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

Abstract

The object of the present invention is to provide a polymerizable composition that can obtain a thick film of a cured product with excellent positional accuracy in a short time. The present invention is a polymerizable composition, which is a polymerizable composition containing a photocationic polymerization initiator, a thermal cationic polymerization initiator and a cationic polymerizable compound, wherein the content of the thermal cationic polymerization initiator is 50 to 1000 parts by mass relative to 100 parts by mass of the photocationic polymerization initiator. Preferably, the photocationic polymerization initiator contains an aromatic sulfonium salt, and further preferably, the thermal cationic polymerization initiator contains a benzylphenylsulfonium salt.

Description

Technical Field

[0001] The present invention relates to a polymerizable composition containing a photocationic polymerization initiator, a thermal cationic polymerization initiator and a cationically polymerizable compound. Background Art

[0002] Cationic curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members, etc. There have been various reports on improvements of such curable compositions.

[0003] In electronic substrates, adhesives are sometimes used as a method for bonding components such as semiconductors and optical components on insulating substrates. Due to the high integration of electronic substrates in recent years, high positional accuracy is required for bonding components. Patent documents 1 and 2 disclose a method in which an adhesive is used to temporarily fix the components by an ultraviolet irradiation process and then formally fix the components by a heating process. In addition, in Patent documents 1 and 2, a composition with an epoxy resin as a main raw material is disclosed as an adhesive for bonding optical components.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-019286

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-073574 Summary of the invention

[0008] Adhesives for fixing members such as electronic components are required to provide a cured product having a relatively high thickness and excellent positional accuracy in a short time, but conventional cation-curable compositions sometimes have insufficient curability.

[0009] Therefore, an object of the present invention is to provide a polymerizable composition capable of obtaining a cured product having excellent positional accuracy and a thickness of 30 μm or more (hereinafter sometimes referred to as a “thick film”) in a short period of time.

[0010] The inventors have repeatedly conducted intensive studies and have come to realize that by using a photocationic polymerization initiator and a thermal cationic polymerization initiator in combination, and preferably increasing the amount of the thermal cationic polymerization initiator used relative to the photocationic polymerization initiator, a cured product having a thickness of 30 μm or more can be obtained by light irradiation alone, thereby achieving the present invention.

[0011] That is, the present invention is a polymerizable composition comprising a photocationic polymerization initiator, a thermal cationic polymerization initiator and a cationically polymerizable compound, wherein the content of the thermal cationic polymerization initiator is 50 to 1000 parts by mass based on 100 parts by mass of the photocationic polymerization initiator. DETAILED DESCRIPTION

[0012] Hereinafter, the polymerizable composition of the present invention will be described based on preferred embodiments.

[0013] The polymerizable composition of the present invention contains a photocationic polymerization initiator, a thermal cationic polymerization initiator, and a cationically polymerizable compound.

[0014] The photocationic polymerization initiator used in the polymerizable composition of the present invention is a compound that can generate cationic species or Lewis acid by light irradiation. It can be any compound, but an onium salt or a derivative thereof that releases Lewis acid by ultraviolet irradiation is preferred from the perspective of excellent curability. Representative examples of such compounds include the general formula [A] m+ [B] m- The salt of the cation and anion represented.

[0015] Here, from the viewpoint of excellent curability, the cationic [A] m+ is an onium ion, whose structure can be represented by the general formula [G a Q] m+ To express.

[0016] In the formula, G is an organic group having 1 to 60 carbon atoms and may also contain several atoms other than carbon atoms. a is an integer of 1 to 5. a Gs are independent of each other and may be the same or different. In addition, from the perspective of excellent curability, it is preferred that at least one G is an organic group having an aromatic ring. 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. In addition, when the atomic valence of Q is set to q, the relationship m=aq must hold (wherein N=N is treated as an atomic valence of 0).

[0017] In addition, the anion [B] m- There are no particular limitations, but halide complexes are preferred from the perspective of excellent curability. The structure thereof can be represented by the general formula [LX b ] m- express.

[0018] In the formula, L is the central atom of the halide complex, i.e., a metal or semimetal (Metalloid), such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, or Co. X is a halogen atom such as fluorine, chlorine, bromine, or iodine. b is an integer of 3 to 7. In addition, when the atomic valence of L is set to p, the relationship m=bp must hold.

[0019] As the anion of the above general formula [LX b ] m- Specific examples include perchlorate ions (ClO4 - ), tetrafluoroborate ion (BF4 - ), hexafluorophosphate ion (PF6 - ), hexafluoroantimonate (SbF6 - ), hexafluoroarsenate (AsF6 - ) and hexachloroantimonate (SbCl6 - ) and other inorganic ions; fluorosulfonate ion (FSO3 - ), toluenesulfonate anion, trinitrobenzenesulfonate ion, camphorsulfonate ion, nonafluorobutanesulfonate ion and hexafluorooctanesulfonate ion and other sulfonate ions; tetraarylborate ion and tetrakis(pentafluorophenyl)borate ion and other borate ions; methanecarboxylate ion, ethanecarboxylate ion, propanecarboxylate ion, butanecarboxylate ion, octanecarboxylate ion, trifluoromethanecarboxylate ion, benzenecarboxylate ion and p-toluenecarboxylate ion and other carboxylate ions; trifluoromethylsulfite ion (CF3SO3 - ), methyl sulfate ion (CH3OSO3 - ), bis(trifluoromethanesulfonyl)imide ion and tris(trifluoromethanesulfonyl)methide ion, etc.

[0020] In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (1) to (3). These can be used alone or in combination of two or more.

[0021] (1) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate

[0022] (2) Diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate and other diaryliodonium salts

[0023] (3) Sulfonium salts formed from sulfonium cations represented by the following group I or group II and hexafluoroantimony ions, tetrakis(pentafluorophenyl)borate ions, etc.

[0024] [Chemical formula 1]

[0025] <Group I>

[0026]

[0027] [Chemical formula 2]

[0028] <Group II>

[0029]

[0030] In addition, other preferred compounds include iron-aromatic complexes such as (η5-2,4-cyclopentadien-1-yl)〔(1,2,3,4,5,6-η)-(1-methylethyl)benzene〕-iron-hexafluorophosphate; mixtures of aluminum complexes such as tri(acetylacetonate)aluminum, tri(ethylacetoneacetyl)aluminum and tri(salicylicaldehyde)aluminum and silanols such as triphenylsilanol, etc.

[0031] Among them, aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferred, and aromatic sulfonium salts represented by the following general formula (1) are particularly preferred because the resulting polymerizable composition has excellent curability.

[0032] [Chemical formula 3]

[0033]

[0034] 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 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 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 or a hydrocarbon group having 1 to 20 carbon atoms, and X1 - It represents a monovalent anion.

[0035] Among the aromatic sulfonium salts represented by the general formula (1), it is more preferred that Z is a group represented by the following general formula (1a) from the viewpoint of excellent curability of the polymerizable composition.

[0036] [Chemical formula 4]

[0037]

[0038] In the formula, R 19 , R 20 , R 21 , R 22 and R 23 Each independently 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 * represents a bonding point.

[0039] Examples of the halogen atom in the general formula (1) include fluorine, chlorine, bromine and iodine.

[0040] The alkyl group having 1 to 10 carbon atoms in the general formula (1) also includes a group in which a hydrogen atom in the group is substituted by a halogen atom, and a group in which a methylene group in the group is substituted by -O-, -S-, -CO-, -OCO-, -COO-, -C=C-, -NHCO-, -NH- or -CONH-. Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, 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, tridecafluorohexyl, pentafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-oxoethyl, methoxyethyl, methoxyethoxymethyl, methyl t-Butylthiomethyl, ...

[0041] Examples of the alkoxy group having 1 to 10 carbon atoms in the general formula (1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxyethoxyethoxy, methoxyethoxyethoxyethoxy, 3-methoxybutoxy, 2-methylthioethoxy and trifluoromethoxy.

[0042] Examples of the ester group having 2 to 10 carbon atoms in the general formula (1) include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetoxy, tert-butylcarbonyloxy, methoxyacetoxy and benzoyloxy.

[0043] 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 containing carbon atoms and hydrogen atoms, and examples thereof include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and arylalkyl groups having 7 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms in the general formula (1) also includes groups in which hydrogen atoms in the group are substituted with halogen atoms, and groups in which methylene groups in the group are substituted with -O-, -S-, -CO-, -OCO-, -COO-, -C=C-, -NHCO-, -NH-, or -CONH-.

[0044] Examples of the alkyl group having 1 to 20 carbon atoms include linear, branched and cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.

[0045] Examples of the alkenyl group having 2 to 20 carbon atoms include straight-chain and cyclic alkenyl groups such as 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-tetradecatrienyl allyl.

[0046] The cycloalkyl group having 3 to 20 carbon atoms refers to a saturated monocyclic or polycyclic alkyl group having 3 to 20 carbon atoms. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentyl, and tetradecahydroanthracenyl.

[0047] The cycloalkylalkyl group having 4 to 20 carbon atoms refers to a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted 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-cyclodecylbutyl, 3-3-adamantylpropyl and decahydronaphthylpropyl can be mentioned.

[0048] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, biphenyl, naphthyl, anthracenyl and phenanthryl groups, and groups in which hydrogen atoms in these groups are substituted with the above-mentioned alkyl groups, the above-mentioned alkenyl groups, carboxyl groups or halogen atoms, such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl and 2,4,6-trimethylphenyl.

[0049] The arylalkyl group having 7 to 20 carbon atoms is a group having 7 to 20 carbon atoms obtained by replacing a hydrogen atom in an alkyl group with an aryl group. Examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, and naphthylpropyl. The arylalkyl group having 7 to 10 carbon atoms is a group having 7 to 10 carbon atoms obtained by replacing a hydrogen atom in an alkyl group with an aryl group. Examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and phenylethyl.

[0050] As X1 in the above general formula (1) - The monovalent anions represented by the above-mentioned anions [LX b ] m- Among the anions exemplified, monovalent anions are included.

[0051] In the aromatic sulfonium salt represented by the general formula (1), R 1 ~R 23 Compounds in which at least one of the halogen atoms is a halogen atom are preferred because the resulting polymerizable composition has high curability, and R 1 ~R 10 A compound in which at least one of R is a halogen atom, particularly a fluorine atom. 3 or R 8 A halogen atom is preferred because the compound has high stability and the curability of the obtained polymerizable composition is high.3 and R 8 Both of them are halogen atoms, especially fluorine atoms. Furthermore, R 15 ~R 18 At least one of them is a halogen atom, particularly a chlorine atom.

[0052] As X1 constituting the aromatic sulfonium salt represented by the above general formula (1): - The monovalent anion represented by is preferably a perchlorate ion (ClO4 - ), tetrafluoroborate ion (BF4 - ), hexafluorophosphate ion (PF6 - ), hexafluoroantimonate (SbF6 - ), hexafluoroarsenate (AsF6 - ) and hexachloroantimonate (SbCl6 - ) and other inorganic ions; borate ions such as tetraarylborate ions and tetrakis(pentafluorophenyl)borate ions; tris(trifluoromethanesulfonyl)methide ions; tri(perfluoroalkyl)phosphine anions, and hexafluorophosphate ions (PF6 - ) and hexafluoroantimonate (SbF6 - ).

[0053] As the photocationic polymerization initiator, commercially available products may be used. Examples thereof include CYRACURE UVI-6970, CYRACURE UVI-6974, CYRACURE UVI-6990, and CYRACURE UVI-950 (all manufactured by Union Carbide Corporation), Irgacure 261, CG-24-61 (all manufactured by BASF), DAICATII (manufactured by Daicel), UVAC1591 (manufactured by Daicel-Allnex Ltd.), CI-2481, CI-2734, CI-2823, and CI-2758 (all manufactured by Nippon Soda Co., Ltd.), FFC509 (manufactured by 3M Co., Ltd.), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, and NDS-103 (all manufactured by Midori Kagaku Corp.). Co., Ltd.), etc.

[0054] The content of the photocationic polymerization initiator is not particularly limited, and 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 cationic polymerizable compound. When the content of the photocationic polymerization initiator is within the above range, the curability of the obtained polymerizable composition is excellent, so it is preferred. The photocationic polymerization initiator can be used alone or in combination of two or more. When two or more are mixed, the above content refers to the total content of the multiple photocationic polymerization initiators.

[0055] The thermal cationic polymerization initiator used in the polymerizable composition of the present invention is a compound capable of generating a cationic species or a Lewis acid by heating, and may be any compound except compounds classified as the above-mentioned photocationic polymerization initiators.

[0056] Examples of the thermal cationic polymerization initiator include sulfonium salts, iodonium salts, diazonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, thiophenium salts, tetrahydrothiophenium salts, benzyl ammonium salts, pyridinium salts, and hydrazinium salts; imide sulfonates such as naphthimide sulfonates and phthalimide sulfonates; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; meta-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; Aromatic polyamines; polyepoxy addition modified products produced by reacting the above polyamines 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 by conventional methods; amidated modified products produced by reacting the above organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by conventional methods; polyamines produced by reacting the above polyamines with aldehydes such as formaldehyde and phenol, cresol, xylenol, tert-butylphenol and resorcinol in the nucleus Mannich modified products produced by reacting phenols having at least one hydroformylation-reactive site by conventional methods; polycarboxylic acids (aliphatic dicarboxylic acids such as 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-methylpentanedicarboxylic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as styryl acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimers of trimellitic acid, trimesic acid and castor oil fatty acid; anhydrides of tetracarboxylic acids such as pyromellitic acid; sulfonates such as benzoin toluenesulfonate, p-nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl toluenesulfonate, 2,6-dinitrobenzyl toluenesulfonate and 2,4-dinitrobenzyl toluenesulfonate; dicyandiamide, imidazoles, carboxylates, amine imides and halogen compounds, etc., which can be used alone or in combination of two or more.

[0057] As the thermal cationic polymerization initiator, sulfonium salts are preferred from the viewpoint of good curability of the obtained polymerizable composition. In particular, monophenylsulfonium salts are preferred because they are easily available industrially, and examples of the monophenylsulfonium salts include benzyl p-hydroxyphenylmethylsulfonium salt, p-hydroxyphenyldimethylsulfonium salt, p-acetoxyphenyldimethylsulfonium salt, benzyl p-hydroxyphenylmethylsulfonium salt, and benzylphenylsulfonium salt.

[0058] Among them, benzylphenylsulfonium salts are preferred because the resulting polymerizable composition has excellent deep curability, and benzylphenylsulfonium salts represented by the following general formula (2) are particularly preferred.

[0059] [Chemical formula 5]

[0060]

[0061] 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 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 32 With R 33 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 38 With R 39 and R 40 With R 41 They may also be bonded to each other to form a ring having 3 to 10 carbon atoms. 34 represents an alkyl group having 1 to 10 carbon atoms or a group containing an aromatic ring having 6 to 20 carbon atoms, X2 - It represents a monovalent anion.

[0062] The halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and ester groups having 2 to 10 carbon atoms in the above general formula (2) are the same as the halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and ester groups having 2 to 10 carbon atoms in the above general formula (1).

[0063] 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 acetoacetyl.

[0064] 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.

[0065] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group.

[0066] Examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group, a fluorenyl group, an indenyl group, and a 9-fluorenylmethyl group.

[0067] As R 32 With R 33 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 38 With R 39 and R 40 With R 41 Examples of the ring having 3 to 10 carbon atoms formed by mutually bonding 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.

[0068] In the benzylphenylsulfonium salt represented by the general formula (2), R 31 A compound having a hydrogen atom or an acyl group having 2 to 10 carbon atoms is preferred because the deep curability of the resulting polymerizable composition is improved, and an acyl group compound is particularly preferred.

[0069] In R 32 With R 33 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 38 With R 39 and R 40 With R 41 When they 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 A hydrogen atom is preferred. A compound having such a structure is preferred because it is chemically stable and the resulting polymerizable composition also has excellent deep curing properties.

[0070] R 32 With R 33 , R 35 With R 36 , R 37 With R 38 , R 38 With R 39 and R40 With R 41 A compound in which one or more of the monomers are bonded to each other to form a benzene ring is preferred because the deep curability of the obtained polymerizable composition is improved, and R is particularly preferred. 35 With R 36 , R 36 With R 37 , R 37 With R 38 and R 38 With R 39 A compound in which any of the above are bonded to each other to form a benzene ring.

[0071] As X2 - The monovalent anion represented by is preferably a perchlorate ion (ClO4 - ), tetrafluoroborate ion (BF4 - ), hexafluorophosphate ion (PF6 - ), hexafluoroantimonate (SbF6 - ), hexafluoroarsenate (AsF6 - ) and hexachloroantimonate (SbCl6 - ) and other inorganic ions, and hexafluorophosphate ions (PF6 - ) and hexafluoroantimonate (SbF6 - ).

[0072] 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-naphthylmethyl p-hydroxyphenylmethylsulfonium salt.

[0073] As the thermal cationic polymerization initiator, commercially available products may be used. Examples thereof include CI-2064, CI-2624, CI-2639, CI-2855, CI-2920, CI-2921, CI-2946, and CI-3128 (all manufactured by Nippon 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, and SI-180L (all manufactured by Sanshin Chemical Co., Ltd.), TA-90, TA-100, TA-120, TA-160, IK-1, and IK-2 (all manufactured by San-Apro Ltd.), Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA), FC-520 (manufactured by 3M), etc.

[0074] The content of the thermal cationic polymerization initiator is 50 to 1000 parts by mass relative 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, the obtained polymerizable composition has excellent deep curing properties, so it is preferred. The thermal cationic polymerization initiator can be used alone or in combination of two or more. When two or more are mixed, the above content refers to the total content of the multiple thermal cationic polymerization initiators.

[0075] 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 by the above-mentioned photocationic polymerization initiator or thermal cationic polymerization initiator. Any compound may be used, and examples thereof include epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic sulfide compounds, spiroorthoester compounds, and vinyl compounds.

[0076] As the cationically polymerizable compound, a polyfunctional cationically polymerizable compound having a plurality of groups that initiate polymerization or crosslinking reaction in the molecule is preferred because it is excellent in deep curing property.

[0077] Among these compounds, epoxy compounds and oxetane compounds are preferred because they are easily available and have good curability.

[0078] Examples of the epoxy compound include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds, among which alicyclic epoxy compounds and aromatic epoxy compounds are preferred. When the cationic polymerizable compound is the above-mentioned compound, the obtained polymerizable composition becomes a composition with excellent curing properties.

[0079] In addition, the epoxy compound is assumed to include all compounds containing an epoxy group. For example, a compound containing both an epoxy group and an oxetanyl group is assumed to be included in the epoxy compound.

[0080] Specific examples of the alicyclic epoxy compounds include polyglycidyl ethers of polyols having at least one aliphatic ring, and compounds containing cycloolefin oxide structures obtained by epoxidizing compounds containing cycloolefin structures such as cyclohexene structures and cyclopentene structures with an oxidizing agent. Examples of the alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 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)-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

[0081] In addition, the epoxy compound which has both an aliphatic ring and an aromatic ring is regarded as an alicyclic epoxy compound.

[0082] Examples of commercially available products that can be preferably used as the alicyclic epoxy compound include UVR-6100, UVR-6105, UVR-6110, UVR-6128, and UVR-6200 (all manufactured by Union Carbide Corporation), 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, and EPOLEAD HD300, EHPE-3150, EHPE-3150CE (all manufactured by Daicel), KRM-2110, KRM-2199 (all manufactured by ADEKA), etc.

[0083] Among the alicyclic epoxy compounds, epoxy resins having a cyclohexene oxide structure are preferred because the resulting polymerizable composition has excellent curability.

[0084] Specific examples of the aromatic epoxy compounds include polyglycidyl ethers of polyphenols having at least one aromatic ring or their alkylene oxide adducts, such as bisphenol A, bisphenol F, and glycidyl ethers of compounds obtained by further adding alkylene oxide to these, and epoxy novolac resins.

[0085] In addition, an aromatic epoxy compound is an epoxy compound which has an aromatic ring and does not have an aliphatic ring.

[0086] An aromatic epoxy compound is preferred because the resulting polymerizable composition has excellent deep curability.

[0087] Specific examples of the aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polyacids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers, and the like. Representative compounds include 1,4-butanediol diglycidyl Glycidyl ethers of polyols such as propylene glycol, propylene glycol, trimethylolpropane, glycerol, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as propylene glycol, trimethylolpropane, and glycerol; diglycidyl esters of aliphatic long-chain dibasic acids, etc. Further examples include monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, and epoxidized polybutadiene, etc.

[0088] In addition, the aliphatic epoxy compound is an epoxy compound which does not have an aromatic ring and a cyclohexene oxide structure.

[0089] Examples of 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, jER604 (all manufactured by Mitsubishi Chemical Corporation), PY-306, 0163, DY-022 (all manufactured by Ciba-Geigy), KRM-2720, EP-4100, EP-4000, EP-4080, EP-4088, EP-4900, ED-505, ED-506 (all manufactured by ADEKA Corporation), 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 (all manufactured by Kyoeisha Chemical Co., Ltd.), Santoto ST0000, YD-716, YH-300, PG-202, PG-207, YD-172, YDPN638 (all manufactured by Nippon Steel Chemical Co., Ltd.), DENACOL EX321, DENACOL EX313, DENACOL 314, DENACOL EX-411, EM-150 (all manufactured by Nagase Chemtex), 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.), etc.

[0090] Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 3-(methyl)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, methyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanyl methyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanyl methyl) ether, dicyclopentadiene (3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyl (3-ethyl-3-oxetanyl methyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanyl methyl) ether, tetrabromophenyl (3-ethyl-3-oxetanyl methyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanyl methyl) ether, tribromophenyl (3-ethyl-3-oxetanyl methyl) ether, 2-tribromophenoxyethyl (3-ethyl-3- 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, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methenyl) propanediyl bis (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, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyl dimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(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 tetra(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetra(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) Ether, caprolactone modified dipentaerythritol penta (3-ethyl-3-oxetanyl methyl) ether, di (trimethylolpropane) tetra (3-ethyl-3-oxetanyl methyl) ether, EO modified bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether, PO modified bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether, PO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanyl methyl) ether and EO modified bisphenol F (3-ethyl-3-oxetanyl methyl) ether, etc.

[0091] Examples of commercially available products that can be preferably used as the oxetane compound include Aron Oxetane OXT-101, OXT-121, OXT-221, OXT-212, and OXT-211 (all manufactured by Toagosei Co., Ltd.), and ETERNACOLL EHO, OXBP, OXTP, and OXMA (all manufactured by Ube Industries, Ltd.).

[0092] A polymerizable composition containing an oxetane compound as a cationic polymerizable compound is preferred because of its excellent deep curability. As the oxetane compound, an oxetane compound having two or more oxetane groups in the same molecule is more preferred, and an oxetane compound having two oxetane groups is particularly preferred.

[0093] 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 relative to 100 parts by mass of the cationic polymerizable compound. When the content of the cationic compound is within the above range, the curability of the obtained polymerizable composition is excellent, so it is preferred.

[0094] Other cationic polymerizable compounds include oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; cyclic acetal compounds such as trioxane, 1,3-dioxolane and 1,3,6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; vinyl sulfide compounds such as ethylene sulfide and thioepichlorohydrin; thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane; cyclic thiophene derivatives such as tetrahydrothiophene derivatives. Thioether compounds; vinyl ether compounds such as ethylene 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; spiroorthoester compounds obtained by the reaction of epoxy compounds with lactones; ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene and polybutadiene, and derivatives of these compounds, etc.

[0095] The polymerizable composition of the present invention may contain a sensitizer.

[0096] A polymerizable composition containing a sensitizer is preferred because of its excellent deep curability. A sensitizer is a substance that is not polymerizable and promotes cationic polymerization by being used in combination with the above-mentioned photocationic polymerization initiator, excluding compounds classified as the above-mentioned photocationic polymerization initiator or the above-mentioned thermal cationic polymerization initiator.

[0097] As the sensitizer, anthracene sensitizers, naphthalene sensitizers and benzocarbazole initiators can be listed, and benzocarbazole sensitizers are preferred because of their particularly excellent reactivity. Two or more of these sensitizers can be used in combination. The following examples show the structure of the preferred sensitizer.

[0098] [Chemical formula 6]

[0099]

[0100] In the formula, R represents an alkyl group having 1 to 10 carbon atoms.

[0101] The content of the sensitizer is not particularly limited, but is preferably 1 to 1000 mol, more preferably 5 to 500 mol, and particularly preferably 10 to 200 mol per 1 mol of the photocationic polymerization initiator. When the content of the sensitizer is within the above range, the resulting polymerizable composition has excellent curability, which is preferred.

[0102] The polymerizable composition of the present invention may contain a sulfate.

[0103] The polymerizable composition containing sulfate is preferred because of its good thermal stability and excellent deep curing property. Among the sulfates, alkyl sulfates are particularly preferred. Examples of anions of the alkyl sulfates include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0104] As the cation ion of the sulfate, a sulfonium ion is preferred, and a sulfonium ion represented by the following general formula (3) is particularly preferred, because the thermal stability of the polymerizable composition is good and the deep curing property is high.

[0105] [Chemical formula 7]

[0106]

[0107] 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 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 With R 53 and R 56 With R 57 They may also be bonded to each other to form a ring having 3 to 10 carbon atoms. 54 and R 55 It represents a hydrocarbon group having 1 to 20 carbon atoms.

[0108] The halogen atoms, acyl groups having 2 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, ester groups having 2 to 10 carbon atoms, and rings having 3 to 10 carbon atoms in the above general formula (3) are the same as the halogen atoms, acyl groups having 2 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, ester groups having 2 to 10 carbon atoms, and rings having 3 to 10 carbon atoms in the above general formula (2). In addition, the hydrocarbon groups having 1 to 20 carbon atoms in the above general formula (3) are the same as the hydrocarbon groups having 1 to 20 carbon atoms in the above general formula (1).

[0109] In the cation represented by the above general formula (3), R 51 Ions that are hydrogen atoms are preferred because the resulting polymerizable composition has good thermal stability and excellent deep curing properties.

[0110] In the cation represented by the above general formula (3), R 52 , R 53 , R 56 and R 57Ions that are hydrogen atoms are preferred because the resulting polymerizable composition has good thermal stability and excellent deep curing properties.

[0111] Examples of the sulfate used in the present invention include aromatic sulfonium alkyl sulfates, and specific examples include 4-hydroxyphenyl (dimethyl) sulfonium methyl sulfate.

[0112] The content of the 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 thermal cationic polymerization initiator. When the content of the sulfate is within the above range, the resulting polymerizable composition has good thermal stability and excellent curability, which is preferred.

[0113] In the polymerizable composition of the present invention, a solvent (a compound that exists as a liquid at atmospheric pressure and 25° C. and does not belong to the above-mentioned components) that can dissolve or disperse the above-mentioned components, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, dichloromethane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, and isopropanol, etc., can be added as needed. In the polymerizable composition of the present invention, the content of the solvent is appropriately selected depending on the use of the polymerizable composition, etc., and is not particularly limited. However, generally, if the solvent is contained so that the solid content (the total content of all components other than the solvent) of the polymerizable composition is 5 to 90% by mass, the operation of forming a coating film, etc. becomes easy.

[0114] In addition, 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; antistatic agents such as cationic surfactants, anionic surfactants, nonionic surfactants and amphoteric surfactants; flame retardants such as halogen compounds, phosphate ester compounds, phosphoric acid amide compounds, melamine compounds, fluororesins or metal oxides, (poly) melamine phosphate and (poly) piperazine phosphate; and lubricants such as hydrocarbon-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based and metal soap-based lubricants may be added as needed. Lubricants; colorants such as pigments and carbon black; silicic acid inorganic additives such as fumed silica, fine silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, stone wool, talc, mica, talc, pyrophyllite and silicon dioxide; fillers such as glass fiber and calcium carbonate; crystallization agents such as nucleating agents and crystallization accelerators; rubber elasticity imparting agents such as silane coupling agents and flexible polymers; other monomers, defoamers, thickeners, leveling agents, plasticizers, inhibitors, antistatic agents, flow regulators, coupling agents and adhesion promoters. The amount of these various additives used in the polymerizable composition of the present invention is set to 50% by mass or less in total.

[0115] The polymerizable composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays, and can be cured to a dry-to-touch state or a solvent-insoluble state usually 0.1 seconds to several minutes after irradiation. As suitable active energy rays, any active energy rays can be used as long as they induce the decomposition of the photoacid generator, preferably electromagnetic wave energy with a wavelength of 200nm to 700nm obtained by 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 semiconductor lasers, YAG lasers, light emitting diodes, CRT light sources, etc., and highly active energy rays such as electron beams, X-rays and radiation.

[0116] The irradiation time of the active energy ray varies depending on the intensity of the active energy ray, the coating thickness, and the cationic polymerizable organic compound, but is generally sufficient for about 0.1 seconds to 10 seconds. However, for relatively thick coatings, it is preferably set to an irradiation time longer than that. Most compositions are dry to touch by cationic polymerization 0.1 seconds to several minutes after irradiation with active energy rays, but in order to promote cationic polymerization, it is also preferred to use heat energy such as heating and using a thermal head depending on the situation.

[0117] The polymerizable composition of the present invention can be cured by heating using 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.

[0118] The heating temperature during heat curing is not particularly limited, but is preferably 70 to 200° C., more preferably 90 to 150° C., from the perspective of promoting 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 perspective of improving productivity.

[0119] Furthermore, the polymerizable composition of the present invention can be cured by irradiation with active energy rays and heating. In this case, the polymerizable composition may be heated after being irradiated with active energy rays, or the polymerizable composition may be irradiated with active energy rays after being heated. From the perspective of improving the positional accuracy when used as a component fixing adhesive, it is preferred to heat the composition after irradiating it with active energy rays.

[0120] When irradiation with active energy rays and heating are used together in curing the polymerizable composition of the present invention, the active energy rays and heating devices used may be those described above without particular limitation, but ultraviolet rays are preferably used as the active energy rays because of excellent deep curing properties.

[0121] The specific uses of the polymerizable composition of the present invention include optical filters; coatings; coating agents; lining agents; adhesives; printing plates; insulating varnishes; insulating sheets; laminates; printed circuit boards; sealants for semiconductor devices, LED packaging, liquid crystal injection ports, organic EL, optical components, electrical insulation, electronic components, and separation membranes; molding materials; putties; glass fiber impregnation agents; fillers; passivation films for semiconductors and solar cells; interlayer insulating films; protective films; printed circuit boards; color filters for color televisions, PC monitors, portable information terminals, and CCD image sensors; electrode materials for plasma display panels; printing inks; dental compositions; photomolding resins; liquid and dry films; micromechanical parts; glass fiber cable coatings; holographic recording materials, and the like, and there are no particular restrictions on the uses.

[0122] Example

[0123] 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.

[0124] [Examples 1 to 32 and Comparative Examples 1 to 10]

[0125] The components and a solvent (propylene carbonate) were mixed in the formulations shown in Tables 1 to 4, and stirred until insoluble matter disappeared, thereby obtaining polymerizable compositions of Examples and Comparative Examples.

[0126] 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, stabilizer E-1, radical polymerizable compounds F-1 to F-2 and photoradical polymerization initiator G-1 are compounds having the following structures respectively.

[0127] [Chemical formula 8]

[0128]

[0129] [Chemical formula 9]

[0130]

[0131] [Chemical formula 10]

[0132]

[0133] [Chemical formula 11]

[0134]

[0135] [Chemical formula 12]

[0136]

[0137] [Chemical formula 13]

[0138]

[0139] [Chemical formula 14]

[0140]

[0141] (Storage stability)

[0142] 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. The composition with a viscosity change rate of less than 10% was set as A, the composition with a viscosity change rate of 10% or more and less than 25% was set as B, the composition with a viscosity change rate of 25% or more and less than 50% was set as C, and the composition with a viscosity change rate of 50% or more was set as D. The composition with less viscosity change has better storage stability and is therefore preferred.

[0143] (Deep curing)

[0144] The polymerizable composition was applied onto a release film (Lumirror T60: manufactured by Toray Industries, Inc.) using a bar coater to a predetermined film thickness (100 μm, 50 μm, and 30 μm), and the film was illuminated using a 365 nm wavelength LED light source (100 mW / cm 2 ) for 500mJ / cm 2 After exposure, the film was left to stand at room temperature for 2 hours. Afterwards, the release film was peeled off and the state of the peeling surface was confirmed. If no stickiness could be confirmed on the peeling surface, it was judged that a cured product was obtained, and a composition with stickiness was judged not to have obtained a cured product. The composition that can obtain a cured product with a thicker film is more preferred as an adhesive for a component. The results are summarized in Tables 1 to 4.

[0145] A: A cured product having a film thickness of 100 μm was obtained.

[0146] 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.

[0147] 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.

[0148] D: A cured product having a film thickness of 30 μm was not obtained.

[0149] (Curing shrinkage)

[0150] The polymerizable composition was applied onto a release film (Lumirror T60: manufactured by Toray Industries, Inc.) using a bar coater to a film thickness of 30 μm, and a 365 nm wavelength LED light source (100 mW / cm 2 ) for 500mJ / cm 2 After exposure, let it stand at room temperature for 2 hours. Then, peel off the release film to obtain a sample. The density of the obtained sample and the sample before curing was measured using a gas pycnometer (JIS Z8837). Then, the curing shrinkage was calculated from the ratio of the density change before and after curing. The smaller the curing shrinkage, the higher the positional accuracy, so it is more preferred as an adhesive for components. The results are summarized in Tables 1 to 4.

[0151] A: Curing shrinkage is less than 4%.

[0152] B: The curing shrinkage is 4% or more and less than 7%.

[0153] C: The curing shrinkage is 7% or more.

[0154]

[0155]

[0156]

[0157]

[0158] As shown in Tables 1 to 4, the polymerizable composition of the present invention is excellent in storage stability, sensitivity, deep curing property and positioning accuracy. The polymerizable composition of the present invention is not limited to its application, but is particularly useful as an adhesive for fixing components such as electronic parts, wiring, and vehicle-mounted materials.

[0159] Industrial Applicability

[0160] The polymerizable composition of the present invention is useful as a polymerizable composition for use in applications requiring a thick cured product because it can obtain a thick cured product with excellent positional accuracy in a short time by irradiation with active energy rays and has high productivity.

Claims

1. A polymerizable composition comprising a photocationic polymerization initiator, a thermal cationic polymerization initiator, a cationic polymerizable compound and an alkyl sulfate, The content of the thermal cationic polymerization initiator is 50 to 1000 parts by mass based on 100 parts by mass of the photocationic polymerization initiator. The photocationic polymerization initiator contains an aromatic sulfonium salt represented by the following general formula (1): 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 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 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 group represented by the following general formula (1a), and X 1 - represents a univalent anion, In the formula, R 19 , R 20 , R 21 , R 22 and R 23 Each independently 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, * represents a bonding point, The thermal cationic polymerization initiator contains a benzylphenylsulfonium salt represented by the following general formula (2): 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 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 32 With R 33 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 38 With R 39 and R 40 With R 41 They may also be bonded to each other to form a ring having 3 to 10 carbon atoms. 34 represents an alkyl group having 1 to 10 carbon atoms or a group containing an aromatic ring having 6 to 20 carbon atoms, and X 2 - represents a univalent anion, The cationically polymerizable compound is an epoxy compound and / or an oxetane compound, The anion of the alkyl sulfate is a methyl sulfate ion, an ethyl sulfate ion or a propyl sulfate ion, The cation of the alkyl sulfate is a sulfonium ion represented by the following general formula (3): 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 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 With R 53 and R 56 With R 57 They may also be bonded to each other to form a ring having 3 to 10 carbon atoms. 54 and R 55 It represents a hydrocarbon group having 1 to 20 carbon atoms.

2. The polymerizable composition according to claim 1, in, The polymerizable composition contains a sensitizer.

3. A cured product of the polymerizable composition according to claim 1 or 2. 4 . A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to claim 1 or 2 with light.

Images