KR20220074926A - Curable composition, cured product, and method of forming cured product - Google Patents

Abstract

To provide a cationically curable curable composition capable of achieving both suppression of coloration of the cured product during curing and good curability, a cured product of the curable composition, and a method for forming a cured product using the curable composition. A curable composition comprising a cationic curing agent (A) and a cationically curable compound (B), wherein the photo-acid generator (A1) comprising an onium salt having a cationic moiety having a specific structure and a gallium-containing anion having a specific structure are combined with an anion moiety A cationic curing agent containing a combination of the thermal acid generator (A2) is used.

Description

Curable composition, cured product, and method of forming cured product

The present invention relates to a curable composition containing a cationic curing agent (A) and a cationically curable compound (B), a cured product of the curable composition, and a method for forming a cured product using the curable composition.

DESCRIPTION OF RELATED ART Conventionally, the cationically polymerizable curable composition containing cationically polymerizable compounds, such as an epoxy compound, as a sclerosing|hardenable component is used for various uses.

As such a curable composition, for example, an aromatic ring-containing alicyclic epoxy compound, a cationically polymerizable compound other than an aromatic ring-containing alicyclic epoxy compound, and a cationically polymerizable thermosetting composition containing a thermal cationic polymerization initiator are known (patents). See Document 1.). By using such a curable composition, a hardened|cured material which has a high glass transition temperature, is hard to yellow even if heated to high temperature, and is excellent in base-material adhesiveness can be formed.

Patent Document 1: Japanese Patent Laid-Open No. 2014-156522

However, in the curable composition containing a thermal cationic polymerization initiator as described in patent document 1, high temperature may be required for hardening, or a long time may be required. This defect can be solved by using an onium salt-based photoacid generator. However, when a curable composition containing an onium salt-based photo-acid generator and a cation-curable compound is cured by exposure, there is a problem in that the cured product is frequently colored during curing.

The present invention has been made in view of the above problems, and uses a cationically curable curable composition that is compatible with both suppression of coloration of the cured product during curing and good curability, a cured product of the curable composition, and the curable composition An object of the present invention is to provide a method for forming a cured product.

The present inventors, in a curable composition comprising a cationic curing agent (A) and a cationically curable compound (B), a photoacid generator (A1) comprising an onium salt having a cationic moiety having a specific structure, and gallium containing a specific structure By using the cationic curing agent containing in combination the thermal acid generator (A2) which has an anion as an anion part, it discovered that said subject could be solved, and came to complete this invention. Specifically, the present invention provides the following.

A 1st aspect of this invention contains a cation hardening agent (A) and a cation-curable compound (B),

As the cationic curing agent (A), a photoacid generator (A1) and a thermal acid generator (A2) are included,

The photoacid generator (A1) is an onium salt having a cation moiety represented by the following formula (ai),

The thermal acid generator (A2) is a curable composition which is an onium salt which has an anion part represented by following formula (Ai).

(R ^a1 ) _t+1 -R ^a2+ ...(ai)

(In formula (ai), R ^a1 is each independently a monovalent organic group, R ^a2 is an element having a valence t of Groups 15 to 17 of the Periodic Table of Elements according to IUPAC notation, and R ^a1 At least one is an aryl group which may have a substituent.)

(R ^A1 ) ₄ -Ga ^- ... (Ai)

(In formula (Ai), R ^A1 is each independently a phenyl group which may have one or more substituents, or a perfluoroalkyl group.)

A second aspect of the present invention is a cured product of the curable composition according to the first aspect.

A third aspect of the present invention is a method for forming a cured product in which exposure and heating are applied to the curable composition according to the first aspect.

According to the present invention, it is possible to provide a cationically curable curable composition capable of achieving both suppression of coloration of the cured product during curing and good curability, a cured product of the curable composition, and a method for forming a cured product using the curable composition have.

«Curable composition»

The curable composition contains a cation curing agent (A) and a cation curing compound (B).

The cationic curing agent (A) contains a photoacid generator (A1) and a thermal acid generator (A2).

A photo-acid generator (A1) is an onium salt which has a cation part represented by following formula (ai).

(R ^a1 ) _t+1 -R ^a2+ ...(ai)

(In formula (ai), R ^a1 is each independently a monovalent organic group, R ^a2 is an element of valence t of Groups 15 to 17 of the Periodic Table of Elements according to IUPAC notation, and R ^a1 At least one is an aryl group which may have a substituent.)

The thermal acid generator (A2) is an onium salt having an anion moiety represented by the following formula (Ai).

(R ^A1 ) ₄ -Ga ^- ... (Ai)

(In formula (Ai), R ^A1 is each independently a phenyl group which may have one or more substituents, or a perfluoroalkyl group.)

By using in combination the said photo-acid generator (A1) which has a cationic part of a specific structure, and said thermal acid generator (A2) which has an anionic part of a specific structure, sclerosis|hardenability of a curable composition is improved, and the time of hardening Coloration of hardened|cured material can be suppressed.

With respect to the coloring of the cured product when the cation-curable compound (B) is cured using the onium salt-based photo-acid generator (A1), when the photo-acid generator (A1) is decomposed by exposure, generating a color-causing substance It is thought to be the cause On the other hand, when the thermal acid generator (A2) is decomposed by heating, a substance causing coloration due to the color-causing substance generated by the decomposition of the photo-acid generator (A1) is not generated, or the thermal acid generator (A2) is not generated. ), it is thought that coloring of the hardened|cured material at the time of hardening is suppressed by exerting some effect|action with respect to the coloring causative substance.

In particular, when the cation-curable compound (B) described later is a compound that imparts a colorless and transparent cured product, a highly colorless and transparent compound suitable for optical use by combining the cation-curing agent (A) with the cation-curable compound (B) A cured product can be formed.

Hereinafter, the essential or arbitrary components contained in a curable composition are demonstrated.

[Mine generator (A1)]

A photo-acid generator (A1) is an onium salt which has a cation part represented by following formula (ai). The anion part which comprises the onium salt as a photo-acid generator (A1) is not specifically limited in the range which does not impair the objective of this invention.

(R ^a1 ) _t+1 -R ^a2+ ...(ai)

(In formula (ai), R ^a1 is each independently a monovalent organic group, R ^a2 is an element having a valence t in Groups 15 to 17 of the Periodic Table of Elements according to IUPAC notation, and at least one of R ^a1 is an aryl group which may have a substituent.)

R ^a1 in the formula (ai), which is a cation moiety, represents an organic group bonded to R ^a2 . As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable. In the case where two or more R ^a1s exist, a plurality of R ^a1s may be the same or different. As R ^a1 , an aryl group having 6 to 14 carbon atoms (aromatic hydrocarbon group) which may have a substituent, an alkyl group having 1 to 18 carbon atoms which may have a substituent, and 7 or more carbon atoms which may have a substituent A 12 or less aralkyl group, a C2 or more 18 or less alkenyl group which may have a substituent, and a C2 or more and 18 or less alkynyl group which may have a substituent are mentioned. In the photoacid generator (A1) having a cation represented by formula (ai) as a cation moiety, R ^a1 is an aryl group having 6 or more and 14 or less carbon atoms, an alkyl group having 1 or more and 18 or less carbon atoms, and 2 carbon atoms. An alkenyl group having 18 or more and 18 or less and an alkynyl group having 2 or more and 18 or less carbon atoms are preferable.

As R ^a1 , an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and a substituent which the alkynyl group may have include an alkyl group having 1 to 18 carbon atoms, a halogenated alkyl group having 1 to 18 carbon atoms, 3 carbon atoms. Aliphatic cyclic group with 18 or more, halogenated alicyclic group with 3 or more and 18 or less carbon atoms, alkenyl group with 2 or more and 18 or less carbon atoms, alkynyl group with 2 or more and 18 or less carbon atoms, 6 or more and 14 or less with carbon atoms. of an aryl group, a nitro group, a hydroxyl group, a cyano group, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aliphatic acyl group having 2 to 19 carbon atoms, the number of carbon atoms 7 or more and 15 or less aromatic acyl group, 2 or more and 19 or less aliphatic acyloxy group, 7 or more and 15 or less aromatic acyloxy group, 1 or more and 18 or less alkylthio group, and 18 or less carbon atoms 6 or more and 14 or less arylthio group, an amino group in which 1 or 2 hydrogen atoms bonded to a nitrogen atom may be substituted with a hydrocarbon group having 1 or more and 18 or less carbon atoms, and a halogen atom are mentioned.

Among these substituents, an alkyl group, a halogenated alkyl group, an aliphatic cyclic group, a halogenated alicyclic group, an alkoxy group, an aryloxy group, an aliphatic acyl group, an aromatic acyl group, an aliphatic acyloxy group, an aromatic acyloxy group, an alkylthio group, an arylthi An amino group which may be substituted with a group and a hydrocarbon group is preferable.

When the substituent which R ^a1 may have as an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and an alkynyl group is an alkyl group, preferred examples of the alkyl group include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pene tyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, straight-chain alkyl groups such as n-hexadecyl group, n-heptadecyl group, and n-octadecyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 2-ethylhexyl group, and 1,1,3,3- Branched chain alkyl groups, such as a tetramethylbutyl group, are mentioned.

When the substituent which R ^a1 may have as an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and an alkynyl group is a halogenated alkyl group, preferred examples of the halogenated alkyl group include a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2 ,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, heptafluoro-n-propyl group, 1,1-difluoro-n-propyl group , 3,3,3-trifluoro-n-propyl group, nonafluoro-n-butyl group, 3,3,4,4,4-pentafluoro-n-butyl group, perfluoro-n-pene a straight-chain halogenated alkyl group such as a tyl group and a perfluoro-n-octyl group; and branched chain halogenated alkyl groups such as hexafluoroisopropyl group, hexachloroisopropyl group, hexafluoroisobutyl group, and nonafluoro-tert-butyl group.

When the substituent which R ^a1 may have as an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and an alkynyl group is an aliphatic cyclic group, preferred examples of the alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. A real group, an adamantyl group, etc. are mentioned.

When the substituent which R ^a1 may have as an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and an alkynyl group is a halogenated aliphatic cyclic group, preferred examples of the halogenated alicyclic group include a pentafluorocyclopropyl group and a nonafluorocyclobutyl group. group, a perfluorocyclopentyl group, a perfluorocyclohexyl group, and a perfluoroadamantyl group.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an alkoxy group, preferred examples of the alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, n-butylox group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group straight-chain alkoxy groups such as , n-tetradisyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, and n-octadecyloxy group; isopropyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, isohexyloxy group, 2-ethylhexyloxy group, and branched chain alkoxy groups such as 1,1,3,3-tetramethylbutyloxy group.

When the substituent which R ^a1 may have as an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and an alkynyl group is an aryloxy group, preferred examples of the aryloxy group include a phenoxy group, α-naphthyloxy group, and β-naphthyloxy group. , a biphenyl-4-yloxy group, a biphenyl-3-yloxy group, a biphenyl-2-yloxy group, an anthryloxy group, and a phenanthryloxy group.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an aliphatic acyl group, preferred examples of the aliphatic acyl group include an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, and a hexa A noyl group, a heptanoyl group, and an octanoyl group etc. are mentioned.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an aromatic acyl group, preferred examples of the aromatic acyl group include a benzoyl group, an α-naphthoyl group, and a β-naphthoyl group. , a biphenyl-4-yl carbonyl group, a biphenyl-3-yl carbonyl group, a biphenyl-2-yl carbonyl group, an anthryl carbonyl group, and a phenanthryl carbonyl group.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an aliphatic acyloxy group, preferred examples of the aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, and a butanoyloxy group. , a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, and an octanoyloxy group.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an aromatic acyloxy group, preferred examples of the aromatic acyloxy group include benzoyloxy group, α-naphthoyloxy group, β -naphthoyloxy group, biphenyl-4-yl carbonyloxy group, biphenyl-3-yl carbonyloxy group, biphenyl-2-yl carbonyloxy group, anthryl carbonyloxy group, and phenanthryl car A bornyloxy group etc. are mentioned.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an alkylthio group or an arylthio group, as a preferable example of the alkylthio group or arylthio group, the above-mentioned alkoxy group or a group in which an oxygen atom in a group suitable as an aryloxy group is substituted with a sulfur atom.

In the case where the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is an amino group which may be substituted with a hydrocarbon group, suitable examples of the amino group which may be substituted with a hydrocarbon group include an amino group, a methylamino group, ethylamino group, n-propylamino group, dimethylamino group, diethylamino group, methylethylamino group, di-n-propylamino group, piperidino group, etc. are mentioned.

When the substituent which the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group may have as R ^a1 is a halogen atom, suitable examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. can

Among the substituents described above, from the viewpoint of high activity of the photoacid generator (A1), a halogenated alkyl group having 1 or more and 8 or less carbon atoms, a halogen atom, a nitro group, and a cyano group are preferable, and having 1 or more and 8 carbon atoms. The following fluorinated alkyl groups are more preferable.

In the formula (ai), when a plurality of R ^{a1s exist, a plurality of R a1 may} form a ring together with R ^a2 . The ring formed by a plurality of R ^a1 and R ^a2 is, in the ring structure, -O-, -S-, -SO-, -SO ₂ -, -NH-, -CO-, -COO-, and -CONH It may contain more than one bond selected from the group which consists of -.

R ^a2 in formula (ai) is an element of valence t in Groups 15 to 17 of the Periodic Table of Elements (IUPAC notation). Incidentally, as R ^a2 , elements of Groups 15 to 17 of the Periodic Table of Elements (IUPAC notation) are elements that can stably exist under the conditions for producing a curable composition, under storage conditions, and under conditions for forming a cured product.

R ^a2 combines with the organic group R ^a1 to form an onium ion. Among the elements of Groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation), preferred elements as R ^a2 are S (sulfur), N (nitrogen), I (iodine), and P (phosphorus). Corresponding onium ions include sulfonium ions, ammonium ions, iodonium ions, and phosphonium ions. Since these are stable and easy to handle, they are preferable. A sulfonium ion and an iodonium ion are more preferable, and a sulfonium ion is especially preferable at the point which is excellent in cationic polymerization performance and crosslinking reaction performance.

That is, in the above formula (ai), it is preferable that R ^a2 is sulfur and t is 2.

Specific examples of the sulfonium ion include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naph Tyldiphenylsulfonium, tris (4-fluorophenyl) sulfonium, tri-1-naphthyl sulfonium, tri-2-naphthyl sulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) ) Phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolyl sulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenyl Thio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, [4- (4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfonium Feed, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulf Feed, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl -2-chlorophenylthio) phenyl bis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenyl bis ( 4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl di- p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl diphenylsulfonium, 2-[(di-p-tolyl) sulfonio]thi Oxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- (9-oxo-9H-thioxanthen-2-yl) thiophenyl-9-oxo-9H-thioxanthene-2- ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl di-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl diphenylsulfonium Phonium, 4-[4-(benzoylphenylthio)]phenyl di-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyl diphenylsulfonium, 5-(4-methoxyphenyl) thianth rhenium, triarylsulfoniums such as 5-phenylthiaanthrenium, 5-tolylthiaanthrenium, 5-(4-ethoxyphenyl)thianthrhenium, and 5-(2,4,6-trimethylphenyl)thianthrhenium; diarylsulfoniums such as diphenylphenacyl sulfonium, diphenyl-4-nitrophenacyl sulfonium, diphenylbenzylsulfonium, and diphenylmethylsulfonium; Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl (2-naphthylmethyl) Methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylphenacyl sulfonium, 4-hydroxyphenylmethylphenacyl sulfonium, 4- Methoxyphenylmethylphenacyl sulfonium, 4-acetocarbonyloxyphenylmethylphenacyl sulfonium, 2-naphthylmethylphenacyl sulfonium, 2-naphthyloctadecylphenacyl sulfonium, and 9-anthracenyl methylphen monoarylsulfonium such as acylsulfonium; and trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

Specific examples of the ammonium ion include tetraalkyl ammonium such as tetramethyl ammonium, ethyltrimethyl ammonium, diethyldimethyl ammonium, triethylmethyl ammonium, and tetraethyl ammonium; pyrrolidinium such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1 imidazoliniums such as ,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N,N'-dimethyltetrahydropyrimidinium; morpholinium such as N,N'-dimethylmorpholinium; piperidinium such as N,N'-diethylpiperidinium; pyridiniums such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium; imidazolium such as N,N'-dimethylimidazolium; quinoliums such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; Acridium, such as benzyl acridium and phenacyl acridium, is mentioned.

Specific examples of the phosphonium ion include tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4- Tetraarylphosphonium, such as methoxyphenyl) phosphonium; triarylphosphonium such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; tetraalkylphosphonium such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium; can

Specific examples of the iodonium ion include diphenyliodonium, di-p-tolyliiodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4- Octyloxyphenyl) phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropyl phenyl (p-tolyl) iodonium ions, such as iodonium and 4-isobutylphenyl (p-tolyl) iodonium.

Examples of the photo-acid generator (A1) include gallium-containing onium salts having an anion moiety represented by the following formula (aii) and boron-containing onium salts having an anion moiety represented by the following formula (aiii).

(In formula (aii), R ^a3 , R ^a4 , R ^a5 , and R ^a6 are each independently a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, and R ^a3 , R ^a4 , R at least one of ^a5 and R ^a6 is an aromatic hydrocarbon group which may have a substituent.)

(In formula (aiii), R ^a7 , R ^a8 , R ^a9 , and R ^a10 are each independently a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, and R ^a7 , R ^a8 , R at least one of ^a9 and R ^a10 is an aromatic hydrocarbon group which may have a substituent.)

Although the number of carbon atoms in the hydrocarbon group or heterocyclic group as R ^a3 to R ^a6 in the formula (aii) is not particularly limited, 1 or more and 50 or less are preferable, 1 or more and 30 or less are more preferable, and 1 or more and 20 or less are particularly preferable. do.

Specific examples of the hydrocarbon group as R ^a3 to R ^a6 include a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and an aralkyl group. and the like.

As described above, at least one of R ^a3 to R ^a6 is an aromatic group which may have a substituent, more preferably 3 or more of R ^a3 to R ^a6 are an aromatic group which may have a substituent, and R ^a3 to R ^a6 It is especially preferable that all are aromatic groups which may have a substituent.

Examples of the hydrocarbon group or the heterocyclic group as R ^a3 to R ^a6 include a halogenated alkyl group having 1 to 18 carbon atoms, a halogenated alicyclic group having 3 to 18 carbon atoms, a nitro group, a hydroxyl group, and a cyano group. , C1-C18 alkoxy group, C6-C14 aryloxy group, C2-C19 aliphatic acyl group, C7-C15 aromatic acyl group, carbon atom An aliphatic acyloxy group having 2 or more and 19 or less, an aromatic acyloxy group having 7 or more and 15 or less carbon atoms, an alkylthio group having 1 or more and 18 or less carbon atoms, an arylthio group having 6 to 14 carbon atoms, a nitrogen atom and an amino group in which 1 or 2 hydrogen atoms bonded to to may be substituted with a hydrocarbon group having 1 or more and 18 or less carbon atoms, and a halogen atom.

When the hydrocarbon group as R ^a3 to R ^a6 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and alkynyl having 2 to 18 carbon atoms. It may be substituted with one or more substituents selected from the group which consists of groups.

When the hydrocarbon group as R ^a3 to R ^a6 has a substituent, the number of the substituents is not particularly limited, and may be one or a plurality of two or more. When the number of substituents is two or more, the said plurality of substituents may be the same or different, respectively.

Suitable specific examples when R ^a3 to R ^a6 are an alkyl group include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n- Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -linear alkyl groups such as a nonadecyl group and an n-icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 2-ethylhexyl group, and 1,1,3,3- Branched chain alkyl groups, such as a tetramethylbutyl group, are mentioned.

Suitable examples when R ^a3 to R ^a6 are an alkenyl group or an alkynyl group include an alkenyl group corresponding to the above group suitable as an alkyl group, and an alkynyl group.

Suitable examples when R ^a3 to R ^a6 are aromatic hydrocarbon groups include phenyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group , and a phenanthryl group.

Suitable examples when R ^a3 to R ^a6 are an alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group such as cyclodecyl group. an alkyl group; and a bridged aliphatic cyclic hydrocarbon group such as a norbornyl group, an adamantyl group, a tricyclodecyl group, and a pinanyl group.

Suitable examples when R ^a3 to R ^a6 are aralkyl groups include benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group.

Suitable examples when R ^a3 to R ^a6 are heterocyclic groups include thienyl, furanyl group, selenophenyl group, pyranyl group, pyrryl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, indole group Diary, benzofuranyl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxarinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenothiazinyl group, phenazinyl group, xanthenyl group, thiantrenyl group, and a phenoxadinyl group, a phenoxatinyl group, a chromanyl group, an isochromanyl group, a dibenzothienyl group, a xantonyl group, a thioxanthonyl group, and a dibenzofuranyl group.

Examples of R ^a7 to R ^a10 in formula (aiii) include the same groups as those described above for R ^a3 to R ^a6 in formula (aii).

As a suitable specific example of the anion part represented by Formula (aii) demonstrated above,

tetrakis(4-nonafluorobiphenyl) gallium anion;

tetrakis(1-heptafluoronaphthyl) gallium anion;

tetrakis (pentafluorophenyl) gallium anion,

tetrakis (3,4,5-trifluorophenyl) gallate anion;

tetrakis (2-nonaphenylbiphenyl) gallium anion,

tetrakis(2-heptafluoronaphthyl) gallium anion;

tetrakis(7-nonafluoroanthryl) gallium anion;

tetrakis (4'-(methoxy) octafluorobiphenyl) gallium anion;

tetrakis(2,4,6-tris(trifluoromethyl)phenyl)gallium anion;

tetrakis(3,5-bis(trifluoromethyl)phenyl)gallium anion;

tetrakis(2,3-bis(pentafluoroethyl)naphthyl)gallium anion;

tetrakis(2-isopropoxy-hexafluoronaphthyl) gallium anion;

tetrakis(9,10-bis(heptafluoropropyl) heptafluoroanthryl) gallium anion;

tetrakis(9-nonafluorophenanthryl) gallate anion;

tetrakis(4-[tri(isopropyl)silyl]-tetrafluorophenyl)gallium anion;

tetrakis(9,10-bis(p-tolyl)-heptafluorophenanthryl) gallium anion;

tetrakis(4-[dimethyl(t-butyl)silyl]-tetrafluorophenyl)gallium anion;

monophenyltris(pentafluorophenyl) gallium anion, and

Monoperfluorobutyltris(pentafluorophenyl) gallium anion etc. are mentioned, More preferably, the following anions are mentioned.

Moreover, as a suitable specific example of the anion part represented by Formula (aiii),

tetrakis(4-nonafluorobiphenyl) boron anion;

tetrakis(1-heptafluoronaphthyl) boron anion;

tetrakis (pentafluorophenyl) boron anion,

tetrakis (3,4,5-trifluorophenyl) boron anion;

tetrakis (2-nonaphenylbiphenyl) boron anion,

tetrakis(2-heptafluoronaphthyl) boron anion;

tetrakis(7-nonafluoroanthryl) boron anion;

tetrakis (4'-(methoxy) octafluorobiphenyl) boron anion,

tetrakis(2,4,6-tris(trifluoromethyl)phenyl)boron anion;

tetrakis(3,5-bis(trifluoromethyl)phenyl)boron anion;

tetrakis (2,3-bis (pentafluoroethyl) naphthyl) boron anion;

tetrakis(2-isopropoxyhexafluoronaphthyl) boron anion;

tetrakis(9,10-bis(heptafluoropropyl) heptafluoroanthryl) boron anion;

tetrakis(9-nonafluorophenanthryl) boron anion;

tetrakis(4-[tri(isopropyl)silyl]-tetrafluorophenyl)boron anion;

tetrakis(9,10-bis(p-tolyl)-heptafluorophenanthryl) boron anion;

tetrakis(4-[dimethyl(t-butyl)silyl]-tetrafluorophenyl)boron anion;

monophenyltris(pentafluorophenyl) boron anion, and

Monoperfluorobutyltris(pentafluorophenyl) boron anion etc. are mentioned, More preferably, the following anions are mentioned.

In addition, as a suitable specific example of the cation part represented by Formula (ai) demonstrated above,

4-isopropylphenyl (p-tolyl) iodonium,

iodonium ions, such as 4-isobutylphenyl (p-tolyl) iodonium;

[4-(2-thioxanthonylthio)phenyl]diphenylsulfonium;

2-[(di-p-tolyl) sulfonio] thioxanthone;

2-[(diphenyl) sulfonio] thioxanthone;

thioxanthone skeleton-containing sulfonium ions such as 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium;

Specifically, the cation part represented by Formula (a1) mentioned later;

In addition, the sulfonium ion shown below; is mentioned.

As mentioned above, the aspect in which a photo-acid generator (A1) has a cation part represented by following formula (a1) is also preferable. When the onium salt as a photo-acid generator (A1) has a cation part represented by Formula (a1), it is excellent in the sensitivity of a photo-acid generator (A1). When the onium salt as a photo-acid generator (A1) contains the cation part represented by following formula (a1), it is easy to advance hardening of the cation-curable compound (B) mentioned later favorably.

(In the formula (a1), R ¹ and R ² independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (a2), and R ¹ and R ² are bonded to each other to form a ring together with the sulfur atom in the formula. may be formed, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, provided that R ¹ and R ² are at the same time , not an alkyl group which may be substituted with a halogen atom.)

(In formula (a2), ring Z ¹ represents an aromatic hydrocarbon ring, R ⁴ is an optionally substituted alkyl group with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, thienyl; Thienylcarbonyl group, furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group represents a no group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more.)

(in formula (a3), R ⁵ is a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom which may be substituted an alkylene group or a group represented by the following formula (a5), R ⁶ is a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, An aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or represents an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (a6), A ² represents a single bond, S, O, a sulfinyl group, or a carbonyl group, and n1 represents 0 or 1.)

(in formula (a4), R ⁷ and R ⁸ are independently a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, An aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or represents an alkylene group optionally substituted with a halogen atom or a group represented by the following formula (a5), R ⁹ and R ¹⁰ independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the formula (a2), R ⁹ and R ¹⁰ may combine with each other to form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, X ⁻ represents a monovalent anion, n2 represents 0 or 1 , provided that R ⁹ and R ¹⁰ are not an alkyl group which may be substituted with a halogen atom at the same time.)

(In the formula (a5), ring Z ² represents an aromatic hydrocarbon ring, R ¹¹ is an optionally substituted alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, Acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly)alkyleneoxy group, substitution An amino group, a cyano group, a nitro group, or a halogen atom may be represented, and m2 represents an integer of 0 or more.)

(in formula (a6), ring Z ³ represents an aromatic hydrocarbon ring, R ¹² is optionally substituted with a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group; Acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more.)

The sulfonium salt having a cation moiety represented by the formula (a1) is characterized in that in the benzene ring in the formula (a1), a methyl group is bonded to a carbon atom ortho-positioned to a carbon atom to which A ¹ is bonded. Since it has a methyl group at the said position, compared with the conventional sulfonium salt, it is easy to generate|occur|produce a proton, and the sensitivity with respect to active energy rays, such as an ultraviolet-ray, is high.

In the formula (a1), it is preferable that both R ¹ and R ² are groups represented by the formula (a2). R ¹ and R ² may be the same as or different from each other.

In the formula (a1), when R ¹ and R ² are bonded to each other to form a ring together with the sulfur atom in the formula, the formed ring is preferably a 3 to 10 membered ring including the sulfur atom, and 5 to 7 It is more preferable that it is a ring. The ring to be formed may be a polycyclic ring, and it is preferable that it is the polycyclic ring which 5-7 membered ring condensed.

In said formula (a1), it is preferable that both R< ¹ > and R< ² > are a phenyl group.

In the formula (a1), R ³ is preferably a group represented by the formula (a3).

In the formula (a1), A ¹ is preferably S or O, and more preferably S.

In the formula (a2), R ⁴ is preferably an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an optionally substituted amino group, or a nitro group. , an alkyl group optionally substituted with a halogen atom, an alkylcarbonyl group, or a thienylcarbonyl group is more preferable.

In the formula (a2), m1 can be selected according to the type of ring Z ¹ , for example, an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 The following integers may be sufficient.

In the formula (a3), R ⁵ is an alkylene group; an alkylene group substituted with a hydroxyl group, an optionally substituted amino group, or a nitro group; Or it is preferable that it is group represented by the said Formula (a5), and it is more preferable that it is group represented by the said Formula (a5).

In the formula (a3), R ⁶ is an alkyl group; an alkyl group substituted with a hydroxyl group, an optionally substituted amino group, or a nitro group; Or it is preferable that it is group represented by the said Formula (a6), and it is more preferable that it is group represented by the said Formula (a6).

In the formula (a3), A ² is preferably S or O, more preferably S.

In the formula (a3), n1 is preferably 0.

In Formula (a4), R ⁷ and R ⁸ are independently an alkylene group; an alkylene group substituted with a hydroxyl group, an optionally substituted amino group, or a nitro group; Or it is preferable that it is group represented by the said Formula (a5), and it is more preferable that it is group represented by the said Formula (a5). R ⁷ and R ⁸ may be the same as or different from each other.

In the formula (a4), it is preferable that both R ⁹ and R ¹⁰ are groups represented by the formula (a2). R ⁹ and R ¹⁰ may be the same as or different from each other.

In the formula (a4), when R ⁹ and R ¹⁰ combine with each other to form a ring together with a sulfur atom in the formula, the formed ring is preferably a 3 to 10 membered ring including a sulfur atom, and 5 to 7 It is more preferable that it is a ring. The ring to be formed may be a polycyclic ring, and it is preferable that it is the polycyclic ring which 5-7 membered ring condensed.

In the formula (a4), A ³ is preferably S or O, and more preferably S.

In the formula (a4), n2 is preferably 0.

In the formula (a5), R ¹¹ is preferably an alkyl group, hydroxy group, optionally substituted amino group, or nitro group which may be substituted with a halogen atom, and more preferably an alkyl group which may be substituted with a halogen atom.

In the formula (a5), m2 can be selected according to the type of ring Z ² , for example, an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 The following integers may be sufficient.

In the formula (a6), R ¹² is preferably an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, an optionally substituted amino group, or a nitro group. , an alkyl group optionally substituted with a halogen atom, an alkylcarbonyl group, or a thienylcarbonyl group is more preferable.

In the formula (a6), m3 can be selected according to the type of ring Z ³ , for example, an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 The following integers may be sufficient.

The counter anion of the cation moiety represented by the formula (a1) is 1 corresponding to an acid generated by irradiating an active energy ray (visible light, ultraviolet light, electron beam, X-ray, etc.) to a sulfonium salt having a cation moiety represented by formula (a1) is an anion of As a counter anion of the cation part represented by Formula (a1), the anion part represented by the said Formula (aii), and the anion part represented by Formula (aiii) are mentioned suitably. Moreover, as a counter anion of the cation part represented by Formula (a1), other monovalent|monohydric polyatomic anions are also mentioned suitably, MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- An anion represented by , R ^x1 _c GaY _4-c ^- , R ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ₃ C ^- , or (R ^x2 SO ₂ ) ₂ N ^- is more preferable. In addition, the counter anion of the cation part represented by Formula (a1) may be a halogen anion, For example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc. are mentioned.

M represents a phosphorus atom, a boron atom, or an antimony atom.

Y represents a halogen atom (a fluorine atom is preferable).

Rf represents an alkyl group (preferably an alkyl group having 1 or more and 8 or less carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group represented by Rf by fluorine substitution include straight-chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl and octyl, etc.), branched-chain alkyl groups (isopropyl, isobutyl, sec-butyl and tert-butyl, etc.) and cycloalkyl groups ( cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl); The ratio in which hydrogen atoms of these alkyl groups are substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably based on the number of moles of hydrogen atoms in the original alkyl group. is 100 mol%. When the substitution ratio by a fluorine atom exists in these preferable ranges, the photosensitivity of a sulfonium salt (Q) becomes more favorable. Particularly preferred Rf is CF ₃ ^- , CF ₃ CF ₂ ^- , (CF ₃ ) ₂ CF ^- , CF ₃ CF ₂ CF ₂ ^- , CF ₃ CF ₂ CF ₂ CF ₂ ^- , (CF ₃ ) ₂ CFCF ₂ ^- , CF ₃ CF ₂ (CF ₃ )CF ^— and (CF ₃ ) ₃ C ^— . The b pieces of Rf are independent of each other and, therefore, may be the same as or different from each other.

P represents a phosphorus atom and F represents a fluorine atom.

R ^x1 represents a phenyl group in which a part of hydrogen atoms are substituted with at least one element or an electron group. A halogen atom is contained as an example of such one element, A fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Among these, a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. c pieces of R ^x1 are independent of each other and, therefore, may be the same as or different from each other.

B represents a boron atom, Ga represents a gallium atom.

R ^x2 represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group and the fluoroalkyl group are linear, branched or Cyclic any may be sufficient, and even if an alkyl group, a fluoroalkyl group, or an aryl group is unsubstituted, it may have a substituent. Examples of the substituent include a hydroxyl group, an amino group which may be substituted (for example, groups exemplified in the following description of the formulas (a2) to (a6) above.), a nitro group, and the like. have.

In addition, the carbon chain in the alkyl group, fluoroalkyl group, or aryl group represented by R ^x2 may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom. In particular, the carbon chain in the alkyl group or fluoroalkyl group represented by R ^x2 is a divalent functional group (eg, an ether bond, a carbonyl bond, an ester bond, an amino bond, an amide bond, an imide bond, a sulfonyl bond, It may have a sulfonylamide bond, a sulfonylimide bond, a urethane bond, etc.).

When the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 has the above substituent, hetero atom, or functional group, the number of the substituent, hetero atom, or functional group may be one or two or more.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.

a represents an integer of 4 or more and 6 or less.

b is preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, particularly preferably 2 or 3.

As for c, an integer of 1 or more and 4 or less is preferable, More preferably, it is 4.

Examples of the anion represented by MY _a ^- include an anion represented by SbF ₆ ^- , PF ₆ ^- or BF ₄ ^- .

As an anion represented by (Rf) _b PF _6-b ^- , (CF ₃ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₂ PF ₄ ^- , ( (CF ₃ ) ₂ CF) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^- can be heard Among them, (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₂ PF An anion represented by ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- is preferred.

As the anion represented by R ^x1 _c BY _4-c ^- , preferably

R ^x1 _c BY _4-c ^-

(Wherein, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron group, Y represents a halogen atom, and c represents an integer of 1 or more and 4 or less.)

and, for example, (C ₆ F ₅ ) ₄ B ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ and an anion represented by BF ₂ ^- , C ₆ F ₅ BF ₃ ^- or (C ₆ H ₃ F ₂ ) ₄ B ^- . Among these, the anion represented by (C ₆ F ₅ ) ₄ B ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- is preferable.

As an anion represented by R ^x1 _c GaY _4-c ^- , (C ₆ F ₅ ) ₄ Ga ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- , (CF ₃ C ₆ H ₄ ) ₄ Ga ^- , and an anion represented by (C ₆ F ₅ ) ₂ GaF ₂ ⁻ , C ₆ F ₅ GaF ₃ ⁻ or (C ₆ H ₃ F ₂ ) ₄ Ga ⁻ . Among these, the anion represented by (C ₆ F ₅ ) ₄ Ga ⁻ or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ is preferable.

Examples of the anion represented by R ^{x 2} SO ₃ ⁻ include trifluoromethane sulfonic acid anion, pentafluoroethane sulfonic acid anion, heptafluoropropane sulfonic acid anion, nonafluorobutane sulfonic acid anion, pentafluorophenyl sulfonic acid anion, p-toluene sulfonic acid anion, benzene sulfonic acid anion, camphor sulfonic acid anion, methane sulfonic acid anion, ethane sulfonic acid anion, propane sulfonic acid anion, butane sulfonic acid anion, and the like. Of these, preferred are trifluoromethane sulfonic acid anion, nonafluorobutane sulfonic acid anion, methane sulfonic acid anion, butane sulfonic acid anion, camphor sulfonic acid anion, benzene sulfonic acid anion or p-toluene sulfonic acid anion.

As an anion represented by (R ^x2 SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₃ F ₇ SO ₂ ) ₃ C ^- or (C and an anion represented by ₄ F ₉ SO ₂ ) ₃ C ⁻ .

As an anion represented by (R ^x2 SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- or (C an anion represented by ₄ F ₉ SO ₂ ) ₂ N ⁻ and the like.

As monovalent polyatomic anions, MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x1 _c GaY _4-c ^- , R ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ) ₃ C ^- or (R ^x2 SO ₂ ) ₂ N ^- In addition to the anion, perhalogenate ions (ClO ₄ ^- , BrO ₄ ^- , etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^- etc.), sulfuric acid ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^- etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^- etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^- etc.), hexa Fluorobismuth ion (BiF ₆ ^- ), Carboxylic acid ion (CH ₃ COO ^- , CF ₃ COO ^- , C ₆ H ₅ COO ^- , CH ₃ C ₆ H ₄ COO ^- , C ₆ F ₅ COO ^- , CF ₃ C ₆ H ₄ COO ^- etc.), aryl borate ion (B(C ₆ H ₅ ) ₄ ^- , CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ^- etc.), thiocyanate ion (SCN ^- ) and nitrate ions (NO ₃ ⁻ ) and the like.

Among these anions, in terms of cationic polymerization performance, MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x1 _c GaY _4-c ^- and (R ^x2 SO ₂ ) ₃ An anion represented by C ^- is preferred, and SbF ₆ ^- , PF ₆ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (C ₆ F ₅ ) ₄ B ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ and (CF ₃ SO ₂ ) ₃ C ⁻ are more preferable, and R ^x1 _c BY _4-c ⁻ is more preferable.

In the formulas (a2), (a5), and (a6), examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (such as a naphthalene ring) Condensed 2 to 4 rings such as C _8-20 condensed bicyclic hydrocarbon ring, preferably C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) aromatic hydrocarbon ring] and the like. It is preferable that it is a benzene ring or a naphthalene ring, and, as for an aromatic hydrocarbon ring, it is more preferable that it is a benzene ring.

In the formulas (a1) to (a6), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the formulas (a1) to (a6), examples of the alkyl group include a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl, etc.), a branched chain alkyl group having 3 or more and 18 or less carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, iso pentyl, neopentyl, tert-pentyl, isohexyl, and isooctadecyl, etc.), and a cycloalkyl group having 3 or more and 18 or less carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl) etc.) and the like. In particular, in the formulas (a1), (a2), and (a4) to (a6), the alkyl group optionally substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. Examples of the alkyl group substituted with a halogen atom include a group in which at least one hydrogen atom in the aforementioned straight chain alkyl group, branched chain alkyl group, or cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, trifluoromethyl, etc.) and the like. Of the alkyl groups which may be substituted with a halogen atom, for R ¹ , R ² , R ⁹ , or R ¹⁰ , a trifluoromethyl group is particularly preferable, and for R ⁴ , R ⁶ , R ¹¹ , or R ¹² , a methyl group is Especially preferred.

In the formulas (a2) to (a6), the alkoxy group is a linear or branched chain alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy) and the like).

In the formulas (a2) to (a6), as the alkyl group in the alkylcarbonyl group, the aforementioned linear alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, or 3 to 18 carbon atoms The following cycloalkyl groups are mentioned, As an alkylcarbonyl group, a C2-C18 linear, branched or cyclic alkylcarbonyl group (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2 -methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl group, and cyclohexanoyl group) etc. are mentioned.

In the formulas (a3) to (a6), examples of the arylcarbonyl group include an arylcarbonyl group having 7 or more and 11 or less carbon atoms (such as benzoyl and naphthoyl).

In the formulas (a2) to (a6), as the alkoxycarbonyl group, a linear or branched alkoxycarbonyl group having 2 or more and 19 or less carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl) carbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl); can

In the formulas (a3) to (a6), examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 or more and 11 or less carbon atoms (phenoxycarbonyl, naphthoxycarbonyl, etc.).

In the formulas (a3) to (a6), examples of the arylthiocarbonyl group include an arylthiocarbonyl group having 7 or more and 11 or less carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

In the formulas (a2) to (a6), as the acyloxy group, a linear or branched acyloxy group having 2 or more and 19 or less carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyl) oxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy); have.

In the formulas (a3) to (a6), as the arylthio group, an arylthio group having 6 or more and 20 or less carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chloro Phenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[ 4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4 -benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- ( 4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio, 4- (p-isopropyl benzoyl) phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio).

In the formulas (a2) to (a6), the alkylthio group is a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, iso butylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio); have.

In the formulas (a3) to (a6), examples of the aryl group include an aryl group having 6 or more and 10 or less carbon atoms (phenyl, tolyl, dimethylphenyl, naphthyl, etc.).

In the formula (a2), as the heterocyclic aliphatic hydrocarbon group, a heterocyclic hydrocarbon group having 2 or more and 20 or less (preferably 4 or more and 20 or less) carbon atoms (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl) , piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.).

In the formulas (a3) to (a6), as the heterocyclic hydrocarbon group, a heterocyclic hydrocarbon group having 4 or more and 20 or less carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrryl, oxazolyl, Thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxarinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxadinyl, phenoxathynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl); can

In the formulas (a3) to (a6), examples of the aryloxy group include an aryloxy group having 6 or more and 10 or less carbon atoms (phenoxy, naphthyloxy, etc.).

In the formulas (a2) to (a6), as the alkylsulfinyl group, a linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butyl sulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl etc.) and the like.

In the formulas (a3) to (a6), examples of the arylsulfinyl group include an arylsulfinyl group having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

In the formulas (a2) to (a6), the alkylsulfonyl group is a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, Butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, and octadecylsulfonyl etc.) and the like.

In the formulas (a3) to (a6), examples of the arylsulfonyl group include an arylsulfonyl group having 6 to 10 carbon atoms (phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc.) can

In the formulas (a2) to (a6), the hydroxy (poly) alkyleneoxy group is HO (AO) _q ^- (wherein AO independently represents an ethyleneoxy group and/or a propyleneoxy group, and q is 1 The hydroxy (poly) alkyleneoxy group etc. represented by the above 5 or less are shown.) are mentioned.

In the formulas (a2) to (a6), the optionally substituted amino group is an amino group (-NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, methylethylamino, Diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenyl amino, ethylphenylamino, n-propylphenylamino, and isopropylphenylamino);

In the formulas (a3) and (a4), the alkylene group is a linear or branched alkylene group having 1 to 18 carbon atoms (methylene group, 1,2-ethylene group, 1,1-ethylene group, propane- 1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group Diyl, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1 ,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, 2-ethylhexane-1,6-diyl group, nonane-1,9 -diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14- diyl group, pentadecane-1,15-diyl group, and hexadecane-1,16-diyl group);

The sulfonium salt which has a cation part represented by Formula (a1) can be synthesize|combined according to the following scheme, for example. Specifically, 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) is reacted with a compound represented by the following formula (b2) in the presence of a base such as potassium hydroxide, and the following formula (b2) is A nitro compound represented by b3) is obtained, followed by reduction in the presence of reduced iron to obtain an amine compound represented by the following formula (b4). This amine compound is reacted with a nitrite salt (for example, sodium nitrite) represented by MaNO ₂ (wherein Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom) to obtain a diazo compound , then, this diazo compound and the cuprous halide represented by CuX' (wherein, X' represents a halogen atom such as a bromine atom. Hereinafter, the same) and a hydrogen halide represented by HX' are mixed, and the reaction is carried out. It proceeds to obtain a halide represented by the following formula (b5). A Grignard reagent is prepared from this halide and magnesium, and then, this Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) in the presence of chlorotrimethylsilane, and represented by the following formula (b7) A sulfonium salt can be obtained. Further, this sulfonium salt is mixed with Mb ⁺ X" ^- (wherein, Mb ⁺ represents a metal cation, for example, an alkali metal cation such as a potassium ion, and X" ^- represents a monovalent anion represented by X ^- (provided that A sulfonium salt represented by the following formula (b8) can be obtained by reacting with a salt represented by the formula (b8). In addition, in the following formulas (b2) to (b8), R ¹ to R ³ and A ¹ are the same as in the formula (a1).

<Scheme>

Specific examples of the cation moiety represented by the formula (a1) include the following cation moieties. As a specific example of the anion part with respect to the cation part represented by said formula (a1), conventionally well-known anion parts, such as the anion part mentioned above, are mentioned. A sulfonium salt having a cationic moiety represented by the formula (a1) can be synthesized according to the above scheme (in the scheme, X ⁻ represents a counter anion), and additionally salt exchanged as necessary to form a cation moiety with a desired anion moiety. It can be combined, and especially the combination of the anion represented by the anion part represented by the said formula (aii) or the anion part represented by said formula (aiii) is preferable.

In the group of the above preferred cation moieties, a cation moiety represented by the following formula is more preferred.

[Thermal acid generator (A2)]

The thermal acid generator (A2) is an onium salt having an anion moiety represented by the following formula (Ai).

(R ^A1 ) ₄ -Ga ^- ... (Ai)

(In formula (Ai), R ^A1 is each independently a phenyl group which may have one or more substituents, or a perfluoroalkyl group.)

Four R ^A1 in formula (Ai) are a phenyl group which may have one or more substituents, or a perfluoroalkyl group. When R ^A1 is a phenyl group, the substituent that the phenyl group may have is not particularly limited as long as the object of the present invention is not impaired. Suitable examples of the substituent which the phenyl group may have include a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group, and a halogen atom.

When the phenyl group as R ^A1 has a plurality of substituents, the plurality of substituents may be the same or different.

1 or more and 8 or less are preferable and, as for the number of carbon atoms of the perfluoroalkyl group as a substituent on a phenyl group, 1 or more and 4 or less are more preferable.

Specific examples of the perfluoroalkyl group as a substituent on the phenyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluoropentyl group, and a straight-chain purple group such as a perfluorooctyl group. Branched chain perfluoroalkyl groups such as luoroalkyl group, heptafluoroisopropyl group, nonafluoroisobutyl group, nonafluoro-sec-butyl group, and nonafluoro-tert-butyl group, perfluoro Perfluorocycloalkyl groups, such as a cyclopropyl group, a perfluorocyclobutyl group, a perfluorocyclopentyl group, and a perfluorocyclohexyl group, are mentioned.

1 or more and 8 or less are preferable and, as for the number of carbon atoms of the perfluoroalkoxy group as a substituent on a phenyl group, 1 or more and 4 or less are more preferable.

Specific examples of the perfluoroalkoxy group as a substituent on the phenyl group include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropyloxy group, a nonafluorobutyloxy group, a perfluoropentyloxy group, and a perfluoro A straight-chain perfluoroalkoxy group such as a rooctyloxy group, a heptafluoroisopropyloxy group, a nonafluoroisobutyloxy group, a nonafluoro-sec-butyloxy group, and a nonafluoro-tert-butyloxy group, etc. and branched chain perfluoroalkoxy.

Examples of the halogen atom as a substituent on the phenyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When R ^A1 is a perfluoroalkyl group, suitable examples of the perfluoroalkyl group are the same as the specific examples of the perfluoroalkyl group as a substituent on the phenyl group.

From the point of the cationic polymerization performance of the thermal acid generator (A2), it is preferable that at least one of R ^A1 is a phenyl group substituted with one or more groups selected from the group consisting of a perfluoroalkyl group and a fluorine atom, and all of R ^A1 are It is more preferable that it is a phenyl group substituted with a perfluoroalkyl group and at least one group selected from the group consisting of a fluorine atom.

Suitable examples of R ^A1 include pentafluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, (trifluoromethyl)phenyl group, bis(trifluoromethyl)phenyl group, (pentafluoroethyl)phenyl group, bis(pentafluoro Roethyl) phenyl group, fluoro (trifluoromethyl) phenyl group, fluorobis (trifluoromethyl) phenyl group, fluoro (pentafluoroethyl) phenyl group, fluorobis (pentafluoroethyl) phenyl group, pentachlorophenyl group , trichlorophenyl group, tetrachlorophenyl group, (trichloromethyl) phenyl group, bis (trichloromethyl) phenyl group, (pentachloroethyl) phenyl group, bis (pentachloroethyl) phenyl group, chloro (trichloromethyl) phenyl group, chloro bis ( trichloromethyl) phenyl group, chloro (pentachloroethyl) phenyl group, chlorobis (pentachloroethyl) phenyl group, nitrophenyl group, cyanophenyl group, and acetylphenyl group.

Among these, a pentafluorophenyl group and a bis(trifluoromethyl)phenyl group are preferable, and a pentafluorophenyl group is more preferable.

The following anions are mentioned as a suitable specific example of the anion part represented by Formula (Ai).

As the cation moiety constituting the onium salt as the thermal acid generator (A2) together with the anion moiety represented by the above formula (Ai), a cation moiety represented by the following formula (Aii) is preferable.

(In formula (Aii), R ^A01 is a monovalent organic group, D is an element of valence u in Groups 15 to 17 of the Periodic Table of Elements (IUPAC notation), and R ^A02 is an alkyl group which may have a substituent or optionally aralkyl group.However, when R ^A02 is optionally substituted alkyl group, at least one of R ^A01 is optionally substituted alkyl group.u is an integer of 1 or more and 3 or less, and a plurality of of R ^A01 may be the same or different, and a plurality of R ^A01 may be bonded to form a ring together with D.)

D in the formula (Aii) is an element with a valency u in Groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation). Incidentally, D is the same as R ^a02 in the above formula (ai).

D combines with an organic group R ^A01 and a benzyl group optionally substituted with R ^A02 to form an onium ion. Among the elements of Groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation), S (sulfur), N (nitrogen), I (iodine), and P (phosphorus) are preferable. Corresponding onium ions are sulfonium ions, ammonium ions, iodonium ions, and phosphonium ions, and these are preferable because they are stable and easy to handle. A sulfonium ion and an iodonium ion are more preferable, and a sulfonium ion is still more preferable at the point excellent in cationic polymerization performance and crosslinking reaction performance.

In formula (Aii), R ^A01 represents the organic group couple|bonded with D, and when two or more R ^A01 exists, several R ^A01 may be same or different. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable. Examples of R ^A01 include an aromatic hydrocarbon group having 6 to 14 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an alkynyl group having 2 to 18 carbon atoms. can

Examples of the aromatic hydrocarbon group, alkyl group, alkenyl group, and alkynyl group as R ^A01 include the same groups as those described above for R ^a1 in formula (ai). When R ^A01 is an aromatic hydrocarbon group, it may have a substituent, and examples of the substituent include a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, and an alkylti group. Group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly)alkyleneoxy group, optionally substituted silyl group, optionally substituted An amino group, a halogen atom, etc. are mentioned.

In addition, in Formula (Aii), when two or more R ^A01 exists, some R ^A01 may form a ring together with D. The ring formed by a plurality of R ^A01 and D is, in the structure between them, -O-, -S-, -SO-, -SO ₂ -, -NH-, -CO-, -COO-, and -CONH- It may contain one or more bonds selected from the group consisting of.

Specific examples of the alkyl group as R ^A02 in formula (Aii) include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-octyl group, n-decyl group, n-dodecyl group, n- A straight-chain alkyl group having 1 to 18 carbon atoms such as tetradecyl group, n-hexadecyl group and n-octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, Branched chain alkyl groups having 3 to 18 carbon atoms, such as neopentyl group, tert-pentyl group, isohexyl group and isooctadecyl group, and cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and 4 -C 3 -C 18 cycloalkyl groups, such as a decyl cyclohexyl group, etc. are mentioned. In the formula (Aii), when R ^A02 is an optionally substituted alkyl group, at least one of R ^A01 is an optionally substituted alkyl group.

In the formula (Aii), specific examples of the aralkyl group as R ^A02 include a lower alkyl group substituted with an aryl group having 6 to 10 carbon atoms, such as a benzyl group, 1-naphthylmethyl group, and 2-naphthylmethyl group. can

Specific examples of the aralkyl group having a substituent as R ^A02 in the formula (Aii) include a lower alkyl group substituted with an aryl group having 6 to 10 carbon atoms which may have a substituent, such as a 2-methylbenzyl group. have.

In the formula (Aii), R ^A02 is preferably an aralkyl group which may have a substituent, and more preferably a cation moiety represented by the following formula (Aiii).

(in formula (Aiii), R ^A01 is a monovalent organic group, D is an element of valence u of Groups 15 to 17 of the Periodic Table of the Elements according to IUPAC notation, R ^A03 is a monovalent organic group, u is an integer of 1 or more and 3 or less, and v is an integer of 0 or more and 5 or less.)

In the formula (Aiii), the monovalent organic group of R ^A03 is preferably a carbon atom-containing group, selected from the group consisting of one or more carbon atoms and H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of one or more selected atoms is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and 1 or more and 50 or less are preferable, and 1 or more and 20 or less are more preferable. The monovalent organic group of R ^A03 is particularly preferably an alkyl group. Examples of the alkyl group as R ^A03 include the same groups as the alkyl group represented by R ^A02 in the formula (Aii). V is preferably 0 or 1. As described for the formula (Aii), it is preferable that D is sulfur and the cation represented by the formula (Aiii) is a sulfonium ion. That is, it is preferable that D is sulfur and u is 2.

The specific example of the cation part represented by Formula (Aii) or Formula (Aiii) is given. D' in the following specific example is an S atom or a Se atom, Preferably it is an S atom.

The content of the cationic curing agent (A) in the curable composition is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the cation-curable compound (B) from the viewpoint of balance between curability and physical properties of the cured product, , 0.05 parts by mass or more and 3 parts by mass or less are more preferable, and 0.1 parts by mass or more and 2 parts by mass or less are particularly preferable.

In addition, the cationic curing agent (A) may contain cationic curing agents other than a photo-acid generator (A1) and a thermal acid generator (A2) in the range which does not impair the objective of this invention. The ratio of the sum of the mass of the photo-acid generator (A1) and the mass of the thermal acid generator (A2) to the mass of the cationic curing agent (A) is preferably 70 mass% or more, more preferably 80 mass% or more, 90 mass % or more is more preferable, and 100 mass % is especially preferable.

In addition, since it is easier to suppress the coloring of the cured product during curing, the ratio of the mass of the photo-acid generator (A1) to the sum of the mass of the photo-acid generator (A1) and the mass of the thermal acid generator (A2) is, 50 mass % or less is preferable, and 30 mass % or less is more preferable. Although a lower limit is not specifically limited, From the point of chemical-resistance and a process margin, 10 mass % or more is preferable, 15 mass % or more is more preferable, 20 mass % or more is still more preferable.

<Cation-curable compound (B)>

As a cation-curable compound (B), the various compound conventionally known as a cation-curable compound can be used. By hardening a cation-curable compound (B) with the above-mentioned cationic curing agent (A), the hardened|cured material excellent in solvent resistance hardened|cured favorably can be formed, and the coloring in hardened|cured material can be suppressed.

As an example of a preferable cation-curable compound, the compound represented by a following formula (b1) is mentioned.

(in formula (b1), W ¹ and W ² are each independently the following formula (b2):

is a group represented by

In formula (b2), ring Z represents an aromatic hydrocarbon ring, X ^B represents a single bond or a group represented by -S-, R ^B1 represents a single bond, an alkylene group having 1 to 4 carbon atoms, or 1 carbon atom represents an alkyleneoxy group of 4 or less, and when R ^B1 is an alkyleneoxy group, an oxygen atom in the alkyleneoxy group is bonded to ring Z, and R ^B2 is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , -SR ^4b A group represented by, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxy group, an amino group, a carbamoyl group, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a sulfo group , or a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a carbon atom contained in the group represented by -N(R ^4d ) ₂ At least a part of the hydrogen atoms bonded thereto is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxy group, an amino group, a carbamoyl group, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a mesyloxy group, or a group substituted with a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, m represents an integer of 0 or more, R ³ is a hydrogen atom, a vinyl group, a tyran-2-yl methyl group, or a glycidyl group,

Both of W ¹ and W ² do not have a hydrogen atom as R ³ ,

ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms; a group represented by -O-, a group represented by -NH-, or a group represented by -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, n1 and n2 are independently It represents an integer of 0 or more and 4 or less.)

In the formula (b2), as ring Z, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C _8-20 condensed 2 Condensed 2 to 4 cyclic aromatic hydrocarbon rings such as a cyclic hydrocarbon ring, preferably a C _10-16 condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) can be heard It is preferable that it is a benzene ring or a naphthalene ring, and, as for ring Z, it is more preferable that it is a naphthalene ring. Incidentally, since W ¹ and W ² in the formula (b1) are each independently a group represented by the following formula (b2), W ¹ and W ² each include a ring Z. The ring Z contained in W ¹ and the ring Z contained in W ² may be the same or different, for example, one ring may be a benzene ring, the other ring may be a naphthalene ring, etc. However, it is particularly preferable that any ring is a naphthalene ring. do.

In addition, the substitution position of the ring Z couple|bonded with X ^B to the carbon atom which both of W< ¹ > and W< ² > couple|connected directly is not specifically limited. For example, when ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.

In the formula (b2), X ^B independently represents a single bond or a group represented by -S-, and is typically a single bond.

In the formula (b2), as R ^B1 , for example, a single bond; The number of carbon atoms, such as a methylene group, an ethylene group, a trimethylene group (-CH ₂ CH ₂ CH ₂ -), a propylene group (-CH ₂ CH(CH ₃ )-), a butane-1,2-diyl group, is 1 or more 4 the following alkylene groups; C1-C4 alkyleneoxy groups, such as a methyleneoxy group, an ethyleneoxy group, and a propyleneoxy group ( _{-CH2CH (} CH3)-O-), are mentioned, Single bond; C _2-4 alkylene group (especially, C _2-3 alkylene group such as ethylene group or propylene group); A C _2-4 alkyleneoxy group (particularly, a C _2-3 alkyleneoxy group such as an ethyleneoxy group or a propyleneoxy group) is preferable, and a single bond is more preferable. Incidentally, when R ^B1 is an alkyleneoxy group, an oxygen atom in the alkyleneoxy group is bonded to the ring Z. In addition, since W ¹ and W ² in Formula (b1) are each independently a group represented by Formula (b2), W ¹ and W ² each include R ^B1 which is a divalent group. R ^B1 contained in W ¹ and RB ¹ contained in W ² may be the same or different.

In the formula ( ^b2 ), as RB2, for example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably C _1-8 An alkyl group, more preferably a C _1-6 alkyl group, etc.), a cycloalkyl group (a C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group, etc.) ), an aryl group (for example, a C _6-14 aryl group such as a phenyl group, tolyl group, xylyl group, or naphthyl group, preferably a C _6-10 aryl group, more preferably a C _6-8 aryl group, etc.) , monovalent hydrocarbon groups such as aralkyl groups (C _6-10 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups); hydroxyl group; Alkoxy group (C _1-12 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc.), cycloalkoxy group (C _5-10 cycloalkoxy group such as cyclohexyloxy group), aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (eg, C _6- such as benzyloxy group) a group represented by -OR ^4a such as ₁₀ aryl-C _1-4 alkyloxy group) [wherein R ^4a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group in the above example)]; An alkylthio group (a C _1-12 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group group), a cycloalkylthio group (such as a C _5-10 cycloalkylthio group such as a cyclohexylthio group), an arylthio group (such as a C _6-10 arylthio group such as a phenylthio group), an aralkylthio group (eg For example, a group represented by -SR ^4b such as a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group [wherein R ^4b is a monovalent hydrocarbon group (monovalent hydrocarbon group in the example above) indicates.]; acyl groups (such as C _1-6 acyl groups such as acetyl groups); an alkoxycarbonyl group (such as a C _1-4 alkoxycarbonyl group such as a methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; An alkyl amino group (such as a methyl amino group, an ethyl amino group, a propyl amino group or a butyl amino group, preferably a C _1-8 alkyl amino group, more preferably _{a C 1-6 alkyl} amino group, etc.), a cycloalkyl amino group ( C _5-10 cycloalkyl amino group such as cyclohexyl amino group, etc.), arylamino group (C _6-10 aryl amino group such as phenyl amino group), aralkyl amino group (eg, C _6-10 aryl-C ₁ such as benzyl amino group) a group represented by -NHR ^4c such as _-4 alkylamino group [wherein R ^4c represents a monovalent hydrocarbon group (monovalent hydrocarbon group in the example above); A di(C _1-12 alkyl) amino group, such as a dialkyl amino group (dimethyl amino group, diethyl amino group, dipropyl amino group, dibutyl amino group, etc., preferably a di (C _1-8 alkyl) amino group, more preferably a di (C _1-6 alkyl) amino group, etc.), dicycloalkyl amino group (di (C _5-10 cycloalkyl) amino group, such as dicyclohexyl amino group, etc.), diaryl amino group (di (C _6-10 aryl, such as diphenyl amino group) A group represented by -N(R ^4d ) ₂ such as an amino group), a diaralkylamino group (eg, a di(C _6-10 aryl-C _1-4 alkyl) amino group such as a dibenzyl amino group) [wherein R ^4d independently represents a monovalent hydrocarbon group (monovalent hydrocarbon group in the above example, etc.); (meth)acryloyloxy group; sulfo group; At a carbon atom contained in the above monovalent hydrocarbon group, the group represented by -OR ^4a , the group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, the group represented by -NHR ^4c , or the group represented by -N(R ^4d ) ₂ At least a part of the hydrogen atoms bonded thereto is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxy group, A group substituted with an amino group, a carbamoyl group, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a mesyloxy group, or a sulfo group [eg, alkoxy aryl group (eg, a C _1-4 alkoxy C _6-10 aryl group such as a methoxy phenyl group), an alkoxy carbonyl aryl group (eg, a C _{1 - 4} alkoxy carbonyl C _6-10 aryl group, etc.)] and the like.

Among these, representatively, ^RB2 is a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, or a group represented by -NHR ^4c group, a group represented by -N(R ^4d ) ₂ , etc. may be sufficient.

Preferred ^RB2 is a monovalent hydrocarbon group [eg, an alkyl group (eg, C _1-6 alkyl group), a cycloalkyl group (eg, C _5-8 cycloalkyl group), an aryl group (eg, C _6-10 aryl group), aralkyl group (eg, C _6-8 aryl-C _1-2 alkyl group)], alkoxy group (C _1-4 alkoxy group, etc.). In particular, R ^2a and R ^2b are monovalent hydrocarbon groups (especially, such as an alkyl group [C _1-4 alkyl group (especially methyl group) etc.], aryl group [eg, C _6-10 aryl group (especially phenyl group) etc.] , an alkyl group) is preferable.

In addition, when m is an integer of 2 or more, some R ^B2 may mutually differ and may be same. ^In addition, ^RB2 contained in W1 ^{and RB2} contained in W2 may be same or different.

In the formula (b2), the number m of R ^B2 can be selected according to the type of ring Z, for example, 0 or more and 4 or less, preferably 0 or more and 3 or less, More preferably 0 or more and 2 or less may be In addition, ^m in W1 and ^m in W2 may be same or different.

In the formula (a3), R ³ is a hydrogen atom, a vinyl group, a tyran-2-ylmethyl group, or a glycidyl group. Incidentally, both of W ¹ and W ² do not have a hydrogen atom as R ³ .

A vinyloxy group, a thiran-2-yl methyl group, and a glycidyl group are all cationically polymerizable functional groups. Therefore, the compound represented by Formula (b1) is a cationically polymerizable compound which has the cationically polymerizable functional group of 1 or 2.

R ³ contained in W ¹ and R ³ contained in W ² may be the same or different as long as both are not hydrogen atoms. R ³ contained in W ¹ and R ³ contained in W ² are preferably a vinyl group, a tyran-2-yl methyl group, or a glycidyl group, and both of them are a vinyl group, tyran-2-yl It is more preferable that it is the same group selected from the group which consists of a methyl group and a glycidyl group.

As R< ³ >, since the synthesis|combination and acquisition of the compound represented by Formula (b1) are easy, a vinyl group or a glycidyl group is preferable.

In the formula (b1), as ring Y ¹ and ring Y ² , for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C such as a naphthalene ring) Condensed 2 to 4 cyclic aromatics such as _8-20 condensed bicyclic hydrocarbon ring, preferably C _10-16 condensed bicyclic hydrocarbon ring) and condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) hydrocarbon ring] and the like. It is preferable that they are a benzene ring or ^a naphthalene ring, and, as ^for ring Y1 and ring Y2, it is more preferable that they are a benzene ring. ^In addition, ring Y1 and ring Y2 may be same or different, for example, ^a benzene ring may be sufficient as one ring, and a naphthalene ring etc. may be sufficient as the other ring.

In the formula (b1), R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, -NH It represents a group represented by - or a group represented by -S-, and is typically a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group) , a C _1-6 alkyl group such as t-butyl group), an aryl group (C _6-10 aryl group such as a phenyl group), etc.], and the hetero atom includes, for example, an oxygen atom, a nitrogen atom, a sulfur An atom, a silicon atom, etc. are mentioned.

In the formula (b1), R ^3a and R ^3b are usually a non-reactive substituent, such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, _. Examples of the alkyl group include C _1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (eg, C _1-4 alkyl group, particularly methyl group). In addition, when n1 is an integer of 2 or more, R ^3a may mutually differ and may be same. In addition, when n2 is an integer of 2 or more, R ^3b may mutually differ and may be same. In addition, R ^3a and R ^3b may be the same or different. In addition, the bonding position (substitution position) of R ^3a and R ^3b with respect to ring Y ¹ and ring Y ² is not specifically limited. Preferred substitution numbers n1 and n2 are 0 or 1, particularly 0. Incidentally, n1 and n2 may be the same as or different from each other.

Since the compound represented by the said Formula (b1) has a cationically polymerizable functional group, maintaining the outstanding optical characteristic and thermal characteristic, it has high reactivity. In particular, when ring Y ¹ and ring Y ² are a benzene ring, and R is a single bond, the compound represented by the formula (b1) has a fluorene skeleton and is further excellent in optical properties and thermal properties.

Furthermore, the compound represented by the said Formula (b1) provides the hardened|cured material which has high hardness, and is preferable as a base material component in a composition.

Among the compounds represented by the formula (b1), particularly preferred specific examples include 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9-bis[4 -[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9,9-bis [4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, 9,9-bis(6-glycidyloxynaphthalen-1-yl)-9H-fluorene and 9,9 Epoxy group-containing fluorene compounds, such as -bis(5-glycidyloxynaphthalen-2-yl)-9H-fluorene; and compounds represented by the following formulas.

Among the compounds represented by formula (b1) described above, the following compounds are particularly preferable.

Preferred examples of the cationically polymerizable compound other than the compound represented by the formula (b1) include a vinyl ether compound containing a vinyloxy group, an epoxy compound containing an epoxy group, and an episulfide compound containing an episulfide group. Hereinafter, a vinyl ether compound, an epoxy compound, and an episulfide compound are demonstrated.

(vinyl ether compound)

The vinyl ether compound as a cation-curable compound (B) other than the compound represented by Formula (b1) has a vinyloxy group, and if it is a compound which can be cationically polymerized, it will not specifically limit.

The vinyl ether compound used together with the compound represented by Formula (b1) may contain an aromatic group, and does not need to contain an aromatic group.

It is preferable that the vinyl ether compound used together with the compound represented by Formula (b1) is a compound which has a vinyloxy group couple|bonded with the aromatic group from the point with favorable thermal decomposition resistance of hardened|cured material.

As suitable specific examples of the vinyl ether compound that can be used together with the compound represented by the formula (b1), vinyl phenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, and 1-vinyloxy-4-chloro Benzene, 1-vinyloxy-3-chlorobenzene, 1-vinyloxy-2-chlorobenzene, 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-dimethylbenzene, 1-vinyloxy -2,5-dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1-vinyloxy-3,5-dimethylbenzene, 1-vinyloxynaphthalene; 2-vinyloxynaphthalene, 2-vinyloxyfluorene, 3-vinyloxyfluorene, 4-vinyloxy-1,1'-biphenyl, 3-vinyloxy-1,1'-biphenyl, 2-vinyloxy aromatic monovinyl ether compounds such as -1,1'-biphenyl, 6-vinyloxytetraline, and 5-vinyloxytetraline; 1,4-divinyloxybenzene, 1,3-divinyloxybenzene, 1,2-divinyloxybenzene, 1,4-divinyloxynaphthalene, 1,3-divinyloxynaphthalene, 1,2-divinyloxybenzene Vinyloxynaphthalene, 1,5-divinyloxynaphthalene, 1,6-divinyloxynaphthalene, 1,7-divinyloxynaphthalene, 1,8-divinyloxynaphthalene, 2,3-divinyloxynaphthalene, 2 ,6-divinyloxynaphthalene, 2,7-divinyloxynaphthalene, 1,2-divinyloxyfluorene, 3,4-divinyloxyfluorene, 2,7-divinyloxyfluorene, 4,4 '-divinyloxybiphenyl, 3,3'-divinyloxybiphenyl, 2,2'-divinyloxybiphenyl, 3,4'-divinyloxybiphenyl, 2,3'-divinyloxybi and aromatic divinyl ether compounds such as phenyl, 2,4'-divinyloxybiphenyl, and bisphenol A divinyl ether.

These vinyl ether compounds may be used in combination of 2 or more types.

(epoxy compound)

Examples of the epoxy compound as the cation-curable compound (B) other than the compound represented by the formula (b1) include a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AD-type epoxy resin, a naphthalene-type epoxy resin, And bifunctional epoxy resins, such as a biphenyl type epoxy resin; novolac epoxy resins such as phenol novolak type epoxy resins, brominated phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, bisphenol A novolak type epoxy resins, and bisphenol AD novolak type epoxy resins; Cyclic aliphatic epoxy resins, such as an epoxide of a dicyclopentadiene type phenol resin; aromatic epoxy resins such as epoxidized products of naphthalene-type phenol resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmethacylylenediamine, and tetraglycidylbisaminomethylcyclohexane; Heterocyclic epoxy resins, such as triglycidyl isocyanurate; Phloroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2-[4-(2,3-epoxypropoxy) phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4-[1-[4-( 2,3-epoxypropoxy) phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy) phenyl]-1-methyl ethyl]phenyl]ethyl]phenoxy]-2-propanol trifunctional epoxy resins such as; tetrafunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl; 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxy methyl)-1-butanol. A 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol is commercially available as EHPE-3150 (manufactured by Daicel Corporation).

Moreover, the polyfunctional epoxy compound of an oligomer or polymer type can also be used suitably as a cation-curable compound (B).

Typical examples include a phenol novolak type epoxy compound, a brominated phenol novolak type epoxy compound, an orthocresol novolak type epoxy compound, a xylenol novolak type epoxy compound, a naphthol novolak type epoxy compound, a bisphenol A novolak type epoxy compound, A bisphenol AD novolak-type epoxy compound, the epoxidized product of a dicyclopentadiene-type phenol resin, the epoxidized product of a naphthalene-type phenol resin, etc. are mentioned.

As another example of a suitable epoxy compound, the polyfunctional alicyclic epoxy compound which has an alicyclic epoxy group is mentioned. When a cation-curable compound (B) contains an alicyclic epoxy compound, it is easy to form the hardened|cured material excellent in transparency using a curable composition.

Specific examples of the alicyclic epoxy compound include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane metadioxane, bis(3,4-epoxycyclohexylmethyl) adipate. , bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε- Caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β -Methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexane) of ethylene glycol -epoxy cyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy cyclohexahydrophthalate dioctyl, and epoxy cyclohexahydrophthalate di2-ethyl hexyl, tricyclodecene oxide group epoxy water In addition, compounds represented by the following formulas (b01-1) to (b01-5) are exemplified.

Among the specific examples of these alicyclic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (b01-1) to (b01-5) are preferable from the viewpoint of providing a cured product with high hardness.

(In formula (b01-1), Z ⁰¹ represents a single bond or a linking group (a divalent group having one or more atoms). R ^b01 to R ^b018 each independently represent a hydrogen atom, a halogen atom, and an organic group. It is a group selected from the group.)

Examples of the linking group Z ⁰¹ include a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, -C( and a divalent group selected from the group consisting of CF ₃ ) ₂ -, and -R ^b019 -O-CO-, and a group in which a plurality of these groups are bonded.

Examples of the divalent hydrocarbon group as the linking group Z ⁰¹ include a linear or branched alkylene group having 1 or more and 18 or less carbon atoms, a divalent alicyclic hydrocarbon group, and the like. As a C1-C18 linear or branched alkylene group, a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, trimethylene group, etc. are mentioned, for example. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, and 1,3-cyclohexylene group. cycloalkylene groups (including a cycloalkylidene group), such as group, 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

R ^b019 is an alkylene group having 1 or more and 8 or less carbon atoms, and is preferably a methylene group or an ethylene group.

(In formula (b01-2), R ^b01 to R ^b018 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^b02 and R ^b010 may be bonded to each other. R ^b013 and R ^b016 may combine with each other to form a ring. m ^b1 is 0 or 1.)

As the alicyclic epoxy compound represented by the formula (b01-2), a compound represented by the following formula (b01-2-1), which corresponds to a compound in which m ^b1 in the formula (b01-2) is 0, is preferable. .

(In formula (b01-2-1), R ^b01 to R ^b012 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^b02 and R ^b010 may combine with each other to form a ring. )

(In formula (b01-3), R ^b01 to R ^b010 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^b02 and R ^b08 may be bonded to each other.)

(In formula (b01-4), R ^b01 to R ^b012 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^b02 and R ^b010 may be bonded to each other.)

(In formula (b01-5), R ^b01 to R ^b012 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

In the formulas (b01-1) to (b01-5), when R ^b01 to R ^b018 are an organic group, the organic group is not particularly limited as long as the object of the present invention is not impaired, and even if it is a hydrocarbon group, a carbon atom and a halogen atom It may be a group consisting of, or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom together with a carbon atom and a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

The organic group is preferably a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, and a group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1 or more and 20 or less are preferable, as for the carbon atom number of an organic group, 1 or more and 10 or less are more preferable, 1 or more and 5 or less are especially preferable.

Specific examples of the hydrocarbon group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexa chain alkyl groups such as decyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; chain alkenyl groups such as a vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group an aryl group such as a group and a phenanthryl group; and aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group.

Specific examples of the halogenated hydrocarbon group include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2, 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, purple halogenated chain alkyl groups such as a luoronyl group and a perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bro halogenated cycloalkyl groups such as a mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, halogenated aryl groups such as 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group and 4-fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3-fluoro halogenated aralkyl groups such as a phenylmethyl group and a 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group chain alkyl group; halogenated cycloalkyl groups such as a 2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group, and a 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-di hydroxyaryl groups such as a hydroxyphenyl group, a 3,4-dihydroxyphenyl group, and a 3,5-dihydroxyphenyl group; hydroxyaralkyl groups such as a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, and a 4-hydroxyphenylmethyl group; Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group Group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyl group chain alkoxy groups such as siloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, and n-icosyloxy group; vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, 3-n-butenyloxy group, etc. a chain alkenyloxy group; Phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, bi aryloxy groups such as phenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group; Methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n -propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, 4-n-propoxy-n-butyl group, etc. alkoxyalkyl group; Methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n- propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and alkoxyalkoxy groups such as 4-n-propoxy-n-butyloxy group; alkoxyaryl groups such as a 2-methoxyphenyl group, a 3-methoxyphenyl group, and a 4-methoxyphenyl group; alkoxyaryloxy groups such as a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group; aliphatic acyl groups such as a formyl group, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, and a decanoyl group; aromatic acyl groups such as a benzoyl group, an α-naphtholyl group, and a β-naphtholyl group; Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and chain alkyloxycarbonyl groups such as n-decyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group, and β-naphthoxycarbonyl group; aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy; aromatic acyloxy groups such as benzoyloxy group, α-naphthoyloxy group, and β-naphthoyloxy group.

R ^b01 to R ^b018 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, particularly mechanical properties Since it is easy to form this excellent cured film, it is more preferable that all of ^Rb01 - ^Rb018 are hydrogen atoms.

In formulas (b01-2) to (b01-5), R ^b01 to R ^b018 are the same as R ^b01 to R ^b018 in formula (b01-1). In the formulas (b01-2) and (b01-4), when R ^b02 and R ^b010 are bonded to each other, in the formula (b01-2), when R ^b013 and R ^b016 are bonded to each other, and In the formula (b01-3), examples of the divalent group formed when R ^b02 and R ^b08 are bonded to each other include -CH ₂ - and -C(CH ₃ ) ₂ -.

Among the alicyclic epoxy compounds represented by formula (b01-1), specific examples of suitable compounds include alicyclic epoxy compounds represented by the following formulas (b01-1a), (b01-1b), and (b01-1c); 2,2-bis(3,4-epoxycyclohexan-1-yl)propane [=2,2-bis(3,4-epoxycyclohexyl)propane] etc. are mentioned.

Among the alicyclic epoxy compounds represented by formula (b01-2), specific examples of suitable compounds include alicyclic epoxy compounds represented by the following formulas (b01-2a) and (b01-2b).

S-spiro[3-oxatricyclo[3.2.1.0 ^2,4 ]octane-6,2'-oxylan] etc. are mentioned as a specific example of a suitable compound among the alicyclic epoxy compounds represented by Formula (b01-3) .

Specific examples of suitable compounds among the alicyclic epoxy compounds represented by formula (b01-4) include 4-vinylcyclohexenedioxide, dipentenedioxide, limonenedioxide, and 1-methyl-4-(3-methyloxylan-2). -yl)-7-oxabicyclo[4.1.0]heptane etc. are mentioned.

Among the alicyclic epoxy compounds represented by Formula (b01-5), 1,2,5,6-diepoxycyclooctane etc. are mentioned as a specific example of a suitable compound.

Furthermore, the compound represented by a following formula (b1-I) can be used suitably as a cation-curable compound (B).

(In formula (b1-I), X ^b1 , X ^b2 , and X ^b3 are each independently a hydrogen atom or an organic group which may contain an epoxy group, and an epoxy group that X ^b1 , X ^b2 , and X ^b3 have The total number of is greater than or equal to 2.)

As the compound represented by the formula (b1-I), a compound represented by the following formula (b1-II) is preferable.

(In formula (b1-II), R ^b20 to R ^b22 are linear, branched or cyclic alkylene group, arylene group, -O-, -C(=O)-, -NH-, and combinations thereof. E ¹ to E ³ are epoxy group, oxetanyl group, ethylenically unsaturated group, alkoxysilyl group, isocyanate group, blocked isocyanate group, thiol group, carboxyl group, hydroxyl group and succinic anhydride At least one substituent or hydrogen atom selected from the group consisting of a group, provided that at least two of E ¹ to E ³ are at least one selected from the group consisting of an epoxy group and an oxetanyl group.)

In the formula (b1-II), at least two of the groups represented by R ^b20 and E ¹ , R ^b21 and E ² , and R ^b22 and E ³ are, for example, groups represented by the following formula (b1-IIa) It is preferable, and it is more preferable that all are groups respectively represented by a following formula (b1-IIa). It is preferable that the groups represented by several formula (b1-IIa) couple|bonded with one compound are the same group.

-LC ^b (b1-IIa)

(In formula (b1-IIa), L is a linear, branched or cyclic alkylene group, arylene group, -O-, -C(=O)-, -NH-, and a group consisting of combinations thereof, C ^b is an epoxy group. In formula (b1-IIa), L and C ^b may combine to form a cyclic structure.)

In the formula (b1-IIa), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is 5 to 10 carbon atoms An arylene group is preferred. In formula (b1-IIa), L is preferably a group consisting of a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C(=O)-, -NH-, and combinations thereof. and at least one of a phenylene group and a linear alkylene group having 1 to 3 carbon atoms, such as a methylene group, or at least one of -O-, -C(=O)-, and NH-; A group consisting of a combination of

In the formula (b1-IIa), when L and C ^b are bonded to form a cyclic structure, for example, a branched alkylene group and an epoxy group are bonded to form a cyclic structure (structure having an alicyclic epoxy group) When forming, organic groups represented by the following formulas (b1-IIb) to (b1-IId) are exemplified.

(In formula (b1-IIb), R ^b23 is a hydrogen atom or a methyl group.)

Hereinafter, although the example of the epoxy compound which has an oxiranyl group or an alicyclic epoxy group is shown as an example of a compound represented by Formula (b1-II), it is not limited to these.

Moreover, the siloxane compound which has two or more glycidyl groups in a molecule|numerator (Hereinafter, it is also simply described as a "siloxane compound.") can be used suitably as a cation-curable compound (B).

A siloxane compound is a compound which has the siloxane skeleton comprised by the siloxane bond (Si-O-Si), and two or more glycidyl groups in a molecule|numerator.

Examples of the siloxane skeleton in the siloxane compound include cyclic siloxane skeleton and cage-type or ladder-type polysilsesquinoxane skeleton.

As the siloxane compound, a compound having a cyclic siloxane skeleton represented by the following formula (b1-III) (hereinafter sometimes referred to as “cyclic siloxane”) is preferable.

In formula (b1-III), R ^b24 and R ^b25 represent a monovalent group or an alkyl group containing an epoxy group. However, among x1 pieces of R ^b24 and x1 pieces of R ^b25 in the compound represented by formula (b1-III), at least two of them are monovalent groups containing an epoxy group. In addition, x1 in a formula (b1-III) represents an integer of 3 or more. Furthermore, R ^b24 and R ^b25 in the compound represented by the formula (b1-III) may be the same or different. In addition, a plurality of R ^b24 may be the same or different. A plurality of R ^b25 may also be the same or different.

Examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group having 1 or more and 18 or less carbon atoms (preferably 1 or more and 6 or less, particularly preferably 1 or more and 3 or less of carbon atoms). ) a linear or branched alkyl group.

x1 in Formula (b1-III) represents an integer of 3 or more, and especially, an integer of 3 or more and 6 or less is preferable at the point which is excellent in the crosslinking reactivity at the time of forming a cured film.

The number of epoxy groups which a siloxane compound has in a molecule|numerator is 2 or more, 2 or more and 6 or less are preferable from the point which is excellent in the crosslinking reactivity at the time of forming a cured film, Especially preferably, they are 2 or more and 4 or less.

As the monovalent group containing the epoxy group, an alicyclic epoxy group and a glycidyl ether group represented by -D ^B -OR ^b26 [ ^DB represents an alkylene group, R ^b26 represents a glycidyl group] are preferable; An alicyclic epoxy group is more preferable, and the alicyclic epoxy group represented by a following formula (b1-IIIa) or a following formula (b1-IIIb) is still more preferable. Examples of the D ^B (alkylene group) include a linear or branched alkylene group having 1 to 18 carbon atoms, such as a methylene group, a methyl methylene group, a dimethyl methylene group, a dimethylene group, and a trimethylene group. can be heard

(In the formulas (b1-IIIa) and (b1-IIIb), D ¹ and D ² each independently represent an alkylene group, and ms represents an integer of 0 or more and 2 or less.)

The curable composition is a cation-curable compound (B), in addition to the siloxane compound represented by the formula (b1-III), an alicyclic epoxy group-containing cyclic siloxane, an alicyclic epoxy group-containing silicone resin described in Japanese Patent Application Laid-Open No. 2008-248169, and Japanese Patent Application Laid-Open No. You may contain the compound which has siloxane frame|skeleton, such as organopolysilsesquinoxane resin which has an at least 2 epoxy functional group in 1 molecule described in 2008-19422 publication.

More specifically, as a siloxane compound, the cyclic siloxane etc. which have 2 or more glycidyl groups in a molecule|numerator represented by a following formula are mentioned. In addition, as a siloxane compound, "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" are, for example, a brand name, for example. (above, the product made by Shin-Etsu Chemical Industry Co., Ltd.) etc. can be used.

<Other ingredients>

In the curable composition, if necessary, a crosslinking agent (for example, P1 or P2 described later is included), a sensitizer, a surfactant, a thermal polymerization inhibitor, an antifoaming agent, a silane coupling agent, a colorant (pigment, dye), an inorganic filler and additives such as organic fillers. Any additive can use a conventionally well-known additive.

In addition, although the curable composition consists substantially of a non-polymer component, it may contain the polymer (known thermosetting resins, such as an epoxy resin, a thermoplastic resin, alkali-soluble resin, etc.) in the range which does not impair the effect of this invention. Content of a polymer is 0 mass % or more and 5 mass % or less with respect to the whole solid content of a curable composition.

As a sensitizer, the well-known sensitizer in particular conventionally used together with various cationic polymerization initiators can be used without a restriction|limiting.

Specific examples of the sensitizer include anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-dipic anthracene compounds such as lopoxyanthracene; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone; phenothiazine compounds such as phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, and N-phenylphenothiazine; xanthone; naphthalene compounds such as 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol; Dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl propan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 4-benzoyl ketones such as -4'-methyl diphenyl sulfide; carbazole compounds such as N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, and N-glycidylcarbazole; chrysene compounds such as 1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene; and phenanthrene compounds such as 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, and 9-hydroxy-10-ethoxyphenanthrene.

You may use these sensitizers in combination of 2 or more type.

Although the usage-amount of a sensitizer is not specifically limited, 1 mass part or more and 300 mass parts or less are preferable with respect to 100 mass parts of energy-sensitive hardening|curing agents (A), and 5 mass parts or more and 200 mass parts or less are more preferable. By using the sensitizer of such a range, it is easy to obtain a desired sensitizing effect.

Examples of the surfactant include compounds such as anionic, cationic, and nonionic, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine compounds. have.

In addition, the curable composition contains a polymerizable compound other than the aromatic vinyl ether compound (B), such as a vinyl ether compound or an epoxy compound that does not have a vinyloxy group on the aromatic group, within the scope not impairing the object of the present invention, there may be

In this embodiment, it is also mentioned as one of the preferable aspect to include an epoxy group containing fluorene compound in a curable composition from a viewpoint of making hardened|cured material high refractive index. Typically, the compound represented by the following formula (P1) containing 9,9-bis(glycidyloxynaphthyl) fluorenes is more preferable.

(in formula (P1), ring Z ^P1 is a condensed polycyclic aromatic hydrocarbon ring, R ^P1 and R ^P2 are a substituent, R ^P3 is a hydrogen atom or a methyl group, k1 is an integer of 0 or more and 4 or less, k2 is an integer of 0 or more , k3 is an integer greater than or equal to 1.)

In the formula (P1), as the condensed polycyclic aromatic hydrocarbon ring represented by the ring Z ^P1 , Condensed 2-4 cyclic hydrocarbon rings, such as a C10-C16 condensed bicyclic hydrocarbon ring) and a condensed tricyclic hydrocarbon ring (For example, anthracene ring, a phenanthrene ring, etc.), etc. are mentioned. A naphthalene ring, an anthracene ring, etc. are mentioned as a preferable condensed polycyclic aromatic hydrocarbon ring, A naphthalene ring is especially preferable. In addition, the two rings Z ^P1 substituting at position 9 of fluorene may be the same or different rings, and usually the same ring may be sufficient as them.

In addition, the substitution position of the ring Z ^P1 substituted at the 9th position of fluorene is not particularly limited, For example, the naphthyl group substituted at the 9th position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, It is especially preferable that it is a 2-naphthyl group.

In the formula (P1), as the substituent represented by R ^P1 , for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group ( C6~C10 aryl group such as phenyl group) etc.], etc. are mentioned, and especially, it is a halogen atom, a cyano group, or an alkyl group (especially an alkyl group) in many cases. Examples of the alkyl group include C1-C6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (eg, a C1-C4 alkyl group, particularly a methyl group). In addition, when k1 is plural (2 or more), R ^P1 may mutually differ and may be same. In addition, R ^P1 substituted for the two benzene rings constituting fluorene (or fluorene skeleton) may be the same or different. In addition, the bonding position (substitution position) of R ^P1 with respect to the benzene ring which comprises fluorene is not specifically limited. Preferred k1 is 0 or 1, especially 0. In addition, in the two benzene rings constituting fluorene, k1 may be the same as or different from each other.

R ^P2 substituted for ring Z ^P1 is, for example, an alkyl group (for example, a C1-C12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably a C1-C8 alkyl group, more preferably a C1-C8 alkyl group preferably a C1-C6 alkyl group, etc.), a cycloalkyl group (eg, a C5-C8 cycloalkyl group such as a cyclohexyl group, preferably a C5-C6 cycloalkyl group, etc.), an aryl group (eg, a phenyl group, a tolyl group, C6~C14 aryl group such as xylyl group, preferably C6~C10 aryl group, more preferably C6~C8 aryl group, etc.), aralkyl group (e.g., C6~C10 aryl group such as benzyl group and phenethyl group) hydrocarbon groups such as an aralkyl group formed by bonding C1-C4 alkyl groups; Alkoxy group (For example, a C1-C8 alkoxy group such as a methoxy group, preferably a C1-C6 alkoxy group, etc.), a cycloalkoxy group (C5-C10 cycloalkyloxy group, etc.), an aryloxy group (C6-C10 aryl) oxy group, etc.) and the like -OR ^P4 [wherein, R ^P4 represents a hydrocarbon group (a hydrocarbon group in the example above)]; groups such as an alkylthio group (eg, a C1-C8 alkylthio group such as a methylthio group, preferably a C1-C6 alkylthio group, etc.) -SR ^P4 (wherein R ^P4 is the same as above); an acyl group (eg, a C1-C6 acyl group such as an acetyl group); an alkoxycarbonyl group (eg, an alkoxycarbonyl group formed by bonding a carbonyl group to a C1-C4 alkoxy group such as a methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); hydroxyl group; nitro group; cyano group; Substituted amino groups (For example, dialkylamino groups, such as a dimethylamino group, etc.) etc. are mentioned.

Among these, R ^P2 is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, or the like, and particularly preferably R ^P2 is , a hydrocarbon group (e.g., an alkyl group (e.g., a C1-C6 alkyl group)], an alkoxy group (such as a C1-C4 alkoxy group), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) .

Incidentally, in the same ring Z ^P1 , when k2 is plural (2 or more), R ^P2 may be different from or the same as each other. In the two rings Z ^P1 , R ^P2 may be the same or different. Further, preferred k2 is 0 or more and 8 or less, preferably 0 or more and 6 or less (for example, 1 or more and 5 or less), more preferably 0 or more and 4 or less, particularly 0 or more and 2 or less (for example, 0 or 1) may be Incidentally, in the two rings Z ^P1 , k2 may be the same as or different from each other.

In addition, in said Formula (P1), R ^P3 is a hydrogen atom or a methyl group, and preferable R ^P3 is a hydrogen atom.

In said formula (P1), k3 may be 1 or more, for example, 1 or more and 4 or less, Preferably 1 or more and 3 or less, More preferably, 1 or 2, and especially 1 may be sufficient. In addition, in each ring Z ^P1 , k3 may be the same or different, and is usually the same in many cases. In addition, the substitution position of an epoxy group-containing group is not specifically limited, What is necessary is just to substitute in the suitable substitution position of ring Z ^P1 . In particular, the epoxy group-containing group is often substituted at least with a hydrocarbon ring different from the hydrocarbon ring bonded at the 9th position of the fluorene (for example, the 5th, 6th, etc. of the naphthalene ring) with respect to the condensed polycyclic hydrocarbon ring.

As a specific compound represented by said Formula (P1), for example, 9,9-bis(glycidyloxynaphthyl)fluorene [for example, 9,9-bis(6-glycidyloxy-2- naphthyl) fluorene, 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene, etc.] and the like, and the like, wherein k 3 is 1 in the formula (P1).

Moreover, in this embodiment, it is also mentioned as one of a preferable aspect to include a hydroxyl-containing fluorene compound in a curable composition from a viewpoint of making hardened|cured material high refractive index. Typically, it is preferable to include a compound represented by the following formula (P2).

In the formula (P2), R ^P1 , R ^P2 , Z ^P1 , k1 , k2 , and k3 are the same as in the formula (P1).

<Solvent (S)>

It is preferable that curable composition contains a solvent (S) for the purpose of adjustment of applicability|paintability and a viscosity. As the solvent (S), an organic solvent is typically used. The type of the organic solvent is not particularly limited as long as the component contained in the energy-sensitive composition can be uniformly dissolved or dispersed. When the curable composition contains the solvent (S), the solid content concentration of the curable composition is, for example, 0.1 mass% or more and 50 mass% or less, and preferably 0.5 mass% or more and 30 mass% or less. By setting it as the said range, applicability|paintability and operability become favorable.

Suitable examples of the organic solvent that can be used as the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethoxypropionate ethyl, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned. These organic solvents can be used individually or in combination of 2 or more types.

The curable composition may contain the high boiling point solvent in the range which does not impair the effect of this invention. A high boiling point solvent is a solvent whose boiling point under atmospheric pressure is 180 degreeC or more.

The high boiling point solvent may be appropriately selected from hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, etc. For example, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decane ol, 1-undetanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2 -Ethyl hexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, Diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n -Butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, (gamma)-butyrolactone etc. can be illustrated, You may use these individually or in mixture. The content of the high boiling point solvent may be prepared, for example, in a range of 0 mass % or more and 25 mass % or less with respect to the whole solvent component, and preferably 0 mass % or more and 10 mass % or less.

«Method for Producing Curable Composition»

A curable composition can be manufactured by mixing each component demonstrated above uniformly in a predetermined|prescribed ratio. In order to remove an insoluble foreign material as needed, you may filter a curable composition using the filter which has an opening of a desired size.

≪Method for forming cured product≫

The formation method of hardened|cured material will not be specifically limited if it is a method which can harden the above-mentioned curable composition shape|molded into a desired shape. The curable composition contains a photoacid generator (A1) and a thermal acid generator (A2). For this reason, when forming hardened|cured material, exposure and a heating are added with respect to a curable composition normally.

Although the shape of the molded object of a hardening composition is not specifically limited, It is preferable that it is a film|membrane (film) because it is easy to apply heat uniformly to a molded object, or it is easy to irradiate exposure light to a molded object uniformly.

The typical example of the method of manufacturing hardened|cured material as a cured film is demonstrated below.

First, a curable composition is apply|coated on board|substrates, such as a glass substrate, and a coating film is formed. Examples of the coating method include a method using a contact transfer coating device such as a roll coater, a reverse coater, or a bar coater, and a non-contact coating device such as a spinner (rotary coating device), a slit coater, or a curtain flow coater.

In addition, after adjusting the viscosity of the curable composition to an appropriate range, the curable composition may be applied according to a printing method such as an inkjet method or a screen printing method to form a coating film patterned into a desired shape.

Then, as needed, volatile components, such as a solvent (S), are removed and a coating film is dried. The drying method is not particularly limited, but for example, drying under reduced pressure at room temperature using a vacuum drying device (VCD), and then using a hot plate at 80°C or more and 120°C or less, preferably 90°C or more and 100°C or less The method of drying time within the range of 60 second or more and 120 second or less at temperature is mentioned.

After the coating film is formed in this way, exposure and heating are performed on the coating film.

The exposure is performed by irradiating active energy rays such as excimer laser light. Although the energy dose to be irradiated varies depending on the composition of the curable composition, for example, 10 mJ/cm ² or more and 2000 mJ/cm ² or less are preferable, 30 mJ/cm ² or more and 1500 mJ/cm ² or less are more preferable, 50 mJ/cm ² or less More than 1200 mJ/cm ² or less is further preferable.

The temperature at the time of heating is not specifically limited, 120 degreeC or more and 280 degrees C or less are preferable, 150 degreeC or more and 260 degrees C or less are more preferable, 200 degreeC or more and 250 degrees C or less are especially preferable. As for the heating time, typically, 1 minute or more and 60 minutes or less are preferable, 10 minutes or more and 50 minutes or less are more preferable, and their 20 minutes or more and 40 minutes or less are especially preferable.

The above-mentioned curable composition hardens|cures favorably by said conditions, for example.

Specifically, the cured product of the above-mentioned curable composition WHEREIN: The epoxy group content measured by the following method becomes like this. Preferably it is 1.8 or less, More preferably, it is 0.8 or more and 1.3 or less. It means that hardening is advancing favorably, so that epoxy group content is small.

The above epoxy group content is the area of the peak representing the epoxy group obtained by measuring the cured product with a Fourier transform infrared spectroscopy (FT-IR) apparatus, and the area of the peak representing benzene obtained by measuring by the same FT-IR apparatus. minus the value

The hardened|cured material formed as mentioned above, especially a cured film, is used suitably for the display panel for image display apparatuses, and OLED lighting.

Example

Hereinafter, although an Example is shown and this invention is further specifically demonstrated, the scope of the present invention is not limited to these Examples.

[Examples 1 to 6, and Comparative Examples 1 to 11]

In Examples and Comparative Examples, A1-1, A1-2, A1-3, and A1-4 were used as the above-mentioned photo-acid generator (A1). The structures of A1-1 and A1-2 are described below.

A1-3 is an anion composed of a cation moiety composed of a triarylsulfonium cation different from the cation moiety contained in A1-1 and A1-2, and an anion of the same kind as the anion moiety contained in A1-1 and A1-2; It is a sulfonium salt consisting of

A1-4 is a sulfonium salt which consists of a cation part of the same kind as the cation part which A1-3 has, and the anion part represented by (C ₆ F ₅ ) ₄ Ga ^- . (C ₆ F ₅ ) In ₄ Ga ⁻ , C ₆ F ₅ is a pentafluorophenyl group.

In Examples and Comparative Examples, A2-1, A2-2, and A2-3 were used as the above-mentioned thermal acid generator (A2). The structures of A2-2 and A2-3 are described below.

A2-1 is a sulfonium salt which consists of the cation part with which A2-2 and A2-3 is equipped, and the anion part with which A1-4 is equipped.

In the Example and the comparative example, the following compound was used as a cation-curable compound (B).

Each of the types and amounts of the cation curing agent (A) described in Table 1 and 99 parts by mass of the cation-curable compound (B) were uniformly dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass, and each run Curable compositions of Examples and Comparative Examples were obtained. Using the obtained curable composition, the appearance, coloring, solvent resistance, and epoxy group content were evaluated about the hardened|cured material of a curable composition according to the following method. Table 1 lists these evaluation results. However, there are examples in which some measurements are not performed with respect to coloration and epoxy group content.

<Appearance of cured product>

After apply|coating the curable composition of each Example and a comparative example with a spin coater on a glass substrate, it heated for 120 second at 100 degreeC, and formed the coating film. The entire surface of the formed coating film was exposed at an exposure amount of 1000 mJ/cm ² . Then, the exposed coating film was heated at 230 degreeC for 20 minutes, and the cured film (film thickness about 1 micrometer) was formed as hardened|cured material.

The formed cured film was visually observed and it was confirmed whether it was transparent or had yellowish taste by coloring.

<Coloring of cured product>

About the cured film used for the appearance evaluation of the hardened|cured material, using the brand name "Hazemeter NDH-5000" manufactured by Nippon Denshoku Kogyo Co., Ltd., measurement of b ^* value in the L ^* a ^* b ^* color system was performed. did.

<solvent resistance>

The cured film formed by the method similar to appearance evaluation of hardened|cured material was immersed in acetone for 2 minutes, and the tolerance with respect to acetone was evaluated. The case where the change amount of the film thickness before and behind immersion was less than 3 % was judged as (circle), and the case where it was 10 % or more was judged as Х. In addition, expression of solvent resistance means that hardening of a cation-curable compound (B) is advancing favorably.

<Epoxy group content>

The cured film formed by the method similar to appearance evaluation of hardened|cured material was measured with a Fourier transform infrared spectroscopy (FT-IR) apparatus. Based on the measurement result, the value shown by the value which subtracted the area of the peak which shows an epoxy group from the area of the peak which shows benzene measured with the same FT-IR apparatus was computed as epoxy group content. It means that hardening of a cation-curable compound (B) is advancing favorably, so that the value of epoxy group content is small.

According to Table 1, a cation curing agent (A) containing a combination of a photo-acid generator (A1) and a thermal acid generator (A2) each satisfying the above-mentioned predetermined requirements, and an epoxy compound as a cation-curable compound (B) It turns out that the curable composition of the Example to be mentioned gives a cured film with little coloring and is transparent and excellent in solvent resistance, and advances hardening favorably by exposure and heating.

On the other hand, according to Table 1, in the curable composition of the comparative example in which at least one of a photo-acid generator and a thermal acid generator does not satisfy predetermined|prescribed requirements, or contains only a photo-acid generator as a cationic curing agent (A), coloring at the time of hardening It turns out that suppression of and favorable advancing of hardening are not compatible.

Claims (8)

A cation curing agent (A) and a cation-curable compound (B),
As the cationic curing agent (A), a photoacid generator (A1) and a thermal acid generator (A2) are included,
The photoacid generator (A1) is an onium salt having a cation moiety represented by the following formula (ai),
The curable composition wherein the thermal acid generator (A2) is an onium salt having an anion moiety represented by the following formula (Ai).
(R ^a1 ) _t+1 -R ^a2+ ...(ai)
(In formula (ai), R ^a1 is each independently a monovalent organic group, R ^a2 is an element having a valence t of Groups 15 to 17 of the Periodic Table of Elements according to IUPAC notation, and R ^a1 At least one is an aryl group which may have a substituent.)
(R ^A1 ) ₄ -Ga ^- ... (Ai)
(In formula (Ai), R ^A1 is each independently a phenyl group which may have one or more substituents, or a perfluoroalkyl group.) The method according to claim 1,
The curable composition wherein the thermal acid generator (A2) is an onium salt having a cationic moiety represented by the following formula (Aiii).
[Tue 1]

(In formula (Aiii), R ^A01 is a monovalent organic group, D is an element of valence u of Groups 15 to 17 of the Periodic Table of Elements according to IUPAC notation, and R ^A03 is a monovalent organic group , u is an integer of 1 or more and 3 or less, and v is an integer of 0 or more and 5 or less.) 3. The method according to claim 2,
The curable composition wherein D is sulfur and u is 2. 4. The method according to any one of claims 1 to 3,
The curable composition wherein R ^a2 is sulfur and t is 2. 5. The method according to claim 4,
The curable composition in which the onium salt represented by said formula (ai) has a cation part represented by following formula (a1).
[Tuesday 2]

(In the formula (a1), R ¹ and R ² independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (a2), and R ¹ and R ² are bonded to each other to form a ring together with the sulfur atom in the formula. may be formed, R ³ represents a group represented by the following formula (a3) or a group represented by the following formula (a4), A ¹ represents S, O, or Se, provided that R ¹ and R ² are at the same time , not an alkyl group which may be substituted with a halogen atom.)
[Tuesday 3]

(In formula (a2), ring Z ¹ represents an aromatic hydrocarbon ring, R ⁴ is an optionally substituted alkyl group with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, thienyl; Thienylcarbonyl group, furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy (poly)alkyleneoxy group, optionally substituted amino group, cyano group represents a no group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more.)
[Tuesday 4]

(in formula (a3), R ⁵ is a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom which may be substituted an alkylene group or a group represented by the following formula (a5), R ⁶ is a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, An aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or represents an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (a6), A ² represents a single bond, S, O, a sulfinyl group, or a carbonyl group, and n1 represents 0 or 1.)
[Tue 5]

(in formula (a4), R ⁷ and R ⁸ are independently a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, An aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or represents an alkylene group optionally substituted with a halogen atom or a group represented by the following formula (a5), R ⁹ and R ¹⁰ independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the formula (a2), R ⁹ and R ¹⁰ may combine with each other to form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, X ⁻ represents a monovalent anion, n2 represents 0 or 1 , provided that R ⁹ and R ¹⁰ are not an alkyl group which may be substituted with a halogen atom at the same time.)
[Tue 6]

(in formula (a5), ring Z ² represents an aromatic hydrocarbon ring, R ¹¹ is optionally substituted with a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, Acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly)alkyleneoxy group, substitution An amino group, a cyano group, a nitro group, or a halogen atom may be represented, and m2 represents an integer of 0 or more.)
[Tue 7]

(in formula (a6), ring Z ³ represents an aromatic hydrocarbon ring, R ¹² is optionally substituted with a halogen atom alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, Acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more.) 6. The method according to any one of claims 1 to 5,
The ratio of the mass of the said photo-acid generator (A1) with respect to the sum total of the mass of the said photo-acid generator (A1), and the mass of the said thermal acid generator (A2) is 50 mass % or less, The curable composition. A cured product of the curable composition according to any one of claims 1 to 6. A method for forming a cured product, wherein exposure and heating are applied to the curable composition according to any one of claims 1 to 6.