benzyl, α-methylbenzyl group, α,α-dimethylbenzyl, and phenylethyl, etc.

As the monovalent anion represented by X ₁ ^- in the above general formula (1), the monovalent anion among the anions exemplified above as the anion [LX _b ] ^m- can be exemplified.

Among the aromatic perylene salts represented by the above-mentioned general formula (1), the compounds in which one or more of R ¹ to R ²³ are halogen atoms are preferred in view of the high curability of the polymerizable composition to be obtained, especially A compound in which one or more of R ¹ to R ¹⁰ is a halogen atom, especially a fluorine atom, is preferable. In terms of higher stability of the compound and higher curability of the polymerizable composition obtained, preferably R ³ or R ⁸ is a halogen atom, preferably both R ³ and R ⁸ are halogen atoms, Especially fluorine atoms. Furthermore, it is also preferable that one or more of R ¹⁵ to R ¹⁸ is a halogen atom, especially a chlorine atom.

As the monovalent anion represented by X ₁ ^- constituting the aromatic perylene salt represented by the above general formula (1), perchlorate ion (ClO ₄ ^- ), tetrafluoroborate ion (BF ₄ ^- ), Inorganic ions such as hexafluorophosphate (PF ₆ ^- ), hexafluoroantimonate (SbF ₆ ^- ), hexafluoroarsenate (AsF ₆ ^- ), and hexachloroantimonate (SbCl ₆ ^- ); tetraarylborates ions and borate ions such as tetrakis(pentafluorophenyl)borate ions; tris(trifluoromethanesulfonyl) methide ions; tris(perfluoroalkyl) phosphine trifluoride anions. Since the curability of the composition is good, hexafluorophosphate ion (PF ₆ ^- ) and hexafluoroantimonate (SbF ₆ ^- ) are particularly preferred.

As the cationic photopolymerization initiator, commercially available products can also be used, for example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (the above are manufactured by Union Carbide), Irgacure 261 , CG-24-61 (made by BASF company above), DAICATII (made by Daicel company), UVAC1591 (made by DAICEL-ALLNEX company), CI-2481, CI-2734, CI-2823, CI-2758 (above are made by Japan Cao Da Company), FFC509 (3M Company), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (the above are Japanese Green Chemical Co., Ltd.), etc.

The content of the cationic photopolymerization initiator is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass, and particularly preferably 0.5 to 3.0 parts by mass relative to 100 parts by mass of the cationically polymerizable compound. When the content of the cationic photopolymerization initiator is within the above-mentioned range, the sclerosing property of the obtained polymerizable composition is excellent, which is preferable. The cationic photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, the above-mentioned content refers to the total content of a plurality of cationic photopolymerization initiators.

The cationic thermal polymerization initiator used in the polymerizable composition of the present invention is a compound that can generate cationic species or Lewis acid by heating, no matter what kind of compound it is, but it is classified as the above-mentioned cationic photopolymerization initiator Except for the compounds of the drug.

As cationic thermal polymerization initiators, pernium salts, iodonium salts, diazonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, thiophenium salts, tetrahydrothiophenium salts, benzyl ammonium salts may, for example, be mentioned. , pyridinium salts, and salts such as oxalic acid salts; imide sulfonates such as naphthyl imide sulfonates and phthalimine sulfonates; diethylenetriamine, triethylenetriamine Amines, polyalkyl polyamines such as tetraethylene pentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophor Alicyclic polyamines such as ketone diamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylene; by using conventional methods to make the above-mentioned polyamines Used with various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, and bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acids Polyepoxy addition modification products produced by reaction; amidation produced by reacting the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by conventional methods Modified product; the above-mentioned polyamines, aldehydes such as formaldehyde, and phenol, cresol, xylenol, tert-butylphenol, and resorcinol, etc., have at least one hydroformylation in the core by conventional methods Mannich-modified products produced by reacting phenols at reactive sites; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid) , sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methylsuberic acid, Aliphatic dicarboxylic acids such as 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid, and dimer acid; phthalic acid, terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such as dicarboxylic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; trimellitic acid, 1,3,5-benzenetricarboxylic acid, and castor oil fatty acid 3 tricarboxylic acids such as polymers; acid anhydrides of tetracarboxylic acids such as pyromellitic acid, etc.); benzoin tosylate, p-nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl Sulfonates such as benzyl benzyl tosylate, 2,6-dinitrobenzyl tosylate, and 2,4-dinitrobenzyl tosylate; dicyandiamide, imidazoles, carboxylic acids Esters, amide imides, halogen compounds, and the like may be used alone or in combination of two or more.

As a cationic thermal polymerization initiator, a periconium salt is preferable in that the sclerosing property of the polymerizable composition obtained is good. In particular, monophenyl perylene salts are preferable because they are easy to obtain industrially, and examples of the monophenyl perylene salts include benzyl-p-hydroxyphenylmethyl perylene salts, p-hydroxyphenyldimethyl perylene salts, p-Acetyloxyphenyl dimethyl perionate salt, benzyl-p-hydroxyphenyl methyl perionate salt, and benzyl phenyl pernium salt, etc.

Among them, since the polymerizable composition obtained is excellent in deep hardening properties, a benzyl phenyl periconium salt is preferable, and a benzyl phenyl periconium salt represented by the following general formula (2) is particularly preferable.

式中，R ³¹表示氫原子、碳原子數為2～10之醯基、或碳原子數為1～10之烷基，R ³²、R ³³、R ³⁵、R ³⁶、R ³⁷、R ³⁸、R ³⁹、R ⁴⁰、及R ⁴¹分別獨立地表示氫原子、鹵素原子、碳原子數為1～10之烷基、碳原子數為1～10之烷氧基、或碳原子數為2～10之酯基，R ³²與R ³³、R ³⁵與R ³⁶、R ³⁶與R ³⁷、R ³⁷與R ³⁸、R ³⁸與R ³⁹、及R ⁴⁰與R ⁴¹可彼此鍵結，形成碳原子數為3～10之環，R ³⁴表示碳原子數為1～10之烷基或碳原子數為6～20之含芳香環之基，X ₂ ^-表示一價陰離子。 [hua 5]

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 R ³² , R ³³ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , and R ⁴¹ each independently represent 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 alkoxy group having 2 to 10 carbon atoms. In the ester group, 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 can be bonded to each other to form a carbon number of A ring of 3 to 10, R ³⁴ represents an alkyl group with 1 to 10 carbon atoms or a group containing an aromatic ring with 6 to 20 carbon atoms, and X ₂ ^- represents a monovalent anion.

The halogen atom, 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 in the above general formula (2) are related to the above general formula ( In 1), the halogen atom, 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 the same.

Examples of the acyl group having 2 to 10 carbon atoms in the general formula (2) include acetyl, propionyl, isopropyl, butyl, isobutyl, benzyl, and chloroacetyl. group, dichloroacetyl group, trichloroacetyl group, trifluoroacetyl group, methoxyacetyl group, and acetoacetyl group and the like.

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, an aralkyl group having 7 to 20 carbon atoms, and the like.

As a C6-C20 aryl group, a phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, for example. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, an indenyl group, an indenyl group, and a 9-indenylmethyl group.

The number of carbon atoms formed as 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 being bonded to each other is 3 to 10. The ring, for example: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopentene ring, cyclopentadiene ring, cyclohexane ring, cyclohexene ring, benzene ring, and cyclooctane ring Wait.

It is preferable that R ³¹ in the benzyl phenyl peronium salt represented by the general formula (2) is a hydrogen atom or a compound having 2 to 10 carbon atoms in order to improve the deep hardening property of the polymerizable composition obtained. The acyl group is particularly preferably a compound in which R ³¹ is an acyl group.

When 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 bonded to each other to form a ring, R ³² , R ³³ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , and R ⁴¹ are preferably hydrogen atoms. The compound of such a structure is chemically stable, and the polymerizable composition obtained is also excellent in deep hardening property, so it is preferable.

Among 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 preferred in terms of enhancing the deep sclerosis of the polymerizable composition obtained. A compound in which one or more are bonded to each other to form a benzene ring, particularly preferably one of R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , and R ³⁸ and R ³⁹ are bonded to each other. Benzene ring compound.

The monovalent anion represented by X ₂ ^- is preferably perchlorate ion (ClO ₄ ^- ), tetrafluoroborate ion (BF ₄ ^- ), hexafluorophosphate ion (PF ₆ ^- ), hexafluoroantimonate Inorganic ions such as (SbF ₆ ^- ), hexafluoroarsenate (AsF ₆ ^- ), and hexachloroantimonate (SbCl ₆ ^- ), and hexafluorophosphate ions are particularly preferred in terms of good curability of the polymerizable composition (PF ₆ ^- ) and hexafluoroantimonate (SbF ₆ ^- ).

Examples of the monophenyl perylene salt represented by the general formula (2) include: benzyl-p-hydroxyphenylmethyl perylene salt, benzyl-p-acetoxyphenyl methyl perylene salt, benzyl- p-Hydroxyphenylmethyl perionium salt, 1-naphthylmethyl-p-hydroxyphenylmethyl perionium salt, and the like.

As a cationic thermal polymerization initiator, a commercial item can also be used, for example, CI-2064, CI-2624, CI-2639, CI-2855, CI-2920, CI-2921, CI-2946, CI- 3128 (the above are manufactured by Japan Soda Co., Ltd.), 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 (the above are manufactured by Sanshin Chemical Co., Ltd.), TA-90, TA-100, TA-120, TA-160, IK-1, IK-2 (the above are It is manufactured by San-Apro Corporation), Adekaopton CP-66, Adekaopton CP-77 (made by ADEKA Corporation above), FC-520 (made by 3M Corporation), etc.

The content of the cationic thermal polymerization initiator is 50 to 1000 parts by mass with respect to 100 parts by mass of the cationic photopolymerization initiator. It is preferably 100 to 500 parts by mass, particularly preferably 150 to 500 parts by mass. When the content of the cationic thermal polymerization initiator is within the above-mentioned range, the obtained polymerizable composition is excellent in deep hardening properties, which is preferable. The cationic thermal polymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, the above content refers to the total content of a plurality of cationic thermal polymerization initiators.

The cationically polymerizable compound used in the polymerizable composition of the present invention is a compound that causes polymerization or crosslinking reaction by cationic species or Lewis acid generated from the above-mentioned cationic photopolymerization initiator or cationic thermal polymerization initiator, regardless of the type. All kinds of compounds are not harmful, for example, epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic sulfide compounds, spiro orthoester compounds, and vinyl compounds, etc. .

The cationically polymerizable compound is preferably a polyfunctional cationically polymerizable compound having a plurality of groups that cause polymerization or a crosslinking reaction in the molecule because it is excellent in deep hardening properties.

Among these compounds, an epoxy compound and an oxetane compound are preferable in terms of easy availability and good curability.

As an epoxy compound, an alicyclic epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, etc. are mentioned, Among them, an alicyclic epoxy compound and an aromatic epoxy compound are preferable. Since the above-mentioned cationically polymerizable compound is the above-mentioned compound, the obtained polymerizable composition is excellent in curability. In addition, the epoxy compound includes all compounds containing an epoxy group. For example, a compound containing both an epoxy group and an oxycyclobutyl group is included in the epoxy compound.

As a specific example of the above-mentioned alicyclic epoxy compound, a compound containing a cycloolefin oxide structure can be exemplified, and the compound containing a cycloolefin oxide structure is obtained by polymerizing a polyol having at least one aliphatic ring with an oxidizing agent. Glycidyl ether and compounds containing cycloolefin structures such as cyclohexene structures and cyclopentene structures are obtained by epoxidizing them. As said alicyclic epoxy compound, hydrogenated bisphenol A diglycidyl ether, 3, 4- epoxy cyclohexane carboxylic acid 3, 4- epoxy cyclohexyl methyl ester, 3, 4- cyclohexyl methyl ester, the Oxy-1-methylhexanecarboxylic acid 3,4-epoxy-1-methylcyclohexyl ester, 6-methyl-3,4-epoxycyclohexanecarboxylic acid 6-methyl-3, 4-Epoxycyclohexylmethylester, 3,4-epoxy-3-methylcyclohexanecarboxylic acid 3,4-epoxy-3-methylcyclohexylmethylester, 3,4-epoxy -5-Methylcyclohexanecarboxylic acid 3,4-epoxy-5-methylcyclohexylmethyl ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-cyclohexyl Oxy) cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate Methyl bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, bis(3,4-epoxycyclohexanecarboxylic acid) ethylene glycol, epoxyhexahydrophthalate Dioctyl formate, Di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-cyclohexane Oxyethylcyclohexane, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate, etc. In addition, the epoxy compound which has both an aliphatic ring and an aromatic ring belongs to an alicyclic epoxy compound.

Examples of commercially available products that can be suitably used as the above-mentioned alicyclic epoxy compound include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (the above are manufactured by Union Carbide), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 2000, Celloxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolead GT-301, Epolead GT-302, Epolead 401, Epolead 403, ETHB, Epolead HD30 , EHPE-3150, EHPE-3150CE (the above are manufactured by Daicel Corporation), KRM-2110, KRM-2199 (the above are manufactured by ADEKA Corporation), etc. Among the above-mentioned alicyclic epoxy compounds, an epoxy resin having an epoxycyclohexane structure is preferable because the obtained polymerizable composition has excellent curability.

Specific examples of the above-mentioned aromatic epoxy compounds include polyphenols having at least one aromatic ring or polyglycidyl ethers of their alkylene oxide adducts, such as bisphenol A, bisphenol F, Further, glycidyl ethers of compounds obtained by adding these alkylene oxides, epoxy novolac resins, and the like. In addition, an aromatic epoxy compound means the epoxy compound which contains an aromatic ring and does not contain an aliphatic ring. Since the obtained polymerizable composition is excellent in deep hardening property, an aromatic epoxy compound is preferable.

Specific examples of the above-mentioned aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polyacids, polyglycidyl esters of Or homopolymers synthesized by vinyl polymerization of glycidyl methacrylate, copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers, etc. Typical compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, and trimethylolpropane triglycidyl ether , the tetraglycidyl ether of sorbitol, the hexaglycidyl ether of dipentaerythritol, the diglycidyl ether of polyethylene glycol, and the glycidyl ether of polyhydric alcohols such as the diglycidyl ether of polypropylene glycol; Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as methyl propane and glycerin; diglycidyl esters of aliphatic long-chain dibasic acids, etc. Furthermore, monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; Glycidyl ester, epoxidized soybean oil, epoxidized octyl stearate, epoxidized butyl stearate, epoxidized soybean oil, and epoxidized polybutadiene, etc. In addition, an aliphatic epoxy compound means the epoxy compound which does not contain an aromatic ring and an epoxy cyclohexane structure.

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

Specific examples of the above-mentioned oxetane compound include, for example, 3-ethyl-3-hydroxymethyl oxetane, 3-(methyl)allyloxymethyl-3-ethyl oxetane Butane, (3-ethyl-3-oxocyclobutylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxocyclobutylmethoxy)methyl]benzene, 4-methyl Oxy-[1-(3-ethyl-3-oxocyclobutylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxocyclobutylmethoxy)ethyl]phenyl ether, isobutyl Oxymethyl (3-ethyl-3-oxocyclobutylmethyl) ether, iso(3-ethyl-3-oxocyclobutylmethyl) ether, iso(3-ethyl-3 -Oxycyclobutyl methyl) ether, 2-ethylhexyl (3-ethyl-3-oxocyclobutyl methyl) ether, ethyl diethylene glycol (3-ethyl-3-oxocyclobutyl methyl) ether, diethylene glycol Cyclopentadiene (3-ethyl-3-oxocyclobutylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, dicyclopentenyl (3- Ethyl-3-oxocyclobutylmethyl) ether, tetrahydrofuranmethyl (3-ethyl-3-oxocyclobutylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2 - Tetrabromophenoxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, tribromophenyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxo Cyclobutylmethyl) ether, butoxyethyl (3-ethyl-3-oxocyclobutylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxocyclobutylmethyl) ether, pentabromophenyl ( 3-Ethyl-3-oxocyclobutylmethyl) ether, xyl (3-ethyl-3-oxocyclobutylmethyl) ether, 3,7-bis(3-oxocyclobutyl)-5-oxa- Nonane, 3,3'-(1,3-(2-Methylene)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[ (3-ethyl-3-oxocyclobutylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxocyclobutylmethoxy)methyl]ethane, 1,3-bis [(3-ethyl-3-oxocyclobutylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxocyclobutylmethyl)ether, dicyclopentenylbis(3-ethyl) -3-oxocyclobutyl methyl) ether, triethylene glycol bis(3-ethyl-3-oxocyclobutyl methyl) ether, tetraethylene glycol bis(3-ethyl-3-oxocyclobutyl methyl) ether, Tricyclodecanediyl dimethylene (3-ethyl-3-oxocyclobutylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxocyclobutylmethyl) ether, 1,4- Bis(3-ethyl-3-oxocyclobutylmethoxy)butane, 1,6-bis(3-ethyl-3-oxocyclobutylmethoxy)hexane, pentaerythritol tris(3-ethyl-3- Oxycyclobutyl methyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxocyclobutyl methyl) ether, polyethylene glycol bis (3-ethyl-3-oxocyclobutyl methyl) ether, dipentaerythritol hexa (3- Ethyl-3 -Oxycyclobutyl methyl) ether, dipentaerythritol penta (3-ethyl-3-oxocyclobutyl methyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxocyclobutyl methyl) ether, caprolactone modified two Pentaerythritol hexa(3-ethyl-3-oxocyclobutyl methyl) ether, caprolactone modified dipentaerythritol penta(3-ethyl-3-oxocyclobutyl methyl) ether, di-trimethylolpropane tetrakis (3 -Ethyl-3-oxocyclobutylmethyl) ether, EO modified bisphenol A bis(3-ethyl-3-oxocyclobutylmethyl) ether, PO modified bisphenol A bis(3-ethyl-3- Oxycyclobutyl methyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxocyclobutyl methyl) ether, PO modified hydrogenated bisphenol A bis (3-ethyl-3-oxocyclobutyl methyl) ) ether, and EO-modified bisphenol F (3-ethyl-3-oxocyclobutylmethyl) ether, etc.

Examples of commercially available products that can be suitably used as the above-mentioned oxetane compound include Aronoxetane OXT-101, OXT-121, OXT-221, OXT-212, OXT-211 (the above are manufactured by Toagosei Co., Ltd.), Eternacoll EHO, OXBP, OXTP, OXMA (the above are manufactured by Ube Industries Co., Ltd.), etc.

A polymerizable composition containing an oxetane compound as a cationically polymerizable compound is preferable because it is excellent in deep-sclerosis|hardenability. As an oxetane compound, the oxetane compound which has two or more oxycyclobutyl groups in the same molecule is more preferable, and the oxetane compound which has two oxycyclobutyl groups is especially 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 particularly preferably 30 to 70 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound. When the content of the cationic compound is within the above-mentioned range, the obtained polymerizable composition has excellent curability, which is preferable.

Examples of other cationically polymerizable compounds include oxycyclopentane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; triacetane, 1,3-dioxolane, and 1,3,6-trioxolane Cyclic acetal compounds such as oxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; thiocyclopropane compounds such as ethylene sulfide and sulfur-representing chlorohydrin; 1,3-propane Alkyne sulfides, and thiocyclobutane compounds such as 3,3-dimethylthiocyclobutane; cyclic sulfide compounds such as tetrahydrothiophene derivatives; ethylene glycol divinyl ether, alkyl vinyl ether, 2-chloroethylene Vinyl ether compounds such as ethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, and propenyl ether of propylene glycol ; Spirocyclic orthoester compounds obtained by the reaction of epoxy compounds and lactones; ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene, and polybutadiene, and derivatives of these compounds things etc.

The polymerizable composition of the present invention may also contain a sensitizer. The polymerizable composition containing a sensitizer is preferable because it is excellent in deep hardening properties. A sensitizer refers to a substance that does not have polymerizability and promotes cationic polymerization by being used in combination with the above-mentioned cationic photopolymerization initiator, excluding compounds classified as the above-mentioned cationic photopolymerization initiator or the above-mentioned cationic thermal polymerization initiator.

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

式中，R表示碳原子數為1～10之烷基。 [hua 6]

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

The content of the sensitizer is not particularly limited, and relative to 1 mol of the cationic photopolymerization initiator, it is preferably 1-1000 mol, more preferably 5-500 mol, and particularly preferably 10-200 mol. When the content of the sensitizer is within the above range, the sclerosing property of the polymerizable composition obtained is excellent, which is preferable.

The polymerizable composition of the present invention may also contain sulfate. The polymerizable composition containing sulfate is preferable because it has good thermal stability and is excellent in deep sclerosis. Among the sulfates, alkyl sulfates are particularly preferred. As anion of an alkyl sulfate, a methyl sulfate ion, an ethyl sulfate ion, and a propyl sulfate ion are mentioned.

The cation of the sulfate is preferably a pericynium ion, and particularly preferably a pericynium ion represented by the following general formula (3), since the polymerizable composition has good thermal stability and high deep hardening properties.

式中，R ⁵¹表示氫原子、碳原子數為2～10之醯基、或碳原子數為1～10之烷基，R ⁵²、R ⁵³、R ⁵⁶、及R ⁵⁷分別獨立地表示氫原子、鹵素原子、碳原子數為1～10之烷基、碳原子數為1～10之烷氧基、或碳原子數為2～10之酯基，R ⁵²與R ⁵³及R ⁵⁶與R ⁵⁷可彼此鍵結而形成碳原子數為3～10之環，R ⁵⁴及R ⁵⁵表示碳原子數為1～20之烴基。 [hua 7]

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 each independently represent a hydrogen atom , halogen atom, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, or ester group with 2 to 10 carbon atoms, R ⁵² and R ⁵³ and R ⁵⁶ and R ⁵⁷ They can 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.

In the above general formula (3), a halogen atom, 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 alkoxy group having 2 carbon atoms Ester group of to 10, and ring of carbon number of 3 to 10, halogen atom, acyl group of carbon number of 2 to 10, alkyl of carbon number of 1 to 10 in the above general formula (2), The alkoxy group having 1 to 10 carbon atoms, the ester group having 2 to 10 carbon atoms, and the ring having 3 to 10 carbon atoms are the same. In addition, the hydrocarbon group having 1 to 20 carbon atoms in the above general formula (3) is the same as the hydrocarbon group having 1 to 20 carbon atoms in the above general formula (1).

Among the cations represented by the above-mentioned general formula (3), those in which R ⁵¹ is a hydrogen atom are preferable in terms of good thermal stability of the polymerizable composition obtained and excellent deep hardening properties.

Among the cations represented by the above-mentioned general formula (3), R 52 , R 53 , R 56 , and R 57 are preferably R ⁵² , R ⁵³ , R ⁵⁶ , and R ⁵⁷ in terms of good thermal stability and excellent deep hardening properties of the polymerizable composition obtained. hydrogen atom.

As a sulfate used for this invention, an aromatic perylene alkyl sulfate is mentioned, for example, 4-hydroxyphenyl (dimethyl) perylene methyl sulfate etc. are mentioned specifically,.

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

In the polymerizable composition of the present invention, a solvent that can dissolve or disperse the above components (compounds that exist in the form of liquid under atmospheric pressure and 25°C and does not belong to the above components), such as acetone, may be added as required. , methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, dichloromethane, hexane, heptane, octane, cyclohexane, benzene, toluene, dichloromethane Toluene, methanol, ethanol, and isopropanol, etc. In the polymerizable composition of the present invention, the content of the solvent is appropriately selected according to the application of the polymerizable composition, etc., and is not particularly limited. Usually, the solid content of the polymerizable composition (the total content of all components except the solvent) is used. ) is 5-90 mass %, when a solvent is contained, operations, such as the case of forming a coating film, become easy.

Moreover, as long as the effect of the present invention is not impaired, the following various additives may be added as needed: benzotriazole-based, tris-based, and benzoate-based ultraviolet absorbers; phenol-based, phosphorus-based, and sulfur-based UV absorbers Antioxidants; antistatic agents such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants; halogen compounds, phosphate ester compounds, amide phosphate compounds, melamine compounds , fluorine resin or metal oxide, (poly) melamine phosphate, and (poly) piperazine phosphate and other flame retardants; hydrocarbon series, fatty acid series, aliphatic alcohol series, aliphatic ester series, aliphatic amide series, and metal Soap-based lubricants; pigments and colorants such as carbon black; fumed silica, micro-particle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, Silica-based inorganic additives such as kaolinite, flint, feldspar powder, vermiculite, etiprite, talc, mica, iron talc, pyrophyllite, and silica; fillers such as glass fiber and calcium carbonate; nucleating agents and Crystallizing agents such as crystallization accelerators; rubber elasticity imparting agents such as silane coupling agents and flexible polymers; other monomers, defoaming agents, tackifiers, leveling agents, plasticizers, polymerization inhibitors, antistatic agents, Flow modifiers, coupling agents and adhesion promoters, etc. In the polymerizable composition of the present invention, the total usage amount of these various additives is 50% by mass or less.

The polymerizable composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays, and is usually cured to a dry state or a solvent-insoluble state after 0.1 seconds to several minutes from the irradiation. As a suitable active energy ray, any active energy ray can be used as long as it induces the decomposition of the photoacid generator, and it is preferable to use self-ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, xenon lamps, carbon arc lamps, Metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various Electromagnetic wave energy with a wavelength of 200 nm to 700 nm obtained by semiconductor laser, YAG (Yttrium Aluminum Garnet, yttrium aluminum garnet) laser, light emitting diode, CRT (cathode-ray tube, cathode ray tube) light source, etc. Electron beams, X-rays, and high-activity energy beams such as radiation.

The irradiation time of the active energy ray varies depending on the strength of the active energy ray, the thickness of the coating film, or 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 than the above. After 0.1 seconds to several minutes after the active energy ray irradiation, most of the composition is dry to the touch due to cationic polymerization, but it is preferable to use thermal energy generated by heating or a thermal induction head as appropriate to promote cationic polymerization.

In addition, the polymerizable composition of the present invention can be hardened by heating with a hot plate such as a hot plate, an air 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 from the viewpoint of accelerating the polymerization of the cationically polymerizable compound, it is preferably 70 to 200°C, more preferably 90 to 150°C. In addition, the curing time is not particularly limited, but from the viewpoint of improving productivity, it is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

Furthermore, the polymerizable composition of the present invention can be cured by combining irradiation with active energy rays and heating. In this case, heating may be performed after irradiating the polymerizable composition with active energy rays, or after heating the polymerizable composition, active energy rays may be irradiated. It is preferable to heat the composition after irradiating the composition with active energy rays, from the viewpoint of improving the positional accuracy when used as a member fixing adhesive.

In the case where irradiation and heating of active energy rays are used in combination with the curing of the polymerizable composition of the present invention, as the active energy rays and heating means to be used, the above-mentioned ones can be used without particular limitation, and they are excellent in deep curing properties. In other words, it is preferable to use ultraviolet rays as the active energy rays.

Specific applications of the polymerizable composition of the present invention include various applications such as: optical filters; coatings; coating agents; lining agents; adhesives; printing plates; insulating varnishes; insulating sheets; laminates; printing Substrates; for semiconductor devices, for LED (light-emitting diode) packaging, for liquid crystal injection ports, for organic EL (Electroluminescence), for optical components, for electrical insulation, for electronic parts, and sealants for separation films; molding materials; putties; glass fiber impregnating agents; blocking agents; passivation films for semiconductors and solar cells; interlayer insulating films; protective films; printed substrates; color TV, PC (Personal Computer, personal computer) monitor, portable information terminal, and CCD (Charge Coupled Device, charge coupled device) image sensor color filter; Electrode material for plasma display panel; Printing ink; Dental composition; Resins for photoforming; liquid and dry films; micro-mechanical parts; glass fiber cable coatings; [Example]

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 composition shown in Tables 1-4, and it stirred until an insoluble thing did not exist, and the polymerizable composition of each Example and a comparative example was obtained. Cationic polymerizable compounds A-1 to A-4, cationic photopolymerization initiators B-1 to B-2, cationic thermal polymerization initiators C-1 to C-3, sensitizers D-1 to D-4 , Stabilizer E-1, radically polymerizable compounds F-1 to F-2, and photoradical polymerization initiator G-1 are compounds having the following structures, respectively.

[hua 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

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

(Deep curability) The polymerizable composition was applied to a release film (Lumirror T60; Toray Corporation) with a bar coater so as to have predetermined film thicknesses (100 μm, 50 μm, and 30 μm), respectively. production), and after exposure at 500 mJ/cm ² using an LED light source (100 mW/cm ² ) with a wavelength of 365 nm, it was left to stand at room temperature for 2 hours. Then, the release film was peeled off, and the state of the peeled surface was confirmed. When the stickiness was not confirmed on the peeled surface, it was judged that a hardened product could be obtained, and when the stickiness was confirmed, it was judged that a hardened product could not be obtained. The thicker the cured product can be obtained, the better it is as an adhesive for components. The results are summarized in Tables 1 to 4. A: A cured product with a film thickness of 100 μm can be obtained. B: Although a cured product with a film thickness of 100 μm could not be obtained, a cured product with a film thickness of 50 μm was obtained. C: Although a cured product with a film thickness of 50 μm could not be obtained, a cured product with a film thickness of 30 μm was obtained. D: A cured product with a film thickness of 30 μm could not be obtained.

(Curing Shrinkage) The polymerizable composition was separately coated on a release film (Lumirror T60; manufactured by Toray Industries) with a film thickness of 30 μm using a bar coater, and an LED with a wavelength of 365 nm was used. After exposure by a light source (100 mW/cm ² ) at 500 mJ/cm ² , it was left to stand at room temperature for 2 hours. After that, the release film was peeled off to obtain a sample. The density of the obtained sample and the sample before hardening was measured using a gas pycnometer (JIS Z8837). Then, the hardening shrinkage rate was calculated from the ratio of the density change before and after hardening. The smaller the hardening shrinkage rate, the higher the positional accuracy, and therefore the better as an adhesive for members. The results are summarized in Tables 1 to 4. A: The hardening shrinkage ratio is less than 4%. B: The hardening shrinkage ratio is 4% or more and less than 7%. C: The hardening shrinkage ratio is 7% or more.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 Cationic polymerizable compound A-1 - - - - 50 50 50 50 - - - - A-2 50 50 - - 50 50 50 50 50 50 - - A-3 50 50 50 50 - - - - 50 50 50 50 A-4 - - 50 50 - - - - - - 50 50 Cationic photopolymerization initiator B-1 1 1 1 1 1 1 1 1 1 1 1 1 B-2 - - - - - - - - - - - - Cationic thermal polymerization initiator C-1 0.5 - - - - - - - 2 - - - C-2 - 0.5 0.5 - 0.5 0.5 0.5 0.5 - 2 2 - C-3 - - - 0.5 - - - - - - - 2 Sensitizer D-1 - - - - 0.05 - - - - - - - D-2 - - - - - 0.033 - - - - - - D-3 - - - - - - 0.05 - - - - - D-4 - - - - - - - 0.05 - - - - stabilizer E-1 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Solvent (Propylene Carbonate) 2 2 2 2 2 2 2 2 2 2 2 2 Evaluation storage stability B A C B A A A A B A C B deep sclerosis A B A A A A A A A B A A Hardening shrinkage A A A A A A A A A A A A

[Table 2] Example 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four Cationic polymerizable compound A-1 50 50 50 50 - - - - 50 50 50 50 A-2 50 50 50 50 50 50 - - 50 50 50 50 A-3 - - - - 50 50 50 50 - - - - A-4 - - - - - - 50 50 - - - - Cationic photopolymerization initiator B-1 1 1 1 1 - - - - - - - - B-2 - - - - 1 1 1 1 1 1 1 1 Cationic thermal polymerization initiator C-1 - - - - 0.5 - - - - - - - C-2 2 2 2 2 - 0.5 0.5 - 0.5 0.5 0.5 0.5 C-3 - - - - - - - 0.5 - - - - Sensitizer D-1 0.05 - - - - - - - 0.05 - - - D-2 - 0.033 - - - - - - - 0.033 - - D-3 - - 0.05 - - - - - - - 0.05 - D-4 - - - 0.05 - - - - - - - 0.05 stabilizer E-1 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Solvent (Propylene Carbonate) 2 2 2 2 2 2 2 2 2 2 2 2 Evaluation storage stability A A A A B A C B A A A A deep sclerosis A A A A A B A A A A A A Hardening shrinkage A A A A A A A A A A A A

[table 3] Example 25 26 27 28 29 30 31 32 Cationic polymerizable compound A-1 - - - - 50 50 50 50 A-2 50 50 - - 50 50 50 50 A-3 50 50 50 50 - - - - A-4 - - 50 50 - - - - Cationic photopolymerization initiator B-1 - - - - - - - - B-2 1 1 1 1 1 1 1 1 Cationic thermal polymerization initiator C-1 2 - - - - - - - C-2 - 2 2 - 2 2 2 2 C-3 - - - 2 - - - - Sensitizer D-1 - - - - 0.05 - - - D-2 - - - - - 0.033 - - D-3 - - - - - - 0.05 - D-4 - - - - - - - 0.05 stabilizer E-1 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Solvent (Propylene Carbonate) 2 2 2 2 2 2 2 2 Evaluation storage stability B A C B A A A A deep sclerosis A B A A A A A A Hardening shrinkage A A A A A A A A

[Table 4] Comparative example 1 2 3 4 5 6 7 8 9 10 Cationic polymerizable compound A-1 - - 50 50 50 50 50 - - - A-2 50 - 50 50 50 50 50 - - - A-3 50 50 - - - - - - - - A-4 - 50 - - - - - - - - Cationic photopolymerization initiator B-1 1 1 1 1 1 1 1 - - - B-2 - - - - - - - - - - Cationic thermal polymerization initiator C-1 - - - - - - - - - - C-2 - - - - - - - - - - C-3 - - - - - - - - - - free radical polymerizable compound F-1 - - - - - - - 100 34 - F-2 - - - - - - - - 66 100 Photoradical Polymerization Initiator G-1 - - - - - - - 2 2 2 Sensitizer D-1 - - - 0.05 - - - - - - D-2 - - - - 0.033 - - - - - D-3 - - - - - 0.05 - - - - D-4 - - - - - - 0.05 - - - stabilizer E-1 - - - - - - - - - - Solvent (Propylene Carbonate) 2 2 2 2 2 2 2 2 2 2 Evaluation storage stability A A A A A A A A A A deep sclerosis D D D D D D D B B B Hardening shrinkage A A A A A A A C C C

As is clear from Tables 1 to 4, the polymerizable composition of the present invention is excellent in storage stability, sensitivity, deep curability, and positional accuracy. The use of the polymerizable composition of the present invention is not limited, and in particular, it can be used as an adhesive for fixing components represented by electronic parts, wiring, and vehicle materials. [Industrial Availability]

The polymer composition of the present invention can obtain a cured product of a thick film with excellent positional accuracy in a short time by irradiating active energy rays, and has high productivity, so it can be used as a polymerizable composition for applications requiring a cured product of a thick film .

Claims (8)

A polymerizable composition comprising a cationic photopolymerization initiator, a cationic thermal polymerization initiator, and a cationic polymerizable compound, The content of the cationic thermal polymerization initiator is 50 to 1000 parts by mass with respect to 100 parts by mass of the cationic photopolymerization initiator. The polymerizable composition according to claim 1, wherein the cationic photopolymerization initiator contains an aromatic perylene salt. The polymerizable composition according to claim 1, wherein the cationic thermal polymerization initiator contains benzyl phenyl perionate. The polymerizable composition of claim 1, wherein the cationically polymerizable compound contains an oxetane compound. The polymerizable composition of claim 1, which contains a sensitizer. The polymerizable composition of claim 1, which contains an alkyl sulfate. A hardened product, which is the hardened product of the polymerizable composition according to any one of claims 1 to 6. A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to any one of claims 1 to 6 with light.