JP7277226B2 - Compound, polymerization initiator, polymerizable resin composition and photosensitive resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a compound useful as a polymerization initiator used in a polymerizable resin composition, a polymerizable resin composition containing the compound and a polymerizable resin, and a cured product of the polymerizable resin composition.

In general, a polymerizable resin composition is obtained by adding a photopolymerization initiator to a polymerizable resin, and can be polymerized and cured by irradiation with energy rays (light) or developed. It is used for plates, various photoresists, photo-curing adhesives, etc.

Photopolymerization initiators are classified into photoradical generators, photoacid generators, and photobase generators, depending on the difference in active species generated by irradiation with energy rays (light). Photoradical generators have advantages such as a fast curing speed and no active species remaining after curing, but they have the disadvantage of requiring a layer to block oxygen when curing a thin film because curing is inhibited by oxygen. There is Photoacid generators have the advantage of not being inhibited by oxygen, but have the disadvantages of corroding metal substrates and denaturing resins after curing due to the residual acid of the active species. Photobase generators are attracting attention because they are less likely to cause problems such as curing inhibition due to oxygen and corrosion due to residual active species, but generally have the problem of low sensitivity (low curability) compared to photoacid generators. . As photobase generators, for example, Patent Document 1 discloses an amine salt having a diphenyl sulfide skeleton, and Patent Document 2 discloses a carbamoyl oxime compound having a carbazole skeleton.

JP 2013-163670 A International publication WO2013/141014

However, the amine salt having a diphenyl sulfide skeleton described in Patent Document 1 has a problem of insufficient sensitivity. Moreover, the carbamoyl oxime compound having a carbazole skeleton described in Patent Document 2 has a problem that the obtained cured product has low transparency.

Accordingly, an object of the present invention is to provide a novel compound having satisfactory sensitivity (base generating ability), a polymerizable resin composition containing the compound as a polymerization initiator, and a cured product thereof having excellent transparency. .

The present inventors conducted intensive studies and found that a compound having a specific structure as a polymerization initiator has high sensitivity (base generating ability), and a polymerizable resin composition containing the polymerization initiator exhibits transparency. It was found that a high cured product can be obtained.

The present invention achieves the above objects by providing the following [1] to [9].

[1] A compound represented by the following general formula (1).

(In the formula, X is the following (a1), (a2), (a3), (a4), (a5), (a6), (a7), (a8), (a9), (a10), ( a11), (a12), (a13), (a14), (a15), (a16) or a group represented by (a17),
R ¹ and R ² each independently represent a hydrogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a thiol group, a halogen atom, an unsubstituted or substituted hydrocarbon having 1 to 20 carbon atoms; group, or a group having 2 to 20 carbon atoms containing an unsubstituted or substituted heterocyclic ring,
R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a cyano group, a nitro group, -OR ⁹ , -COOR ⁹ , -CO-R ⁹ , -SR ⁹ , a halogen atom, represents an unsubstituted or substituted hydrocarbon group of 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group of 2 to 20 carbon atoms,
R ⁹ is a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring containing 2 to 20 carbon atoms represents the group of
R ⁵ and R ⁶ , R ⁶ and R ⁷ and R ⁷ and R ⁸ may together form a ring,
R ⁴ is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. represent,
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral. )

(Wherein, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ¹¹ in the above (a1) , R ¹² and R ¹³ may form a ring together, and the double line consisting of a solid line and a broken line in (a1) above represents a single bond or a double bond,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently the same as R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) represents the group of
Ar ¹ and Ar ² represent an unsubstituted or substituted aromatic ring,
when a plurality of R ¹¹ are present in one group, the plurality of R ¹¹ are the same or different,
When one group has a plurality of R ¹² , the plurality of R ¹² are the same or different,
m and n each independently represents an integer of 1 to 12,
* represents a bond. )

[2] one or more of R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above general formula (1) is a cyano group, a nitro group, -OR ⁹ , -COOR ⁹ , -CO-R; ⁹ , —SR ⁹ , a halogen atom, or a halogenated alkyl group, the compound according to [1].

[3] The compound according to [1] or [2], wherein R ¹ in the general formula (1) is an unsubstituted or substituted aryl group having 6 to 20 carbon atoms.

[4] A polymerization initiator containing the compound according to any one of [1] to [3].

[5] A polymerizable resin composition containing the polymerization initiator (A) according to [4] and a polymerizable resin (B).

[6] A photosensitive resin composition containing the polymerization initiator (A) according to [4] and a polymerizable resin (B).

[7] The polymerizable resin composition according to [5], wherein the polymerizable resin (B) is an epoxy resin (B1) or a phenol resin (B2).

[8] A cured product obtained from the polymerizable resin composition described in [5] or [7] or the photosensitive resin composition described in [6].

[9] A method for producing a cured product, which comprises a step of irradiating the polymerizable resin composition described in [5] or [7] or the photosensitive resin composition described in [6] with an energy ray.

When the compound of the present invention is used as a polymerization initiator, the polymerizable resin can be cured even at a low exposure dose. Moreover, since not only the base but also the radical active species are generated at the time of energy irradiation, the polymerizable resin can be cured by both the active species of the base and the radical.

The unsubstituted or substituted aromatic ring represented by Ar ¹ and Ar ² in the general formula (1) includes an unsubstituted aromatic hydrocarbon ring, an unsubstituted aromatic heterocyclic ring, An aromatic hydrocarbon ring having a substituent and an aromatic heterocyclic ring having a substituent are exemplified.
Although the number of carbon atoms in the unsubstituted or substituted aromatic ring represented by Ar ¹ and Ar ² is not particularly limited, it usually has 4 to 40 carbon atoms, preferably 4 carbon atoms. to 30, more preferably 4 to 20 carbon atoms.
Unsubstituted aromatic hydrocarbon rings include phenyl, naphthyl, phenanthryl, pyrenyl, biphenyl, and the like. Unsubstituted heteroaromatic rings include furan, thienyl, benzothienyl, and the like.

As the substituted aromatic hydrocarbon ring or substituted aromatic heterocyclic ring represented by Ar ¹ or Ar ² , the hydrogen atom of the unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring is replaced by a fluorine atom. , chlorine atom, bromine atom, iodine atom, cyano group, nitro group, —OR, —SR, —COOR, —SO ₂ R, —COR, —NRR′, substituted with a hydrocarbon group having 1 to 20 carbon atoms things, etc.
R and R' each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include groups that can be taken by the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ etc. described below.

The hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁹ and R ¹¹ to R ¹³ in the general formula (1) are not particularly limited, but preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and It represents an arylalkyl group having 7 to 20 carbon atoms, or the like. Since the sensitivity when used as the polymerization initiator (A) is good, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a carbon A cycloalkylalkyl group having 4 to 10 atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like are more preferable.
In the above hydrocarbon group having 1 to 20 carbon atoms, one or more methylene groups in the group are -O-, -COO-, -OCO-, -CO-, -CS-, -S- , -SO-, -SO ₂ -, -NR ²¹ -, -NR-CO-, -CO-NR ²¹ -, -NR ²¹ -COO-, -OCO-NR ²¹ - or -SiR ²¹ R ²² - one or more of the hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms is a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol groups, —NH ₂ , —COOH or —SO ₂ H. R ²¹ and R ²² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and not having the above substituents. The hydrocarbon group having 1 to 20 carbon atoms means a group having 1 to 20 carbon atoms including a group in which a methylene group is substituted or a group in which a hydrogen atom is substituted.

Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl and isooctyl. , 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl and isooctyl. , 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-tetradecatrienyl allyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl and 4-decenyl.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl and tetradecahydroanthracenyl. mentioned. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1. 1.1]pentanyl and the like.

The above-mentioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is replaced with a cycloalkyl group. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclo Butylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3- cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4 -cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl and decahydronaphthylpropyl. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2 -cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4 -cyclopentylbutyl, 4-cyclohexylbutyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms include, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, etc., and one or more of the alkyl group, the alkenyl group, the carboxyl group, the halogen atom, and the like. Substituted phenyl, biphenylyl, naphthyl, anthryl and the like, such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and the like, the alkyl group, the alkenyl group, the carboxyl group, and phenyl substituted with one or more halogen atoms. , biphenylyl, naphthyl, anthryl and the like, such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of an alkyl group is replaced with an aryl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl. The arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which a hydrogen atom of an alkyl group is replaced with an aryl group, such as benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like.

Substituents that may substitute the hydrocarbon group having 1 to 20 carbon atoms include the alkyl group having 1 to 20 carbon atoms; the alkenyl group having 2 to 20 carbon atoms; and the alkenyl group having 3 to 20 carbon atoms. a cycloalkyl group having 4 to 20 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a nitro group; a hydroxyl group; a thiol ^group ; —SO ₂ H. The above hydrocarbon group having 1 to 20 carbon atoms may be substituted at one site or may be substituted at multiple sites. R ³¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which does not have the above substituents.

The heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹ to R ⁹ in the general formula (1) is not particularly limited, but may be an aliphatic heterocyclic group or an aromatic heterocyclic group. A cyclic group can be mentioned.

Examples of the aliphatic heterocyclic group include tetrahydrofuryl, dioxolanyl, pyranyl, tetrahydropyranyl, pyrrolidinyl, pyrazolyl, piperidyl, piperazyl, pyrrolidyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4- dioxyimidazolidin-3-yl, morpholyl and 2,4-dioxyoxazolidin-3-yl;
Examples of the aromatic heterocyclic group include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, furyl, thienyl, benzoxazol-2-yl, imidazolyl, thiazolyl, isothiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isoxazolyl, triazyl, triazyl. methyl, quinolyl, isoquinolyl, benzimidazolyl, 2,4-dioxyimidazolidin-3-yl, triazolyl, furanyl, benzofuranyl, thiophenyl, benzothiophenyl, indolyl and the like.

Substituents that may substitute the group containing a heterocyclic ring and having 2 to 20 carbon atoms include the above alkyl group having 1 to 20 carbon atoms; the alkenyl group having 2 to 20 carbon atoms; 3 to 20 cycloalkyl groups; the above 4 to 20 carbon atom cycloalkylalkyl groups; halogen atoms such as fluorine, chlorine, bromine and iodine atoms; cyano groups; nitro groups; hydroxyl groups; thiol groups; ³¹ ; and —SO ₂ H. Groups of 2 to 20 carbon atoms containing heterocyclic rings may be singly substituted or multiply substituted. R ³¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which does not have the above substituents.

Specific examples of heterocyclic ring-containing groups having 2 to 20 carbon atoms, including substituents, include groups having the following structures.

(In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms, and * means a bond.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the alkyl groups having 1 to 20 carbon atoms described above. can.
Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include those obtained by removing one hydrogen atom from the above alkyl group having 1 to 6 carbon atoms.

Examples of the ring that can be formed by combining R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ in the general formula (1) include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, 5- to 7-membered rings such as benzene ring, piperidine ring, morpholine ring, lactone ring and lactam ring are preferred.

Halogen atoms represented by R ¹ to R ³ and R ⁵ to R ⁸ in the general formula (1) include fluorine, chlorine, bromine and iodine.

Examples of q-valent anions represented by An ^q- in the general formula (1) include halogen ions such as chloride anions, bromine anions, iodine anions, and fluorine anions; perchlorate anions; , chlorate anion, thiocyanate anion, phosphate hexafluoride anion, antimony hexafluoride anion, arsenic hexafluoride anion, boron tetrafluoride anion; methanesulfonic acid ions, fluorosulfonate anions, benzenesulfonate anions, toluenesulfonate anions, 1-naphthylsulfonate anions, 2-naphthylsulfonate anions, trifluoromethanesulfonate anions, pentafluoroethanesulfonate anions, Heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, undecafluoropentanesulfonate anion, tridecafluorohexanesulfonate anion, pentadecafluoroheptanesulfonate anion, heptadecafluorooctanesulfonate anion , perfluoro-4-ethylcyclohexanesulfonate ion, N-alkyl (or aryl) diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion, 2-amino-5- Nitrobenzenesulfonate anions, sulfonate anions described in JP-A-2004-53799, camphorsulfonate anions, fluorobenzenesulfonate anions, difluorobenzenesulfonate anions, trifluorobenzenesulfonate anions, Sulfonate anions such as tetrafluorobenzenesulfonate anion and pentafluorobenzenesulfonate anion; octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion phosphate anions such as 2,2′-methylenebis(4,6-di-t-butylphenyl)phosphonate anions; bis(trifluoromethanesulfone)imide ion, bis(pentafluoroethanesulfone)imide ion, phthalimide ion , o-sulfobenzimide, bis(heptafluoropropanesulfone)imide ion, bis(nonafluorobutanesulfone)imide ion, bis(undecafluoropentanesulfone)imide ion, bis(pentadecafluoroheptanesulfone)imide ion, bis(tridecafluoro hexanesulfone)imide ion, bis(heptadecafluorooctanesulfonimide)ion, (trifluoromethanesulfone)(nonafluorobutanesulfone)imide ion, (methanesulfone)(trifluoromethanesulfone)imide ion, cyclo-hexafluoropropane-1,3- Imido ions such as bis (sulfonyl) imide anions; Borate anion, borate anion described in JP-A-6-184170, borate anion described in JP-A-2002-526391, boron described in JP-A-2007-285538 Tetraarylborate anions such as acid anions; Carboxylate anions such as benzoate anions, trifluoroacetate anions and 2-oxo-2-phenylacetate anions; N,N-diethyldithiocarbamate anions dithiocarbamic acid anions such as; Examples include imides and fluoro-substituted alkylsulfonimides substituted with an acryloyloxy group or methacryloyloxy group, or those substituted with an aliphatic cyclic alkyl group such as a norbornyl group or an adamantyl group. In addition, quencher anions that have the function of deexciting (quenching) active molecules in an excited state and ferrocene having anionic groups such as carboxyl groups, phosphonic acid groups, and sulfonic acid groups on the cyclopentadienyl ring Anions of metallocene compounds such as luteocene and the like can also be used as necessary.
Among the q-valent anions represented by An ^q- , halogen ions, inorganic halide anions, sulfonate anions, and tetraarylborate anions are preferred because of the high curability of the resin composition by the generated base. , carboxylate anions and dithiocarbamate anions are preferred, tetraarylborate anions, triarylalkylborane anions, thiocyanate anions, dithiocarbamate anions, phthalimide anions, iodine anions, sulfobenzimide anions, tetrafluoroboron anions, Phosphorus hexafluoride anion and trifluoromethanesulfonate anion are more preferable, and among them, tetraarylborate anion, triphenylalkylborane anion and thiocyanate anion are particularly preferable.

The cation of the compound represented by the general formula (1) is R ¹¹ , R ¹² or R ¹³ from the viewpoint of excellent UV sensitivity, strong basicity of generated base, curability, storage stability, and nonvolatility. , alkyl, diamine via an alkyl chain; rings formed by combining R ¹¹ , R ¹² and R ¹³ in (a1) above (e.g. imidazole, triazole, azabicycloamine) and these rings A cation that is a group substituted with an alkyl group is preferred, and among them, a cation that is imidazole, triazole, azabicycloamine formed by combining R ¹¹ , R ¹² and R ¹³ with each other and a group in which these rings are substituted with an alkyl group. more preferred. A ring formed by combining R ¹¹ , R ¹² and R ¹³ together means a ring formed by combining at least two of R ¹¹ , R ¹² and R ¹³ with each other. When the formed ring is a monocyclic ring, it means a ring formed by combining two of R ¹¹ , R ¹² and R ¹³ with each other, and when the formed ring is a condensed ring , R ¹¹ , R ¹² and R ¹³ are all combined to form a ring. A double line consisting of a solid line and a broken line in (a1) above represents a single bond or a double bond.

R ¹ in the general formula (I) has 6 carbon atoms, which is unsubstituted or substituted, from the viewpoint of obtaining a compound having excellent UV sensitivity, a long absorption wavelength, and excellent solubility in resins. ~20 aryl group, phenyl group, naphthyl group, nitro group, -COOH or hydrocarbon group having 1 to 20 carbon atoms (-O-, -COO-, -OCO-, -CO- It is more preferably a phenyl group or naphthyl group substituted with (including those interrupted by ), more preferably a phenyl group or naphthyl group.

One or more of R ³ and R ⁵ to R ⁸ in general formula (I) is a cyano group, from the viewpoint of obtaining a compound having excellent UV sensitivity, a long absorption wavelength, and excellent solubility in resins. A nitro group, -OR ⁹ , -COOR ⁹ , -CO-R ⁹ , -SR ⁹ , a halogen atom and a halogenated alkyl group are preferred.
The halogenated alkyl group may be an alkyl group in which one or more hydrogen atoms are substituted with halogen. In the present invention, the number of carbon atoms in the halogenated alkyl group is preferably from 1 to 10, more preferably from 1 to 4, since the ability to generate a base is enhanced. Further, in the halogenated alkyl group, some of the hydrogen atoms in the alkyl group may be substituted with halogens, or all of the hydrogen atoms in the alkyl group may be substituted with halogens. The halogenated alkyl group is preferably one in which all of the hydrogen atoms in the alkyl group are substituted with halogen, since the ability to generate a base increases. Particularly preferred halogenated alkyl groups include trifluoromethyl group and pentafluoroethyl group.

R ² in the general formula (I) is a hydrogen atom; , a cycloalkyl group having 3 to 20 carbon atoms and a cycloalkylalkyl group having 4 to 20 carbon atoms and other aliphatic hydrocarbon groups having 1 to 20 carbon atoms (including those interrupted by —O—) or preferably an unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms such as an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms, and a hydrogen atom or a number of carbon atoms 1 to 20 unsubstituted aliphatic hydrocarbons are more preferred.

A compound in which the X group in the general formula (I) is (a3) or (a5) is preferable from the viewpoint of high reactivity with an epoxy group.

Specific examples of the compound represented by the general formula (1) include the following compound Nos. 1 to No. 78 can be mentioned. However, the present invention is not limited by the following compounds.

The compound represented by the general formula (1) can be produced, for example, by the following method.

（式中、Ｒ^１～Ｒ^８、Ｘ、Ａｎ、及びｑは上記一般式（１）と同じである。）

(Wherein, R ¹ to R ⁸ , X, An, and q are the same as in general formula (1) above.)

In addition, the compound of the present invention may be coordinated with the amine used in the above synthesis process, and the compound is also included in the compounds represented by the general formula (1) of the present invention. .

The compound of the present invention can be suitably used as a photobase generator and a polymerization initiator which is a radical generator, which will be described below. Further, the compounds of the present invention can be used for chemically amplified resists and the like.

Next, the polymerizable resin composition of the present invention will be explained. In addition, the explanation for the compound of the present invention applies appropriately to points that are not particularly explained. The polymerizable resin composition of the present invention is a composition containing a polymerization initiator (A) and a polymerizable resin (B).

<Polymerization initiator (A)>
The polymerization initiator (A) contained in the polymerizable resin composition of the present invention contains at least one compound represented by the general formula (1). The content of the compound represented by the general formula (1) in the polymerization initiator (A) is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.
The content of the polymerization initiator (A) in the polymerizable resin composition of the present invention is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the polymerizable resin composition. If the content of the polymerization initiator (A) is less than 1 part by mass, poor curing may occur due to insufficient sensitivity. there is a possibility.

<Polymerizable resin (B)>
The polymerizable resin (B) used in the present invention is a resin polymerized by active species (base and radical) generated by irradiating the polymerization initiator (A) with energy rays, or a curing temperature using the active species as a catalyst. It is a low temperature resin. The resin polymerized by basic active species and the resin whose curing temperature is lowered by the use of basic active species as a catalyst have anionic polymerizable functional groups. Examples of the anionic polymerizable functional group include epoxy groups, episulfide groups, cyclic monomers (σ-valerolactone, ε-caprolactam), catalysts for forming urethane bonds with isocyanates and alcohols, Michael addition catalysts for (meth)acrylic groups, and the like. Examples of polymerizable resins include epoxy resins (B1), phenol resins (B2), polyamide resins, polyurethane resins, nylon resins, polyester resins, and the like. These resins may be used alone or in combination of two or more. Among them, the epoxy resin is preferable because the reaction progresses quickly and the adhesiveness is good.
Moreover, the resin polymerized by the radical active species has an unsaturated double bond group. Examples of the unsaturated double bond group include those having a methacryl group, an acryl group, an allyl group, and the like. Examples of polymerizable resins include methacrylates, acrylates, unsaturated polyester resins, and carboxylic acid resins having unsaturated double bond groups. These resins may be used alone or in combination of two or more. Among them, methacrylate and acrylate are preferable because the reaction progresses rapidly.
The polymerizable resin composition of the present invention preferably contains an epoxy resin (B1) or a phenol resin (B2) as a polymerizable resin having a high polymerization initiator effect. The epoxy resin (B1) and the phenol resin (B2) can be used alone or in combination, and the effect of the present invention becomes more remarkable. B2) is preferably used in combination. Further, the polymerizable resin composition of the present invention is preferably used in combination with the epoxy resin (B1) and the carboxylic acid resin having an unsaturated double bond group, since the effect of the present invention becomes more remarkable. .

Examples of the epoxy resin (B1) include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis ( ortho cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4′-dihydroxybenzophenone, isopropylidene bis (ortho cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfo Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as bisphenol, oxybisphenol, phenol novolak, ortho-cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, and terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexane Polyglycidyl ether of polyhydric alcohols such as diol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as methylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N,N-diglycidylaniline, bis(4-(N- Epoxy compounds having a glycidylamino group such as methyl-N-glycidylamino)phenyl)methane, diglycidylorthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxy Epoxidized products of cyclic olefin compounds such as cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized polybutadiene , epoxidized acrylonitrile-butadiene copolymers, epoxidized styrene-butadiene copolymers and other epoxidized conjugated diene polymers, and heterocyclic compounds such as triglycidyl isocyanurate. Further, these epoxy resins may be internally cross-linked with a prepolymer having a terminal isocyanate, or may be polymerized with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). .
Among the above epoxy resins, those having a glycidyl group are preferable, and those having a bifunctional or more glycidyl group are more preferable from the viewpoint of excellent curability.

As the phenol resin (B2), a phenol resin having two or more hydroxy groups in one molecule is preferable, and generally known resins can be used. Examples of phenolic resins include bisphenol A-type phenolic resin, bisphenol E-type phenolic resin, bisphenol F-type phenolic resin, bisphenol S-type phenolic resin, phenol novolac resin, bisphenol A novolac-type phenolic resin, glycidyl ester-type phenolic resin, and aralkyl novolak. type phenolic resin, biphenyl aralkyl-type phenolic resin, cresol novolac-type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene-type phenolic resin, naphthalene skeleton modified novolac-type phenolic resin, phenol aralkyl-type phenol Resins, naphthol aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, alicyclic phenolic resins, polyol-type phenolic resins, phosphorus-containing phenolic resins, polymerizable unsaturated hydrocarbon group-containing phenolic resins, and hydroxyl group-containing Examples include silicone resins, but are not particularly limited. These phenol resins can be used singly or in combination of two or more.

As the polyimide resin, the acid dianhydride is ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride. 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , as diamines, (o-, m- or p-) phenylenediamine, (3,3'- or 4,4'-) diaminodiphenyl ether, diaminobenzophenone, (3,3'- or 4,4'- ) resins made from diaminodiphenylmethane or the like.

As the diisocyanate, polyfunctional isocyanate such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate and polyol (polyfunctional alcohol) such as polyether polyol, polyester polyol and polycarbonate polyol are used as raw materials for the polyurethane resin. and resins to be used.

Examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryllactam.

Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

The methacrylate and acrylate are not particularly limited, and examples thereof include urethane methacrylate and urethane acrylate having a urethane bond, and epoxy acrylate derived from a compound having a glycidyl group and acrylic acid.

The above urethane methacrylate and urethane acrylate are not particularly limited, and examples thereof include derivatives of diisocyanates such as isophorone diisocyanate and reactive compounds that undergo an addition reaction with isocyanates such as acrylic acid and hydroxyethyl acrylate. These derivatives may be chain-extended with caprolactone, polyol, or the like. Examples of commercially available products include U-122P, U-3, 40P, U-4HA, and U-1084A (manufactured by Shin-Nakamura Chemical Co., Ltd.); KRM7595, KRM7610, and KRM7619 (manufactured by Daicel Cytec Co., Ltd.). mentioned.

The epoxy acrylate is not particularly limited, and examples thereof include epoxy methacrylates and epoxy acrylates derived from epoxy resins such as bisphenol A type epoxy resins and propylene glycol diglycidyl ether, and methacrylic acid or acrylic acid. Examples of commercially available products include EA-1020, EA-6320, EA-5520 (manufactured by Shin-Nakamura Chemical Co., Ltd.); Epoxy Ester 70PA and Epoxy Ester 3002A (manufactured by Kyoeisha Chemical Co., Ltd.).

Other methacrylates and acrylates include, for example, methyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1 ,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, glycerol dimethacrylate and the like.

As the polymerizable resin (B), a resin having one or more anionically polymerizable functional groups and one or more unsaturated double bond groups in one molecule can also be suitably used.
Examples of such a resin include, for example, a compound obtained by reacting a portion of the epoxy group of the above epoxy resin with methacrylic acid or acrylic acid in the presence of a basic catalyst, and 1 mol of a difunctional or higher isocyanate. A compound obtained by reacting 1/2 mol of a methacrylic monomer or acrylic monomer having a hydroxyl group followed by 1/2 mol of glycidol, a compound obtained by reacting a methacrylate or acrylate having an isocyanate group with glycidol, and the like. Examples of commercially available epoxy/methacrylic resins or epoxy/acrylic resins include UVAC1561 (manufactured by Daicel Cytec) and 4HBAGE (manufactured by Nippon Kasei Co., Ltd.).

As the polymerizable resin (B) used in the present invention, the specific resins described above can be freely mixed and used.

<Additive>
The polymerizable resin composition of the present invention may contain, as optional components, a latent additive, a chain transfer agent, a sensitizer, an inorganic compound, a coloring material, a latent epoxy curing agent, a solvent, as long as the effects of the present invention are not impaired. Additives such as can be used.

The latent additive is inactive at room temperature, in the photoexposure step and in the prebaking step, and is activated by heating at 100 to 250°C or by heating at 80 to 200°C in the presence of an acid/base catalyst. It is something to do. Effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling properties, recoating properties, adhesion properties, and the like.
As the latent additive, those described in WO2014/021023 pamphlet can be preferably used.

Commercially available products can be used as the latent additive, such as Adeka Arcules GPA-5001.

A sulfur atom-containing compound is generally used as the chain transfer agent. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-( 2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis Mercapto compounds such as (3-mercaptopropionate), disulfide compounds obtained by oxidation of the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid iodinated alkyl compounds such as trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio Propionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate , pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound Nos. Aliphatic polyfunctional thiol compounds such as C1 and trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, Showa Denko Karenz MT BD1, PE1, NR1 and the like.

Examples of sensitizers include indolines, thiazines, triarylmethanes, xanthones, thioxanthones, oxazines, acridines, phenazines, rhodamines and the like. , phenazines, and rhodamines can be preferably used.

In the polymerizable resin composition of the present invention, the amount of the chain transfer agent or sensitizer used is preferably 50 parts by mass or less, and 0.1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (A). is more preferred.

Examples of the inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; Magnesium carbonate, cobalt-based, manganese-based, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Examples include gold, silver, and copper. These inorganic compounds are used as, for example, fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink generating agents, and the like.

Examples of the coloring material include pigments, dyes, and natural pigments. These coloring materials can be used alone or in combination of two or more.

Examples of the pigments include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; ∼200 mg/g resin adsorbed, acid or alkaline surface treated carbon black, carbon black with average particle size of 8 nm or more and DBP oil absorption of 90 ml/100 g or less, volatile content at 950 ° C. Carbon black whose total oxygen content calculated from CO and CO2 is 9 mg or more per 100 m2 of surface area; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black , Pigment Black 7, Titanium Black; Chrome Oxide Green, Miloli Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine Blue, Prussian Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate, Yellow Lead , zinc yellow, red iron oxide (iron(III) oxide red), cadmium red, synthetic iron black, amber, and other organic or inorganic pigments can be used. These pigments can be used alone or in combination.

Commercially available pigments can also be used as the above pigments. 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110; Pigment Green Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, and phthalocyanine dyes. , dyes such as cyanine dyes, etc., and these may be used in combination.

The above-mentioned latent epoxy curing agent means a compound that is solid at room temperature and cures an epoxy resin or the like by heating above its melting point. sulfones, boron trifluoride amine complex salts, imidazoles, guanamines, imidazoles, ureas, melamine and the like. The content of the latent epoxy curing agent in the polymerizable resin composition of the present invention is preferably 1 to 200 parts by mass, preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the polymerizable resin (B), from the viewpoint of curing speed. 100 parts by mass is more preferable, and 20 to 40 parts by mass is even more preferable.

The solvent is usually a solvent capable of dissolving or dispersing each component (polymerization initiator (A), polymerizable resin (B), etc.), such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, and methyl isopropyl. ketones such as ketones, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate , ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, ester solvents such as texanol; cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate, Ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane Solvent; terpene hydrocarbon oil such as turpentine oil, D-limonene, pinene; paraffinic solvent such as mineral spirit, Swasol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon chloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents; Aniline; Triethylamine; Pyridine; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide; Can be used as a solvent.
Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are preferably used in terms of alkali developability, patterning properties, film forming properties, and solubility.
In the polymerizable resin composition of the present invention, the content of the solvent is not particularly limited. However, the amount of the solid content (all components other than the solvent) in the polymerizable resin composition of the present invention is generally 10 to 90% by mass. It is preferable to contain the solvent.

The polymerizable resin composition of the present invention can also improve the properties of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, and the like.
When the above organic polymer is used, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable resin (B).

Surfactants, silane coupling agents, melamine compounds and the like can be used in combination with the polymerizable resin composition of the present invention.

Examples of the above-mentioned surfactants include perfluoroalkyl phosphates, fluorine-based surfactants such as perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates, and alkyl sulfates; Cationic surfactants such as amine halides and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides; Amphoteric surfactants; Silicone surfactants Surfactants such as active agents can be used, and they may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. A silane coupling agent is preferably used.

As the melamine compound, all or part (at least 2) is an alkyl-etherified compound.
Here, the alkyl group constituting the alkyl ether includes a methyl group, an ethyl group and a butyl group, which may be the same or different. In addition, methylol groups that are not alkyl-etherified may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
Among these, alkyl-etherified melamine such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable in terms of solubility in solvents and resistance to crystal precipitation from the polymerizable resin composition.

In the polymerizable resin composition of the present invention, the amount of optional components other than the polymerization initiator (A) and the polymerizable resin (B) (excluding inorganic compounds, coloring materials, and solvents) is determined according to the purpose of use. Although it is appropriately selected and not particularly limited, the total amount is preferably 50 parts by mass or less with respect to 100 parts by mass of the polymerizable resin (B).

The polymerizable resin composition of the present invention can be cured by heating, irradiation with energy rays, or the like. The cured product is formed into an appropriate shape according to the application. For example, when forming a film-like cured product, the polymerizable resin composition of the present invention is applied by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion. It can be applied on supporting substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, plastics and the like. In addition, once applied onto a supporting substrate such as a film, it can be transferred onto another supporting substrate, and there are no restrictions on the method of application.

Among the polymerizable resin compositions of the present invention, a photosensitive resin composition that is cured by irradiation with energy rays is preferable because it shortens the process time and causes less damage to peripheral members due to heating.

Examples of the energy ray light source used for curing the polymerizable resin composition of the present invention include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, and carbon lamps. Electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., high energy such as electron beams, X-rays, and radiation. Rays can be used, but ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm are preferably used.

Furthermore, by using laser light as the exposure light source, the laser direct writing method, which forms images directly from digital information such as computers without using a mask, improves not only productivity but also resolution and positional accuracy. As the laser light, light with a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser , various semiconductor lasers and YAG lasers that emit light in the visible to infrared region can also be used. When using these laser beams, a sensitizing dye that absorbs in the visible to infrared region is preferably added.

In the method for producing the cured product of the present invention, it is usually necessary to heat after the irradiation with the energy beam, and heating at about 40 to 150° C. is preferable in terms of curing rate.

The polymerizable resin composition of the present invention is a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; Color filters for CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; solder resists; resists for making color filters for various display applications or forming their structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; encapsulating electrical and electronic components. magnetic recording materials; micromechanical components; waveguides; optical switches; plating masks; etching masks; color test systems; holographic recording materials; image recording materials; fine electronic circuits; decolorizing materials; decolorizing materials for image recording materials; It can be used in various applications such as resist materials; photoresist materials for UV and visible laser direct imaging systems; photoresist materials or protective films used for forming dielectric layers in the sequential lamination of printed circuit boards; is not particularly limited.

The polymerizable resin composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for the purpose of forming projections for vertically aligned liquid crystal display elements. In particular, it is useful as a polymerizable resin composition for simultaneously forming projections and spacers for vertical alignment type liquid crystal display devices.

The spacer for a liquid crystal display panel described above is prepared by (1) forming a coating film of the polymerizable resin composition of the present invention on a substrate, (2) applying an energy beam through a mask having a predetermined pattern on the coating film. (3) baking after exposure; (4) developing the film after exposure; and (5) heating the film after development.

The polymerizable resin composition of the present invention to which a colorant is added is suitably used as a resist forming each pixel such as RGB in a color filter, or as a black matrix resist forming partition walls of each pixel. Furthermore, in the case of a black matrix resist to which an ink-repellent agent is added, it is preferably used for partition walls for ink-jet type color filters having a profile angle of 50° or more. As the ink repellent agent, a fluorosurfactant and a composition containing the fluorosurfactant are preferably used.

When it is used for the partition wall for the ink-jet type color filter, the partition wall formed from the polymerizable resin composition of the present invention partitions the transfer material, and droplets are applied to the partitioned recesses on the transfer material by an inkjet method. The optical element is manufactured by a method of application to form an image area. In this case, it is preferable that the droplet contains a coloring agent and the image area is colored. It has at least partition walls separating each pixel group and each colored region of the pixel group.

The polymerizable resin composition of the present invention can also be used as a composition for protective films or insulating films. In this case, an ultraviolet absorber, an alkylated modified melamine and/or an acrylic modified melamine, a mono- or bifunctional (meth)acrylate monomer containing an alcoholic hydroxyl group in the molecule, and/or silica sol can be contained.

The insulating film is used for the insulating resin layer in a laminate in which the insulating resin layer is provided on a peelable support base material, and the laminate can be developed with an alkaline aqueous solution, and the insulating resin layer is preferably 10 to 100 μm.

The polymerizable resin composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound. The photosensitive paste composition can be used to form fired patterns such as partition wall patterns, dielectric patterns, electrode patterns and black matrix patterns of plasma display panels.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

Examples 1 and 2 show synthesis examples of the compound (polymerization initiator) of the present invention, and Examples 3 to 8 and Comparative Examples 1 and 2 are preparation examples and evaluation of the present invention and comparative polymerizable resin compositions. indicates

[Example 1] Compound no. Synthesis of 1 <Step 1> Synthesis of Intermediate 1A Nitrogen flow to a 100 ml four-neck flask, 4.87 g (3.0 × 10 ^-2 mol) of the following indole derivative 1 and 8.30 g (6.0 g) of potassium carbonate ×10 ⁻² mol) and 30.0 g of dimethylformamide were added, and the mixture was stirred at 5° C. on an ice bath. 5.61 g (3.6×10 ⁻² mol) of ethyl iodide was added dropwise thereto. After completion of dropping, the mixture was heated and stirred at 60° C. for 12 hours on an oil bath. After cooling to room temperature, it was poured into 50.0 g of deionized water. The solution was transferred to a separating funnel, and ethyl acetate was added for extraction. The organic layer was washed twice with ion-exchanged water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. 5.26 g of the following intermediate 1A was obtained with a yield of 92%.

<Step 2> Synthesis of Intermediate 1B A 100 ml four-necked flask was flushed with nitrogen, 4.95 g (2.6 × 10 ^-2 mol) of Intermediate 1A and 0.08 g of dichloroethane were added, and the reaction was performed at 5 °C on an ice bath. Agitation was performed. 7.28 g (5.46×10 ⁻² mol) of aluminum chloride was added thereto. Further 4.42 g (2.86×10 ⁻² mol) of phenylacetyl chloride were added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours. After cooling to room temperature, it was poured into 20.0 g of 5% hydrochloric acid. The solution was transferred to a separatory funnel for oil-water separation. The organic layer was washed twice with ion-exchanged water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was isolated by silica gel column chromatography (solvent: chloroform). 2.15 g of the following intermediate 1B was obtained as a pale yellow powder in a yield of 27%.

<Step 3> Synthesis of Intermediate 1C A 50 ml four-necked flask was flushed with nitrogen, 1.02 g (3.3×10 ⁻³ mol) of Intermediate 1B was added with 6.40 g of chloroform, and the reaction was performed at 5° C. on an ice bath. Agitation was performed. 0.58 g (3.36×10 ⁻³ mol) of bromine was added dropwise thereto. After the dropwise addition was completed, the mixture was stirred at 5°C on an ice bath, and the reaction was tracked by HPLC. After confirming the consumption of the raw materials, the mixture was cooled to 5°C in an ice bath. An aqueous sodium thiosulfate solution was added dropwise thereto. After oil-water separation, the organic layer was washed with ion-exchanged water three times. The organic layer was evaporated under reduced pressure. A black oil was obtained in 2.12 g. The resulting black oil was dissolved in chloroform, washed with 5% HCl, washed with water twice, dried over anhydrous sodium sulfate, and concentrated by an evaporator. The residue was isolated and purified with a silica gel column (solvent: chloroform). Intermediate 1C below was obtained as a light gray powder, 0.25 g, 19% yield.

<Step 4> Compound No. Synthesis of 1 0.096 g (2.5×10 ⁻⁴ mol) of intermediate 1C and 0.42 g of THF were added to a 50 ml four-neck flask under nitrogen flow, and the mixture was stirred at 5° C. on an ice bath. 50.06 g (3.25×10 ⁻⁴ mol) of the following imidazole compound 1 was added dropwise thereto. After completion of dropping, the mixture was stirred at room temperature for 12 hours. White crystals precipitated and were collected by filtration. Compound no. 0.11 g of 1 was obtained as a fine powder in a yield of 78%.

[Example 2] Compound no. Synthesis of 2

<Step 1> Synthesis of Intermediate 2A A 50 ml four-necked flask was flowed with nitrogen, 0.096 g (2.5 × 10 ^-4 mol) of Intermediate 1C and 0.36 g of THF were added, and the reaction was performed at 5 °C on an ice bath. Agitation was performed. The following imidazole body 2 was added dropwise thereto. After completion of dropping, the mixture was stirred at room temperature for 5 hours. White crystals precipitated and were collected by filtration. 0.10 g of Intermediate 2A was obtained as the Br salt compound as a pale yellow powder in a yield of 83%.

<Step 2> Compound No. Synthesis of 2 0.099 g (2.1×10 ⁻⁴ mol) of Intermediate 2A and 1.48 g of chloroform were added to a 50 mL eggplant flask and dissolved at room temperature. This was transferred to a separating funnel, and salt exchange reaction was carried out three times with an aqueous solution prepared by dissolving 0.107 g (3.15×10 ⁻⁴ mol) of tetraphenylboronium sodium salt in ion-exchanged water. After the organic layer was concentrated under reduced pressure using an evaporator, 5 g of THF was added, and dispersion washing was performed at room temperature. The crystals were collected by filtration, and the target compound No. 2 was obtained. 0.11 g of 2 was obtained in 74% yield.

compound no. 1 and compound no. The melting point and 1H-NMR of 2 were measured. The results are shown in [Table 1] and [Table 2], respectively.

[Evaluation Example 1 and Comparative Evaluation Example 1] Evaluation of Optical Resolution Compound No. 1 and Comparative Compound No. 1 below were adjusted to 1.0×10 ⁻⁴ mol of acetonitrile solution and placed in a lidded quartz cell. The sample was irradiated with light from an ultra-high pressure mercury lamp at 100 mJ/cm ² , 500 mJ/cm ² and 1000 mJ/cm ² (accumulated light intensity at 365 nm) to examine the decomposability. For the evaluation of degradability, the amount of decomposition was expressed in % by setting the peak at the time of non-irradiation to 0 using HPLC. The results are shown in [Table 3].
HPLC: manufactured by Hitachi High Technology, UV detector: Chrom master5430
Developing solvent: acetonitrile/water/ammonium acetate = 90/10/0.2
Flow rate: 1ml/min
Column: Inertsil ODS-2
Column temperature: 40°C
Detection: 254nm

From the results of [Table 3] above, the compound of the present invention has high decomposability to UV light, generates a large amount of base by decomposition, and exhibits highly sensitive curability in a polymerizable resin composition. It became clear that it was.

[Examples 4 to 8 and Comparative Examples 1 and 2] Evaluation of photosensitive resin composition Photosensitive resin composition No. 1 was prepared with the formulation described in [Table 4]. 1 and no. 2 and comparative photosensitive resin composition No. 1 and no. got 2. In addition, the numerical value of the composition in a table|surface represents a mass part. The symbols in the table represent the following components.
A-1: Compound No. 1
A-2: Compound No. 2
A'-3: Comparative compound No. 1
A'-4: Comparative compound No. 2
B-1: EPPN-201 (phenol novolac type epoxy resin, epoxy equivalent 193 g / eq., manufactured by Nippon Kayaku Co., Ltd.)
B-2: TRR-5010G (cresol novolac type phenolic resin, hydroxyl equivalent 120 g/eq., Mw = 8,000, manufactured by Asahi Organic Chemicals Industry Co., Ltd.)
C-1: FZ-2122 (polyether-modified polysiloxane, manufactured by Dow Corning Toray Co., Ltd.) D-1: Cyclopentanone (solvent)

[Evaluation of photosensitive resin composition and cured product]
Photosensitive resin composition No. 1, photosensitive resin composition No. 2 and comparative photosensitive resin composition No. 1 and the cured product, the line width sensitivity and the residual film rate of the cured product were evaluated by the following procedure. The results are shown in [Table 5].

[Method for preparing evaluation sample and evaluation method]
Photosensitive resin composition No. 1, photosensitive resin composition No. 2 and comparative photosensitive resin composition No. 1 (coating amount of about 2.0 cc) was applied to a glass substrate with a spin coater (500 rpm × 2 seconds → 1800 rpm × 15 seconds → slope × 5 seconds), and pre-baked on a hot plate (90 ° C. × 120 seconds).
After that, divisional exposure was performed using a Topcon exposure machine (60 mJ/cm ² , 120 mJ/cm ² , gap: 20 μm, illuminance: 20.0 mW/cm ² ).
After exposure, it was post-baked on a hot plate (120°C x 5 minutes), and then developed with PGMEA (temperature: 23°C): 200 rpm x 10 seconds → IPA cleaning (200 rpm x 10 seconds → drying: 500 rpm x 5 seconds). ).
With respect to the obtained samples, the line width and residual film ratio of a pattern with a mask opening of 20 μm at each exposure dose were measured. The results are shown in Table 5 below. Photosensitive resin composition No. of Evaluation Examples 2 and 3 in Table 5. 1, and photosensitive resin composition Nos. 4 and 5 of Evaluation Examples 4 and 5; 2 is included in the scope of the present invention. Comparative photosensitive resin composition No. of Comparative Evaluation Examples 2 and 3 in Table 5. 1 is outside the scope of the present invention.
The larger the line width, the higher the sensitivity. When the exposure amount is 60 mJ/cm ² , the line width is preferably 12 μm or more, and when the exposure amount is 120 mJ/cm ² , the line width is 20 μm or more. is preferred.
The higher the residual film ratio, the higher the curability. When the exposure dose is 60 mJ/cm ² , the residual film ratio is preferably 30% or more, and when the exposure dose is 120 mJ/cm ² , the residual film ratio. A rate of 45% or more is preferred.

From the results shown in [Table 5] above, the photosensitive resin composition of the present invention exhibits a large line width (high sensitivity) and a high residual film ratio (high curability) compared to the comparative photosensitive resin composition. Therefore, it is clear that the compound of the present invention is excellent as a polymerization initiator.

<Transparency>
Photosensitive resin composition No. 1, photosensitive resin composition No. 2 and comparative photosensitive resin composition No. 2, (coating amount about 2.0 cc) was applied to each glass substrate with a spin coater (500 rpm × 2 seconds → 1800 rpm × 15 seconds → slope × 5 seconds) and pre-baked on a hot plate (90 ° C. x 120 seconds).
After that, the entire surface was exposed using a Topcon exposure machine (1,000 mJ/cm ² , gap: 20 μm, illuminance: 20.0 mW/cm ² ).
After exposure, post-baking was performed on a hot plate (120° C.×5 minutes), and the transmittance of light with a wavelength of 400 nm was compared. The transmittance was measured with a spectrophotometer U-3900 manufactured by Hitachi High-Tech Science. The results are shown in Table 6 below. Photosensitive resin composition No. 6 of Evaluation Examples 6 and 7 in Table 6. 1 and 2 are included in the scope of the present invention. Comparative photosensitive resin composition No. of Comparative Evaluation Example 4 in Table 6. 2 is outside the scope of the present invention.

From the results in [Table 6] above, it is clear that the photosensitive resin composition of the present invention is superior in transparency to the comparative photosensitive resin composition.

[Production Example 1] Carboxylic acid resin No. Preparation of 1 184 g 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane, 58 g acrylic acid, 0.26 g 2,6-di-tert-butyl-p-cresol, 0 A reaction vessel was charged with 11 g of tetra-n-butylammonium bromide and 105 g of PGMEA and stirred at 120° C. for 16 hours to obtain a reaction solution. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added to the cooled reaction solution and stirred at 120° C. for 4 hours. Then, 20 g of tetrahydrophthalic anhydride was added and stirred at 120° C. for 4 hours, 100° C. for 3 hours, 80° C. for 4 hours, 60° C. for 6 hours and 40° C. for 11 hours. After that, carboxylic acid resin No. PGMEA was added so that the content of carboxylic acid resin No. 1 was 45% by mass. A PGMEA solution of 1 was obtained (Mw=5000, Mn=2100, acid value (solid content) 92.7 mgKOH/g).

[Example 2-1 and Comparative Example 2-1] Preparation of photosensitive resin composition Photosensitive resin composition No. 2 was prepared according to the formulation described in [Table 7]. 2-1 and comparative photosensitive resin composition No. 2-1 to 2-2 were obtained. In addition, the numerical value in Table 7 represents a mass part. B-1, C-1 and D-1 in Table 7 are as described above. In addition, comparative compound No. in Table 7. 3 and No. 4 is the following compound.

[Method for preparing evaluation sample and evaluation method]
Photosensitive resin composition No. 2-1, and comparative photosensitive resin composition No. Each of 2-1 and 2-2 (coating amount of about 4.0 cc) was applied to a glass substrate by a spin coater (500 rpm×2 sec→900 rpm×10 sec→slope×5 sec) to form a coating film. A step tablet was placed on the formed coating film and exposed to ultraviolet light (365 nm) using an LED exposure machine (3000 mJ/cm ² , illuminance: 50.0 mW/cm ² ). After exposure, it was baked on a hot plate (100° C.×20 minutes), developed with PGMEA (30 seconds), and washed with IPA (isopropyl alcohol) (10 seconds). With respect to the obtained samples, the number of stages in which the film remained after development was recorded. The higher the number of stages, the better the sensitivity.

As is clear from Table 8, a photosensitive resin composition containing an epoxy resin, a carboxylic acid resin (latent curing agent) and the compound of the present invention has excellent curability. From this, it is clear that the compound of the present invention is excellent as a polymerization initiator for a composition containing an epoxy resin and a carboxylic acid resin (latent curing agent).

[Example 3-1 and Comparative Example 3-1] Preparation of photosensitive resin composition Photosensitive resin composition No. 1 was prepared according to the formulation described in [Table 9]. 3-1, and comparative photosensitive resin composition No. 3-1 and 3-2 were prepared. Numerical values for formulations in the table represent parts by mass. C-1 in Table 9 is as described above.

[Method for preparing evaluation sample and evaluation method]
Photosensitive resin composition No. 3-1, and comparative photosensitive resin composition No. 3-1 and 3-2 (coating amount of about 4.0 cc) are each applied to a glass substrate with a spin coater (500 rpm × 2 seconds → 1000 rpm × 15 seconds → slope × 5 seconds) to form a coating film. The coated film was pre-baked on a hot plate (100° C.×10 minutes). The pre-baked coating film was subjected to divisional exposure to ultraviolet light (240 nm to 405 nm) using a Topcon exposure machine (1000 mJ/cm ² or 3000 mJ/cm ² , gap: 20 µm, illuminance: 20.0 mW/cm ² ). After exposure, the coating film was developed with an aqueous potassium carbonate solution at 23° C. (200 rpm×10 seconds) and dried at 500 rpm for 5 seconds. The dried coating film was post-baked at 230° C. for 30 minutes in an oven to obtain an evaluation sample. The line width and residual film ratio of a pattern with a mask opening of 20 μm were measured for each exposure amount of the obtained evaluation samples. Specifically, the results are shown in Table 10. The line width of the pattern was measured using an optical microscope (keyence microscope). The residual film ratio was calculated by measuring the initial film thickness and the film thickness after post-baking, and calculating the obtained values based on the following formula. Coating thickness was measured using a DeKTak contact thickness gauge. In this specification, the line width and the residual film ratio were all measured by the same method.

Remaining film ratio (%) = film thickness of coating film after post-baking/film thickness of initial coating film

As is clear from Table 10, the photosensitive resin composition of Example 3-1 has a large line width and a high residual film ratio. From this, it is clear that the compound of the present invention acts as a highly sensitive polymerization initiator in the acrylic polymerizable resin composition.

Claims (8)

A compound represented by the following general formula (1).

(In the formula, X is the following (a1), (a2), (a3), (a4), (a5), (a6), (a7), (a8), (a9), (a10), ( a11), (a12), (a13), (a14), (a15), (a16) or a group represented by (a17),
R ¹ and R ² each independently represent a hydrogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a thiol group, a halogen atom, an unsubstituted or substituted hydrocarbon having 1 to 20 carbon atoms; group, or a group having 2 to 20 carbon atoms containing an unsubstituted or substituted heterocyclic ring,
R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a cyano group, a nitro group, -OR ⁹ , -COOR ⁹ , -CO-R ⁹ , -SR ⁹ , a halogen atom, represents an unsubstituted or substituted hydrocarbon group of 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group of 2 to 20 carbon atoms,
one or more of R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a cyano group, a nitro group, -OR ⁹ , -COOR ⁹ , -CO-R ⁹ , -SR ⁹ , halogen atom, halogenated alkyl is the basis,
R ⁹ is a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring containing 2 to 20 carbon atoms represents the group of
R ⁵ and R ⁶ , R ⁶ and R ⁷ and R ⁷ and R ⁸ may together form a ring,
R ⁴ is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. represent,
An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a coefficient that keeps the charge neutral. )

(Wherein, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ¹¹ in the above (a1) , R ¹² and R ¹³ may form a ring together, and the double line consisting of a solid line and a broken line in (a1) above represents a single bond or a double bond,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently the same as R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) represents the group of
Ar ¹ and Ar ² represent an unsubstituted or substituted aromatic ring,
when a plurality of R ¹¹ are present in one group, the plurality of R ¹¹ are the same or different,
When one group has a plurality of R ¹² , the plurality of R ¹² are the same or different,
m and n each independently represents an integer of 1 to 12,
* represents a bond. ) The compound according to claim 1 , wherein R ¹ in the general formula (1) is an unsubstituted or substituted aryl group having 6 to 20 carbon atoms. A polymerization initiator containing the compound according to claim 1 or 2 . A polymerizable resin composition comprising the polymerization initiator (A) according to claim 3 and a polymerizable resin (B). 5. The polymerizable resin composition according to claim 4 , wherein the polymerizable resin (B) is an epoxy resin (B1) or a phenol resin (B2). A photosensitive resin composition comprising the polymerization initiator (A) according to claim 3 and a polymerizable resin (B). A cured product obtained from the polymerizable resin composition according to claim 4 or 5 or the photosensitive resin composition according to claim 6 . A method for producing a cured product, comprising the step of irradiating the polymerizable resin composition according to claim 4 or 5 or the photosensitive resin composition according to claim 6 with an energy ray.