WO2015125745A1 - Novel compound, photo-acid generator comprising said compound, and photosensitive resin composition comprising said photo-acid generator - Google Patents

Abstract

A compound represented by formula (1) [in formula (1), the ring Ar represents an aromatic ring, a heterocyclic ring or the like; R₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an arylcarbonyl group or the like; R₂ and R₃ independently represent a hydrogen atom, an aromatic residue or the like; R₄ represents a hydrogen atom or an aliphatic hydrocarbon residue; X₁ and X₂ independently represent a nitrogen atom or the like; and Y₁ and Y₂ independently represent a sulfur atom, an oxygen atom, a selenium atom or the like).

Description

Novel compound, photoacid generator containing the compound, and photosensitive resin composition containing the photoacid generator

The present invention relates to a novel compound, a photoacid generator containing the compound, and a photosensitive resin composition containing the photoacid generator.

Photosensitive resin compositions have been put into practical use in the fields of printing inks, paints, coatings, various resist inks and the like from the viewpoints of energy saving and high production efficiency. Many of these photosensitive resin compositions use photo radical polymerization reactions of compounds having unsaturated double bonds such as acrylate compounds, but on the other hand, photoacid generation occurs in epoxy compounds (resins) and the like. Studies have also been actively conducted on the photocationic polymerization reaction using a photosensitive resin composition containing an agent. The method of photocationic polymerization of cationically polymerizable compounds such as epoxy compounds by irradiating active energy rays such as ultraviolet rays and electron beams is compared with the method of photoradical polymerization of acrylate compounds by irradiation of active energy rays. It has various characteristics that are advantageous compared with a method of curing by radical photopolymerization, such as small curing shrinkage and no influence of oxygen during curing.

Examples of the photoacid generator contained in the photocationically polymerizable photosensitive resin composition include ionic light such as triarylsulfonium salts (see Patent Document 1) and phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2). Acid generators are known. However, ionic photoacid generators tend to lack compatibility (solubility) with hydrophobic cationic polymerizable compounds and solvents used in photosensitive resin compositions. A photoacid generator has also been studied. The use of a nonionic photoacid generator not only improves the above problems, but nonionic photoacid generators generally have absorption in a longer wavelength region than ionic photoacid generators. In addition, an effect of excellent sensitivity is expected when the photosensitive resin composition is cured using i-line or g-line such as medium pressure / high pressure mercury lamp (see Patent Document 3).
However, the acid generation quantum yield of conventionally known nonionic photoacid generators is about 0.1 to 0.3, and a highly sensitive nonionic photoacid generator having a high acid generation quantum yield is high. Development is desired.

Japanese Patent Laid-Open No. 50-151997 JP 09-118663 A Japanese Patent Laid-Open No. 10-213899

It is an object of the present invention to provide a highly sensitive nonionic photoacid generator having high solubility in hydrophobic cationically polymerizable compounds and solvents and having a high acid generation quantum yield for i-line and g-line.

As a result of diligent efforts to solve the above problems, the present inventors have found that the above problems can be solved by using a photoacid generator containing a novel compound having a specific structure, and the present invention is completed. It came to.
That is, the present invention
(1) The following formula (1)

(In the formula (1), the ring Ar is a benzene ring, naphthalene ring, thiophene ring, benzothiophene ring, furan ring, benzofuran ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, imidazolidinium ring, benzoimidazolium. Represents a ring, a cyclopentene ring, a cyclohexene ring, a cyclopentene ring, an indole ring or a pyrrole ring.
R ₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group, an alkoxysulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an arylcarbonyl group.
R ₂ and R ₃ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl Represents a group, an acyl group or a trimethylsilyl group.
R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue.
X ₁ represents CR ₅ or a nitrogen atom.
R ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group. , R ₂ and R ₅ may be linked to form a ring.
X ₂ represents CR ₆ or a nitrogen atom.
R ₆ represents a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group or acyl group. , R ₃ and R ₆ may be linked to form a ring.
Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom, a selenium atom, or CR ₇ R ₈ .
R ₇ and R ₈ represent a hydrogen atom or an aliphatic hydrocarbon residue. )
A compound represented by
(2) The following formula (2)

(In the formula (2), R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y ₂ are R ₁ to R ₄ , X ₁ , X ₂ , in the formula (1) described in (1), Y ₁ and Y ₂ have the same meaning, and R ₉ to R ₁₂ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amido group, an alkoxy group group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or the .Y ₃ representing the acyl group represents a sulfur atom, an oxygen atom or a selenium atom.)
The compound according to item (1), which is represented by:
(3) The compound according to item (2), wherein R ₁ is an alkylsulfonyl group having 1 to 4 carbon atoms,
(4) The compound according to item (2), wherein X ₁ and X ₂ are nitrogen atoms,
(5) The compound according to item (2), wherein Y ₁ to Y ₃ are each independently a sulfur atom or an oxygen atom,
(6) The following formula (3)

(In the formula (3), R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y ₂ are R ₁ to R ₄ , X ₁ , X ₂ , in the formula (1) described in (1), Y ₁ and Y ₂ have the same meaning, R ₁₃ to R ₁₈ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amido group, an alkoxy group A group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group.)
The compound according to item (1), which is represented by:
(7) The compound according to item (6), wherein R ₁ is an alkylsulfonyl group having 1 to 4 carbon atoms,
(8) X ₁ is CR ₅ and R ₂ and R ₅ are linked to form a benzene ring, and X ₂ is CR ₆ and R ₃ and R ₆ are linked The compound according to item (6), which forms a benzene ring,
(9) The compound according to item (6), wherein Y ₁ and Y ₂ are a sulfur atom or an oxygen atom,
(10) A photoacid generator containing the compound according to any one of (1) to (9) above,
(11) A photosensitive resin composition comprising the photoacid generator according to (10) above and a compound polymerizable by the photoacid generator,
(12) A cured product obtained by curing the photosensitive resin composition according to (11) above,
About.

By using the novel compound having a specific structure represented by the formula (1) of the present invention, it has high solubility in a hydrophobic cationically polymerizable compound or a solvent, and has a high acid generation quantum yield with respect to active energy rays. It is possible to provide a highly sensitive nonionic photoacid generator having

FIG. 1 is a ¹ H-NMR spectrum of a sample containing propylene oxide alone and a sample obtained by adding methanesulfonic acid to propylene oxide. FIG. 2 shows a sample obtained by dissolving the compound represented by the formula BT-OMs obtained in Example 1 and propylene oxide in deuterated chloroform, and a sample irradiated with ultraviolet rays having a wavelength of 365 nm. ¹ H-NMR spectrum of FIG. 3 is a ¹ H-NMR spectrum of a sample prepared by dissolving a compound represented by the formula BT-OMs in deuterated chloroform. FIG. 4 is a ¹ H-NMR spectrum of a sample prepared by dissolving propylene oxide in deuterated chloroform.

The present invention is described in detail below.
The compound of the present invention has a structure represented by the following formula (1). A feature of the compound represented by the formula (1) is that an acid induced from a substituent represented by R ₁ O in the formula when the compound is irradiated with active energy rays such as i-line and g-line. In this case, the eliminated acid can function as a polymerization initiator for the cationically polymerizable compound.

In formula (1), ring Ar is a benzene ring, naphthalene ring, thiophene ring, benzothiophene ring, furan ring, benzofuran ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, imidazolidinium ring, benzoimidazolium ring , Cyclopentene ring, cyclohexene ring, cyclopentene ring, indole ring or pyrrole ring.
The ring Ar may have a substituent, and specific examples of the substituent which may be present include an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, Examples include amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group. The term “ring Ar having a substituent” as used herein means a ring structure in which a hydrogen atom on the ring Ar is substituted with the above substituent. There may be a plurality of substituents, and the plurality of substituents may be different from each other.
The heterocyclic ring represented by the ring Ar may form a cyclic ketone or a cyclic thioketone.

The aromatic residue as a substituent that the ring Ar may have means an aromatic ring or a group obtained by removing one hydrogen atom from a condensed ring containing an aromatic ring, and the aromatic residue is a substituent. You may have. Specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, perylene ring, terylene ring, indene ring, azulene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrazole ring, pyrazolidine ring, Thiazolidine ring, oxazolidine ring, pyran ring, chromene ring, pyrrole ring, pyrrolidine ring, benzimidazole ring, imidazoline ring, imidazolidine ring, imidazole ring, triazole ring, triazine ring, diazole ring, indoline ring, thiophene ring, thienothiophene ring , Furan ring, oxazole ring, oxadiazole ring, thiazine ring, thiazole ring, indole ring, benzothiazole ring, benzothiadiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, indolenine ring, Nzoindorenin ring, a quinoline ring, a quinazoline ring, include a fluorene ring and a carbazole ring, and is preferably an aromatic ring or a group obtained by removing one hydrogen atom from a condensed ring containing an aromatic ring having 4 to 20 carbon atoms.

Examples of the aliphatic hydrocarbon residue as a substituent that the ring Ar may have include a saturated or unsaturated, linear, branched or cyclic alkyl group, and the aliphatic hydrocarbon residue is It may have a substituent. The aliphatic hydrocarbon residue has preferably 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of these aliphatic hydrocarbon residues include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl. Group, n-hexyl group, n-heptyl 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 Group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, cyclohexyl group, vinyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl group, isohexenyl group, cyclohexenyl Group, cyclopentadienyl group, ethynyl group, propynyl group, pentynyl group, hexynyl group, isohexynyl group, cyclohexyl group Group, and the like. Examples of the cyclic alkyl group include a cycloalkyl group having 3 to 8 carbon atoms.

Examples of the halogen atom as a substituent that the ring Ar may have include fluorine, chlorine, bromine, iodine and the like.
Examples of the amide group as a substituent that the ring Ar may have include an amide group, an acetamide group, and an alkylamide group. Specific examples thereof include an amide group, an acetamido group, an N-methylamide group, and an N-ethylamide group. Group, N- (n-propyl) amide group, N- (n-butyl) amide group, N-isobutylamide group, N- (sec-butylamide) group, N- (t-butyl) amide group, N, N -Dimethylamide group, N, N-diethylamide group, N, N-di (n-propyl) amide group, N, N-di (n-butyl) amide group, N, N-diisobutyramide group, N-methylacetamide Group, N-ethylacetamide group, N- (n-propyl) acetamide group, N- (n-butyl) acetamide group, N-isobutylacetamide group, N- (sec-butyl) acetate Amide group, N- (t-butyl) acetamide group, N, N-dimethylacetamide group, N, N-diethylacetamide group, N, N-di (n-propyl) acetamide group, N, N-di (n- Butyl) acetamide group, N, N-diisobutylacetamide group, phenylamide group, naphthylamide group, phenylacetamide group and naphthylacetamide group.

Examples of the alkoxy group as a substituent that the ring Ar may have include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group. Etc.
Examples of the aryloxy group as a substituent that the ring Ar may have include a phenoxy group and a naphthoxy group.
Examples of the alkoxycarbonyl group as a substituent that the ring Ar may have include an alkoxycarbonyl group having 1 to 10 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentene. A tooxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group.

The arylcarbonyl group as a substituent that the ring Ar may have represents, for example, a group in which an aryl group such as benzophenone or naphthophenone and carbonyl are linked.
Examples of the acyl group as a substituent that the ring Ar may have include, for example, an alkylcarbonyl group having 1 to 10 carbon atoms, an arylcarbonyl group, etc., preferably an alkylcarbonyl group having 1 to 4 carbon atoms, Specific examples include an acetyl group, a propionyl group, a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a benzoyl group, and a naphthoyl group.
A plurality of substituents on the ring Ar may be bonded to each other to form a ring. Examples of the ring that may be formed are the same as the specific examples of the aromatic ring described in the paragraph of the aromatic residue as a substituent that the ring Ar of the formula (1) may have.
As the substituent that the aromatic residue and the aliphatic hydrocarbon residue as the substituent that the ring Ar may have, the ring Ar of the formula (1) may have. The same thing as a substituent is mentioned.

The ring Ar in the formula (1) is preferably a heterocyclic ring containing a sulfur atom, and more preferably a thiophene ring. Moreover, a benzene ring is preferable as a ring formed by bonding substituents on the ring Ar.

In Formula (1), R ₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group, an alkoxysulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an arylcarbonyl group.
Examples of the aliphatic hydrocarbon residue represented by R ₁ include the same as those described in the paragraph of the aliphatic hydrocarbon residue as a substituent that the ring Ar of formula (1) may have.
As the alkyl group in the alkylsulfonyl group and the alkylcarbonyl group represented by R ₁ in the formula (1), described in the paragraph of the aliphatic hydrocarbon residue as a substituent that the ring Ar in the formula (1) may have. The same as the saturated or unsaturated, linear, branched or cyclic alkyl group, and halogenated alkyl groups such as fluorinated alkyl group, alkyl iodide group, alkyl chloride group and alkyl iodide group are also included. It is included in the category of the alkyl group in the alkylsulfonyl group and the alkylcarbonyl group.
The alkoxysulfonyl group represented by R _{1 in the} formula (1) and the alkoxy group in the alkoxycarbonyl group are the same as those described in the paragraph of the alkoxy group as a substituent that the ring Ar in the formula (1) may have. Things.
As the aryl group in the arylsulfonyl group and arylcarbonyl group represented by R ₁ in the formula (1), the aryl group described in the section of the arylcarbonyl group as a substituent which the ring Ar in the formula (1) may have The same thing is mentioned.
R _{1 in} formula (1) is preferably an alkylsulfonyl group, more preferably an alkylsulfonyl group having 1 to 8 carbon atoms, and still more preferably an alkylsulfonyl group having 1 to 4 carbon atoms. .

In formula (1), R ₂ and R ₃ are each independently a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, an aryloxy group, Represents an alkoxycarbonyl group, an arylcarbonyl group, an acyl group or a trimethylsilyl group;
As the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by R ₂ and R _{3 in} the formula (1), An aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group as a substituent that the ring Ar in formula (1) may have And the same as those described in the item of acyl group.
R ₂ and R ₃ in Formula (1) are preferably each independently an aromatic residue, more preferably a benzene ring residue (phenyl group). As will be described later, when X ₁ and X ₂ are CR ₅ and CR ₆ respectively, R ₂ and R ₅ are linked to form a ring, and R ₃ and R ₆ are linked. It is preferable to form a ring, and it is more preferable that both are benzene rings.

In formula (1), R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue.
The aliphatic hydrocarbon residue represented by R ₄ in the formula (1) is the same as that described in the paragraph of the aliphatic hydrocarbon residue as a substituent that the ring Ar in the formula (1) may have. Things.
R ₄ in Formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula (1), X ₁ represents CR ₅ or a nitrogen atom, and R ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group. Represents an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group. When X ₁ is CR ₅ , R ₂ and R ₅ may be linked to form a ring, and the formed ring may have a substituent.
As the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by R ₅ , ring Ar in formula (1) is As described in the paragraphs of the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group as substituents that may have The same thing is mentioned.
When X ₁ is CR _5, the ring formed by R ₂ and R ₅ is the aromatic ring described in the paragraph of the aromatic residue as the substituent that the ring Ar of formula (1) may have Examples of the substituent that the ring formed may have may be the same as those described in the section of the substituent that the ring Ar of formula (1) may have. The same thing is mentioned.

In the formula (1), X ₂ represents CR ₆ or a nitrogen atom, and R ₆ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group. Represents an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group. When X ₂ is CR ₆ , R ₃ and R ₆ may be linked to form a ring, and the formed ring may have a substituent.
As the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by R ₆ , ring Ar in formula (1) is As described in the paragraphs of the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group as substituents that may have The same thing is mentioned.

When X ₂ is CR _6, the ring formed by R ₃ and R ₆ is the aromatic ring described in the section of the aromatic residue as the substituent that the ring Ar of formula (1) may have Examples of the substituent that the ring formed may have may be the same as those described in the section of the substituent that the ring Ar of formula (1) may have. The same thing is mentioned.
As X < ₁ > and X < ₂ > in Formula (1), it is preferable that both are nitrogen atoms. When X ₁ and X ₂ are CR ₅ and CR ₆ , R ₂ and R ₅ are connected to form a ring, and R ₃ and R ₆ are connected to form a ring. It is preferable that both of the rings formed are benzene rings.

In formula (1), Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom, a selenium atom or CR ₇ R ₈ , and R ₇ and R _{8 each} represent a hydrogen atom or an aliphatic hydrocarbon residue.
Examples of the aliphatic hydrocarbon residue represented by R ₇ and R ₈ are the same as those described in the paragraph of the aliphatic hydrocarbon residue as a substituent that the ring Ar of formula (1) may have. Can be mentioned.
As Y < ₁ > and Y < ₂ > in Formula (1), it is preferable that it is a sulfur atom or an oxygen atom each independently, and it is more preferable that both are sulfur atoms.

As the compound represented by the formula (1), a compound represented by the following formula (2) is preferable.

Wherein _{(2), R 1 ~ R} 4, X 1, X 2, Y 1 and _{Y 2, R} 1 _{~ R 4} in the formula _{(1), X 1, X} 2, Y 1 and _{Y 2} means the same The preferred examples are also the same.
In the formula (2), R ₉ to R ₁₂ are each independently a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, an aryloxy group Represents an alkoxycarbonyl group, an arylcarbonyl group or an acyl group.
As the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by R ₉ to R _{12 in} the formula (2), Aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group specifically exemplified as the substituent that ring Ar in formula (1) may have , Arylcarbonyl group and acyl group are the same.

R ₉ to R ₁₂ in Formula (2) are preferably a hydrogen atom or an aliphatic residue, more preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and all are hydrogen atoms. More preferably, it is an atom.
In formula (2), Y ₃ represents a sulfur atom, an oxygen atom or a selenium atom, preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom.

As the compound represented by the formula (1), a compound represented by the following formula (3) is also preferable.

Wherein _{(3), R 1 ~ R} 4, X 1, X 2, Y 1 and _{Y 2, R} 1 _{~ R 4} in the formula _{(1), X 1, X} 2, Y 1 and _{Y 2} means the same The preferred examples are also the same.
In formula (3), R ₁₃ to R ₁₈ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group Represents an alkoxycarbonyl group, an arylcarbonyl group or an acyl group.
As the aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by R ₁₃ to R _{18 in} the formula (3), Aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group specifically exemplified as the substituent that ring Ar in formula (1) may have , Arylcarbonyl group and acyl group are the same.
R ₁₃ to R _{18 in} the formula (3) are preferably each independently a hydrogen atom or a halogen atom. It is more preferable that each is independently a halogen atom, and it is still more preferable that all are fluorine atoms.

Preferred combinations of the rings Ar, R ₁ to R ₄ , X ₁ to X ₂ and Y ₁ to Y _{2 in} the formula (1) are the above-mentioned rings Ar, R ₁ to R ₄ , X ₁ to X ₂ and Y ₁ to Y ₁ . It is a combination of what is considered to be preferable in each of Y ₂ , and more preferable combinations are as follows.

That is, the compound represented by the formula (2), wherein R ₁ in the formula (2) is an alkylsulfonyl group, R ₂ and R ₃ are each independently an aromatic residue, R ₄ is a hydrogen atom or a carbon number of 1 A compound having _{1 to} 8 alkyl groups, X ₁ and X ₂ are nitrogen atoms, Y ₁ , Y ₂ and Y ₃ are sulfur atoms or oxygen atoms, and R ₉ to R ₁₂ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. Or a compound represented by formula (3), wherein R ₁ in formula (3) is an alkylsulfonyl group, R ₄ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ₁ and X ₂ are CR ₅ and CR ₆ , R ₂ and R ₅ form a ring, and R ₃ and R ₆ form a ring, and Y ₁ and Y ₂ are each independently a sulfur atom or an oxygen atom, R ₁₃ to R 6 A compound in which R ₁₈ is independently a hydrogen atom or a halogen atom Is more preferable.

And a compound represented by formula (2), wherein R ₁ in formula (2) is an alkylsulfonyl group having 1 to 4 carbon atoms, R ₂ and R ₃ are benzene ring residues, and R ₄ is a hydrogen atom or A compound having 1 to 4 carbon atoms, a compound in which X ₁ and X ₂ are nitrogen atoms, Y ₁ , Y ₂ and Y ₃ are sulfur atoms, and R ₉ to R ₁₂ are hydrogen atoms, or a compound represented by formula (3) Wherein R ₁ in Formula (3) is an alkylsulfonyl group having 1 to 4 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ₁ and X ₂ are CR ₅ and CR ₆ and R ₂ and R ₅ form a benzene ring, and R ₃ and R ₆ form a benzene ring, Y ₁ and Y ₂ are sulfur atoms, and R ₁₃ to R ₁₈ are each independently a halogen atom. More preferred are compounds that are atoms.
The compound represented by the formula (1) of the present invention is suitably used as a photoacid generator.

The compound represented by the formula (1) of the present invention can be synthesized using various reactions. The synthesis examples and examples described later are examples thereof, and the synthesis method of the compound represented by the formula (1) of the present invention is not limited to the methods described in the synthesis examples and examples. By using compounds having different substituents and partial structures from the raw material compounds used in Examples and Examples, it is possible to synthesize compounds having various structures included in Formula (1).

Specific examples of the compound represented by the formula (2) are shown in Tables 1 to 3. In each table, Ph means a phenyl group, and Np means a naphthyl group.

Specific examples of the compound represented by the formula (3) are shown in Tables 4 to 8. In each table, Ph means a phenyl group, Np means a naphthyl group, and B ring means a benzene ring.

The photosensitive resin composition of the present invention contains a compound (photoacid generator) represented by the formula (1) of the present invention and a cationically polymerizable compound.
Examples of the cationic polymerizable compound that can be used in the photosensitive resin composition of the present invention include cyclic ether compounds such as epoxy compounds (resins) and oxetane compounds (resins), (meth) acrylates, and vinyl ethers and styrene. Examples thereof include ethylenically unsaturated compounds.

Specific examples of the epoxy compound include phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde) Polycondensates of benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc .; phenols and various diene compounds (terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, Tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenyl Polymers with phenyl, butadiene, isoprene, etc.); Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); Polycondensates of phenols with bischloromethylbiphenyl; Polycondensates of phenols and bischloromethylbenzene; glycidyl ether epoxy compounds obtained by glycidylation of polycondensates of bisphenols and various aldehydes or alcohols; 4-vinyl-1-cyclohexene diepoxide and 3,4- Alicyclic epoxy compounds typified by epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate; glycidyl typified by tetraglycidyldiaminodiphenylmethane and triglycidyl-p-aminophenol Triethanolamine-based epoxy compounds; but glycidyl ester epoxy compounds and the like, but is not limited thereto as long as it is a compound having an epoxy group.

Specific examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, Butoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3- Ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3- Oxe Nylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) Ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Enyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1 , 3- (2-Methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl- -Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3 -Oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3- Oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxy) Cetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl -3- (4-methylphenoxy) methyl oxetane, 3-ethyl-3- (4-fluorophenoxy) methyl oxetane, 3-ethyl-3- (1-naphthoxy) methyl oxetane, 3-ethyl-3- (2- Naphthoxy) methyl oxetane, 3-ethyl-3-{[3- (ethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxetane, phenol novolac oxetane and the like, but any compound having an oxetane ring is limited thereto. What No.

Specific examples of (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, Sphenol-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) Acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayrad RP-1040 (Nippon Kayaku), Kayarad DPCA-30 (Nippon Kayaku), UA-33H (Shin Nakamura Chemical), UA-53H (Shin Nakamura Chemical) and M-8060 (Tojo) (Meth) acrylate monomers such as adult, Ltd.), but (meth) without any particular limitation as long as it has an acrylate group, can be used any of the monomers and oligomers. The (meth) acrylate referred to in the present invention refers to both acrylate and methacrylate.

Specific examples of the ethylenically unsaturated compound include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, 2-acetoxy. Aliphatic monovinyl ethers such as ethyl vinyl ether, diethylene glycol monovinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether, 2-acryloyloxyethyl vinyl ether; 2-phenoxyethyl vinyl ether, Phenyl vinyl ether, p-meth Aromatic monovinyl ethers such as xylphenyl vinyl ether; butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, 1,4-benzene divinyl ether, hydroquinone divinyl ether, cyclohexane dimethanol divinyl ether (1,4-bis Polyfunctional vinyl ethers such as [(vinyloxy) methyl] cyclohexane), diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether; styrene, α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, etc. Styrenes; and cationically polymerizable nitrogen-containing monomers such as N-vinylcarbazole and N-vinylpyrrolidone.

The compounding ratio of the compound represented by the formula (1) in the photosensitive resin composition of the present invention excludes the solvent such as the essential component of the compound represented by the formula (1) and the cationic polymerizable compound and the optional component described later. It is usually 0.1 to 15% by mass, preferably 0.2 to 8% by mass, based on the total mass of the solid content. By setting the compounding ratio of the compound represented by the formula (1) within the above range, a photosensitive resin composition having economical and good curability can be obtained.

In the photosensitive resin composition of the present invention, a solvent can be used to lower the viscosity of the resin composition and improve the coating properties. The solvent is an organic solvent that is usually used for ink, paint, etc., and can dissolve each constituent component of the photosensitive resin composition and does not cause a chemical reaction with the constituent component. Can be used without limitation. Specific examples of the solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone and other ketones, toluene, xylene, methoxybenzene and other aromatic hydrocarbons, dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether, Glycol ethers such as propylene glycol monomethyl ether, ethyl lactate, ethyl acetate, butyl acetate, methyl-3-methoxypropionate, carbitol acetate, propylene glycol monomethyl ether acetate, esters such as γ-butyrolactone, methanol, ethanol, etc. Alcohols, aliphatic hydrocarbons such as octane and decane, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

These solvents can be used alone or in admixture of two or more. The solvent component is added for the purpose of adjusting the film thickness and applicability when applied to the base material, in order to properly maintain the solubility of the main component, the volatility of the component, the liquid viscosity of the composition, etc. The content of the solvent is preferably 95% by mass or less, particularly preferably 10 to 90% by mass, based on the total amount of the photosensitive resin composition containing the solvent.

In the photosensitive resin composition of the present invention, a sensitizer is further used to absorb ultraviolet light and donate the absorbed light energy to the photocationic polymerization initiator, in particular, an aromatic iodonium complex salt. Also good. As the sensitizer, for example, thioxanthones and anthracene compounds having an alkoxy group at the 9th and 10th positions (9,10-dialkoxyanthracene derivatives) are preferable. Examples of the alkoxy group include C1-C4 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The 9,10-dialkoxyanthracene derivative may further have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C1-C4 alkyl group, sulfonic acid alkyl ester group, carboxylic acid alkyl ester group and the like. Examples of the alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester include C1-C4 alkyl. The substitution position of these substituents is preferably the 2-position.

Specific examples of the thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, and the like. Nippon Kayaku Co., Ltd., trade name Kayacure DETX-S) and 2-isopropylthioxanthone are preferred.

Examples of the 9,10-dialkoxyanthracene derivative include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dimethoxy-2. -Ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester 9,10-diethoxyanthracene-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester, and the like.

These can be used alone or in combination of two or more, but the use of 2,4-diethylthioxanthone or 9,10-dimethoxy-2-ethylanthracene is most preferred. Since the sensitizer component exerts an effect in a small amount, its use ratio is preferably 30% by mass or less, particularly preferably 20% by mass or less, based on the mass of the compound represented by the formula (1).

In the photosensitive resin composition of the present invention, various additives such as a thermoplastic resin, a colorant, a coupling agent, a thickener, an antifoaming agent, and a leveling agent can be used as necessary. Examples of the thermoplastic resin include polyethersulfone, polystyrene, and polycarbonate. Examples of the curing agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, anthraquinone red, quinacridone red, and diketopyrrolopyrrole red. When using these additives, etc., the amount used is, in the photosensitive resin composition of the present invention excluding the solvent, for example, 30% by mass or less is a rough guide, but the purpose of use and the requirement of the cured film It can be increased or decreased as appropriate according to the function. As coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Etc. Examples of the thickener include olben, benton and montmorillonite, and examples of the antifoaming agent include antifoaming agents such as silicone, fluoroalkyl and polymer. When these additives are used, the amount used is 10% by weight or less, for example, based on the amount of the photosensitive resin composition material of the present invention excluding the solvent. Depending on the quality, it can be adjusted appropriately.

Further, the photosensitive resin composition of the present invention includes, for example, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, montmorillonite, mica powder, etc. Any inorganic filler can be used. The amount used is 60% by mass or less based on the amount of the photosensitive resin composition material of the present invention excluding the solvent, but can be appropriately increased or decreased depending on the purpose of use and the required function of the cured film. Similarly, organic fillers such as polymethylmethacrylate, rubber, fluoropolymer, polyurethane powder can be incorporated.

The photosensitive resin composition of the present invention comprises an essential component of the compound represented by the formula (1) and the cationic polymerizable compound, and, if necessary, optional components such as a solvent, a coupling agent, an ion catcher, a thermoplastic resin, and coloring. It adjusts by mixing and stirring an agent, a thickener, an antifoamer, a leveling agent, an inorganic filler, etc. by a normal method. In mixing and stirring, a disperser such as a dissolver, a homogenizer, or a three roll mill may be used as necessary. Moreover, after mixing, you may filter using a mesh, a membrane filter, etc. further.

The photosensitive resin composition of the present invention can be easily cured by irradiating active energy rays such as ultraviolet rays. For curing, the photosensitive resin composition of the present invention is usually made to a thickness of about 0.01 to 1 mm and then irradiated with active energy rays. Any suitable active energy ray may be used as long as it has an energy that induces the decomposition of the photoacid generator represented by the formula (1), preferably a high-pressure mercury lamp, a medium-pressure mercury lamp, or a xenon lamp. , Metal halide lamps, germicidal lamps, laser light, electromagnetic energy having a wavelength of 2000 to 7000 angstroms, and light energy rays such as electron beams, X-rays, and ultraviolet rays. The irradiation time of the active energy ray is usually about 0.1 to 10 seconds, although it depends on its intensity. However, it is preferable to take more time for a coating film having a relatively thick film thickness. 0.1 to several minutes after irradiation with active energy rays, most photosensitive resin compositions are cured with a photoacid generator and dried with the touch of a finger. If necessary, the photosensitive resin composition is irradiated with active energy rays. Sometimes, by heating to about 30 to 100 ° C., it is possible to effectively accelerate the polymerization reaction and further improve the curing rate. Further, the cured product obtained by irradiation with active energy rays may be further heat-treated at 50 to 250 ° C. for the purpose of completing the curing by polymerization. In the case of heat treatment, in consideration of the heat resistance of the base material on which the photosensitive resin composition is coated and the resulting cured product, when heat treatment is performed at a high temperature of 100 ° C. or higher, it is preferable to perform the heat treatment in as short a time as possible. preferable.
In addition, by using the photosensitive resin composition of the present invention, a fine pattern of a cured product of the resin composition by applying a conventionally known photolithography technique, that is, a technique including coating, pattern irradiation, and development process. It is also possible to obtain.

Specific uses of the photocurable resin composition of the present invention include paints, coating agents, inks, resists, liquid resists, adhesives, molding materials, putty, glass fiber impregnating agents, sealing agents, and optical modeling. Examples of the base material that can be applied as a coating agent include metals, wood, rubber, plastics, glass, and ceramic products.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents parts by weight.

In the following examples, the following experimental apparatus and measuring apparatus were used.
・ High performance liquid chromatography
[Normal phase HPLC]
Analytical pump ------------------------------------- HTACHI Pump L2130
Detector ---------------------------------- HITACHI UV Detector L-2400
Recorder --------------------------------------------- HITACHI D -2500
Column --------------------------------------------- COSMOSIL 5SL-II
・ Medium pressure preparative liquid chromatography --------- Yamazen EPCLC-W-Prep 2XY A-Type
・ Nuclear magnetic resonance system ---------------------------- JEOL JNM-AL300 (300 MHz)
・ Double Convergence Mass Spectrometer (EI-HRMS) --------------- JEOL JMS-700 MSation
・ DART Mass Spectrometer -------------------------- JEOL JMS-Q1000TD
・ Small organic X-ray structure analyzer ------------- Rigaku R-AXIS RAPID / S (3kW)
・ UV-Vis spectrophotometer -------------------------------------- JASCO V-660
・ Nanosecond time-resolved spectrometer --------- UNISOKU TSP-1000M
・ Fluorescence spectrophotometer -------------- HITACHI H7000
・ Absolute luminescence quantum yield measurement system ------------------------ Hamamatsu C9920-02
・ Photoreaction quantum yield measurement system ------------ Shimadzu Corporation QYM-01
・ Spectro cryostat -------------- OXFORD INSTRUMENTS OptistatDN
・ Light source 1kW Super high pressure mercury lamp -------------------------- USHIO SX-UI-501HQ
Monochrome meter ------------------ Shimadzu Corporation SPG-120
Nanosecond pulsed Nd: YAG laser ---------- Continuum Minilite II
High power nanosecond pulse Nd: YAG laser ------------ Continuum Surelite II
Nanosecond Optical Parametric Oscillator --- Continuum Panther EX OPO
・ Microwave synthesizer ---------------------------------------- Biotage Initiator

Synthesis example 1
In a 500 mL eggplant-shaped flask, 19.1 g (142 mmol) of benzo [b] thiophene was dissolved in 200 mL of chloroform, and then 16 mL (312 mmol) of bromine was added dropwise and stirred at room temperature for 24 hours. After quenching with 100 mL of 10% aqueous sodium thiosulfate solution, extraction with ethyl acetate, drying over anhydrous magnesium sulfate, distilling off the solvent and washing with hexane gave 41.7 g of a compound represented by the following formula 1 (yield) About 100%) was obtained as a purple solid. The measured values of the compound represented by the formula 1 by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ 7.77-7.71 (m, 2H), 7.47-7.36 (m, 2H)

Synthesis example 2
In a 500 mL eggplant-shaped flask, 5.05 g (40.3 mmol) of glycine methyl ester hydrochloride was dissolved in 200 mL of dichloromethane, and then cooled to 0 ° C. with an ice bath. Triethylamine (11.3 mL, 81 mmol) was added, and benzoyl chloride (4.7 mL, 40.5 mmol) was added dropwise over 10 minutes. The mixture was then warmed to room temperature and stirred overnight. After the reaction, 100 mL of a saturated aqueous sodium hydrogen carbonate solution was added, followed by extraction with dichloromethane, drying over anhydrous magnesium sulfate, and evaporation of the solvent to remove 7.43 g of a compound represented by the following formula 2 (yield 95.5). %) As a white solid. The measured values of the compound represented by the formula 2 using a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.84-7.81 (m, 2H), 7.56-7.46 (m, 3H), 6.67 (sl, 1H), 4.28-4.26 (d, J = 5.1 Hz, 2H ), 3.81 (s, 3H)

Synthesis example 3
100 mL of chloroform was placed in an eggplant-shaped flask, molecular sieve (4A) was added, and nitrogen bubbling was performed for 30 minutes. On the other hand, in a flame-dried four-necked flask, while flowing nitrogen, 4.72 g (24.4 mmol) of the compound represented by Formula 2 obtained in Synthesis Example 2 and 8.04 g (36.2 mmol) of diphosphorus pentasulfide. Was substituted with argon. 70 mL of the above chloroform was added using a syringe and heated at 80 ° C. for 24 hours. After the reaction, the precipitate was decomposed while gradually adding 50 mL of 5% aqueous sodium hydroxide solution, and extracted with chloroform. The extract was dried over anhydrous magnesium sulfate, the solvent was distilled off, and purified by passing through a short column using hexane / diethyl ether to obtain 3.91 g of a compound represented by the following formula 3 (yield: 83.5). %) As a brown oil. The measured values of the compound represented by Formula 3 by the nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.82-7.73 (m, 2H), 7.44-7.36 (m, 3H), 7.13 (s, 1H), 3.97 (s, 3H)

Synthesis example 4
In a 100 mL brown eggplant-shaped flask, 3.90 g (20.4 mmol) of the compound represented by Formula 3 obtained in Synthesis Example 3 and 5.48 g (30.8 mmol) of NBS (N-bromosuccinimide) were placed. Dissolved in 53 mL of chloroform. After stirring at room temperature for 4 hours, 30 mL of a 10% aqueous sodium thiosulfate solution was added, and the mixture was extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and purified by silica gel column chromatography (chloroform: hexane = 1: 1) to obtain 3.95 g (yield 71.7%) of a compound represented by the following formula 4 as a white solid. The measured values of the compound represented by the formula 4 using a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.84-7.80 (m, 2H), 7.42-7.40 (m, 3H), 4.04 (s, 3H)

Synthesis example 5
In a 500 mL eggplant-shaped flask, 20.2 g (147 mmol) of thiobenzamide and 34.0 g (219 mmol) of a 50 wt% chloroacetaldehyde aqueous solution were dissolved in 100 mL of ethanol, and then heated to reflux for 3 hours. The reaction product was extracted with chloroform, dried over anhydrous magnesium sulfate, and purified by passing through a silica gel short column (developing solvent: chloroform) to obtain 25.2 g of a compound represented by the following formula 5 (yield: about 100%). Was obtained as a yellow oil. The measured values of the compound represented by the formula 5 by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ8.00-7.96 (m, 2H), 7.89-7.87 (d, J = 3.3 Hz, 1H), 7.48-7.44 (m, 3H), 7.35-7.34 (d , J = 3.3 Hz, 1H)

Synthesis Example 6
In a 300 mL brown eggplant-shaped flask, 8.36 g (51.9 mmol) of the compound represented by Formula 5 obtained in Synthesis Example 5 and 14.0 g (78.7 mmol) of NBS are dissolved in 120 mL of chloroform and heated for 16 hours. Refluxed. A 10% aqueous sodium thiosulfate solution (50 mL) was added, and the mixture was extracted with chloroform. This was dried over anhydrous magnesium sulfate, the solvent was distilled off, and recrystallization was performed with methanol to obtain 11.8 g (yield 94.4%) of a compound represented by the following formula 6 as a light brown solid. The measured values of the compound represented by the formula 6 using a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ 7.89-7.85 (m, 2H), 7.74 (s, 1H), 7.46-7.44 (m, 3H)

Synthesis example 7
Distilled 3.3 mL (23.5 mmol) of diisopropylamine was placed in a four-necked flask that was flame-dried and purged with argon, and cooled to 0 ° C. After dropwise addition of 13.5 mL (21.6 mmol) of n-butyllithium hexane solution, the mixture was warmed to room temperature and diluted with a small amount of dry THF (tetrahydrofuran). The flame-dried four-necked flask was purged with argon, and 1.78 g (7.41 mmol) of the compound represented by formula 6 obtained in Synthesis Example 6 was dissolved in 35 mL of dry THF. After stirring at 0 ° C. for 10 minutes, 20 mL of LDA (lithium diisopropylamide) was added dropwise and allowed to stir at 0 ° C. for 30 minutes. After the reaction, it was quenched with water, extracted with diethyl ether, and dried over anhydrous magnesium sulfate to obtain 1.68 g (yield 94.4%) of a compound represented by the following formula 7 as a light brown solid. The measured values of the compound represented by the formula 7 by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.96-7.93 (m, 2H), 7.47-7.44 (m, 3H), 7.22 (s, 1H)

Synthesis example 8
1.69 g (6.26 mmol) of the compound represented by Formula 4 obtained in Synthesis Example 4 was dissolved in 26 mL of dry THF in a four-necked flask that had been subjected to flame drying and purged with argon, and was dissolved at −78 ° C. Cooled to. 4.1 mL (6.56 mmol) of n-butyllithium hexane solution was added dropwise and stirred for 30 minutes while maintaining the cooled temperature. 1.8 mL of tributyl chlorostannane (6.64 mmol) was added, and the mixture was stirred at −78 ° C. for 30 minutes, warmed to room temperature, and further stirred for 30 minutes. Aqueous potassium fluoride was added, and the mixture was extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 3.14 g (yield 98.7%) of the compound represented by the following formula 10 as a yellow oily substance. Got as. The measured values of the compound represented by the formula 10 using a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.86-7.83 (m, 2H), 7.38-7.35 (m, 3H), 3.94 (s, 3H), 1.65-0.87 (m, over 27H)

Synthesis Example 9
In a microwave synthesis vial, 1.56 g (6.50 mmol) of the compound represented by Formula 7 obtained in Synthesis Example 7, 1.65 g (6.51 mmol) of bispinacolatodiboron, Pd ₂ (dba) ₃ ) 0.187 g (0.204 mmol) of adduct of chloroform, 0.280 g (0.998 mmol) of tricyclohexylphosphine and 0.959 g (9.77 mmol) of potassium acetate were dissolved in 19 mL of 1,4-dioxane, and microwaves were used. And stirred at 170 ° C. for 150 minutes. The reaction solution was filtered through celite with ethyl acetate, the solvent was distilled off, water was added, the mixture was extracted with ethyl acetate, and dried over anhydrous magnesium sulfate to obtain 1.87 g of a compound represented by the following formula 11 (reaction rate: 100). %) As a yellow oil. The measured values of the compound represented by the formula 11 by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): 8.06-8.03 (m, 2H), 7.98 (s, 1H), 7.44-7.41 (m, 3H), 1.39 (s, 12H)

Synthesis Example 10
In a four-necked flask, 1.65 g (5.65 mmol) of the compound represented by Formula 1 obtained in Synthesis Example 1 and 1.52 g (5.64 mmol) of the compound represented by Formula 4 obtained in Synthesis Example 4 were obtained. ), 0.168 g (0.641 mmol) of triphenylphosphine, 11 mL of 2M tripotassium phosphate aqueous solution and 125 mL of 1,4-dioxane were added, and nitrogen bubbling was performed for 30 minutes. While nitrogen was flowing, 0.326 g (0.282 mmol) of Pd (PPh ₃ ) ₄ was added and heated to reflux for 24 hours. Aqueous ammonium chloride was added for neutralization, and the mixture was extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and purification by silica gel column chromatography (hexane: chloroform = 1: 1) gave 1.75 g (yield 77.1%) of the compound represented by the following formula 12. Obtained as a white solid. The measured values of the compound represented by the formula 12 by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.93-7.89 (m, 3H), 7.83-7.80 (m, 1H), 7.49-7.38 (m, 5H), 4.11 (s, 3H)

Synthesis Example 11
In a four-necked flask, 1.87 g (6.50 mmol) of the compound represented by Formula 11 obtained in Synthesis Example 9 and 2.62 g (6.50 mmol) of the compound represented by Formula 12 obtained in Synthesis Example 10 were obtained. ), 0.158 g (0.602 mmol) of triphenylphosphine, 12 mL of a 2M tripotassium phosphate aqueous solution and 160 mL of 1,4-dioxane were added, and nitrogen bubbling was performed for 30 minutes. While nitrogen was flowing, 0.402 g (0.348 mmol) of Pd (PPh ₃ ) ₄ was added and heated to reflux for 24 hours. Aqueous ammonium chloride was added for neutralization, and the mixture was extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and purification by silica gel column chromatography (chloroform) and normal phase HPLC (chloroform) gave 1.34 g of a compound represented by the following formula BT-OMe (1) (yield) 42.7%) was obtained as a pale yellow solid. The nuclear magnetic resonance apparatus measured for the compound represented by the formula BT-OMe (1) was as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ8.08-8.01 (m, 3H), 7.89-7.86 (m, 1H), 7.82-7.79 (m, 2H), 7.47-7.43 (m, 3H), 7.40 -7.36 (m, 5H), 7.30 (s, 1H), 3.73 (s, 3H)
EI-HRMS (m / z): calcd for C ₂₇ H ₁₈ N ₂ OS ₃ , 482.0581; found, 482.0587 (M + H) ⁺

Synthesis Example 12
In a four-necked flask, 1.85 g (6.34 mmol) of the compound represented by Formula 1 obtained in Synthesis Example 1 and 1.80 g (6.25 mmol) of the compound represented by Formula 11 obtained in Synthesis Example 9 Then, 0.192 g (0.732 mmol) of triphenylphosphine, 12 mL of 2M tripotassium phosphate aqueous solution and 110 mL of 1,4-dioxane were added, and nitrogen was bubbled for 30 minutes. While flowing nitrogen, 0.548 g (0.474 mmol) of Pd (PPh ₃ ) ₄ was added and heated to reflux for 24 hours. The mixture was neutralized with an aqueous ammonium chloride solution, and extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and purification by silica gel column chromatography (hexane: chloroform = 1: 1) gave 2.07 g (yield: 89.0%) of a compound represented by the following formula 13 as white. Obtained as a solid. The measured values of the compound represented by the formula 13 using a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ8.35 (s, 1H), 8.07-8.04 (m, 2H), 7.89-7.83 (m, 2H), 7.50-7.42 (m, 5H)

Synthesis Example 13
In a four-necked flask, 2.50 g (5.21 mmol) of the compound represented by Formula 10 obtained in Synthesis Example 8 and 1.49 g (4.00 mmol) of the compound represented by Formula 13 obtained in Synthesis Example 12 were used. ), 1.39 g (9.17 mmol) of cesium fluoride and 45 mL of toluene were added, and nitrogen was bubbled for 30 minutes. While nitrogen was flowing, 0.321 g (0.278 mmol) of Pd (PPh ₃ ) ₄ was added and heated to reflux for 24 hours. 100 mL of an aqueous potassium fluoride solution was added, and the mixture was extracted with ethyl acetate. It was dried over anhydrous magnesium sulfate, the solvent was distilled off, and purified by silica gel column chromatography (chloroform) and normal phase HPLC (chloroform) to obtain 1.32 g of a compound represented by the following formula BT-OMe (2) (yield) 68.5%) was obtained as a white solid. The measured values of the compound represented by the formula BT-OMe (2) by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ8.02-7.93 (m, 4H), 7.90-7.87 (m, 1H), 7.67-7.63 (m, 1H), 7.46-7.43 (m, 6H), 7.38 -7.35 (m, 2H), 7.21 (s, 1H), 3.81 (s, 3H)
EI-HRMS (m / z): calcd for C ₂₇ H ₁₈ N ₂ OS ₃ , 482.0581; found, 482.0584 (M + H) ⁺

Measurement of Photoreaction Quantum Yield of Intermediate After irradiating a hexane solution of the compound represented by Formula BT-OMe (1) obtained in Synthesis Example 11 with ultraviolet rays (365 nm), a photoreaction quantum species rate measuring device ( When the photoreaction quantum yield was measured using QYM-01, manufactured by Shimadzu Corporation, the quantum yield of the ring closure reaction was 0.33. Further, when the photoreaction quantum yield was measured by the same method as described above using the compound represented by the formula BT-OMe (2) obtained in Synthesis Example 13, the quantum yield of the ring closure reaction was 0.64. Met.
Based on this result, the following synthesis was performed using a compound represented by the formula BT-OMe (2), which has a better quantum yield.

Synthesis Example 14
In a two-necked flask subjected to flame drying and purged with argon, 0.269 g (0.557 mmol) of the compound represented by the formula BT-OMe (2) obtained in Synthesis Example 13 was dissolved in about 15 mL of dichloromethane, and the whole system was dissolved. Was covered with aluminum foil. Boron tribromide (1.46 mL, 2.8 mmol) was added dropwise, and the mixture was stirred at room temperature for 3 days, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a compound represented by the following formula BT-OH. 0.337 g (yield> 100%) of the compound obtained was obtained as a red solid. With respect to the compound represented by Formula 10, the disappearance of the signal derived from the methoxy group was confirmed by measurement with a nuclear magnetic resonance apparatus ( ¹ H NMR (300 MHz, CDCl ₃ )).

Example 1
In a frame-dried two-necked flask, 0.234 g of the compound represented by the formula BT-OH obtained in Synthesis Example 14 was added, and the whole system was covered with aluminum foil. 4 mL of dichloromethane was added and cooled to 0 ° C. with an ice bath, and 500 μL of triethylamine was added. 0.143 g (1.25 mmol) of methanesulfonyl chloride was added and stirred at 0 ° C. for 2 hours. Water was added, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. The compound represented by the following formula BT-OMs by distilling off the solvent and purifying with medium pressure silica gel chromatography (chloroform: hexane = 1: 1), preparative GPC (chloroform) and normal phase HPLC (chloroform) ( 16 mg (corresponding to compound 1 in Table 1) was obtained as a white solid. The measured values of the compound represented by the formula BT-OMs by a nuclear magnetic resonance apparatus were as follows.
¹ H NMR (300 MHz, CDCl ₃ ): δ7.98-7.89 (m, 5H), 7.48-7.40 (m, 9H), 7.25 (s, 1H), 2.65 (s, 3H)

In order to confirm that the compound represented by BT-OMs obtained in Example 1 is a compound capable of generating an acid upon irradiation with active energy rays, the following evaluation was performed.

First, propylene oxide was used to confirm the change in ¹ H-NMR spectrum before and after epoxy ring opening. Specifically, ¹ H-NMR spectra were measured for a sample of propylene oxide alone and a sample obtained by adding methanesulfonic acid to propylene oxide and stirring for 1 hour at room temperature. The results are shown in FIG.

From the results of FIG. 1, it can be seen that in the sample to which methanesulfonic acid was added, the peak attributed to propylene oxide disappeared, and the peak attributed to oligopropylene glycol produced by the ring-opening reaction appeared (in FIG. 1). (See spectrum above). From this, it was found that the presence or absence of propylene oxide ring-opening reaction can be confirmed by the measurement result of ¹ H-NMR spectrum.

Next, a sample obtained by dissolving the compound represented by the formula BT-OMs obtained in Example 1 and propylene oxide in deuterated chloroform was irradiated with ultraviolet rays (365 nm), and the change in ¹ H-NMR spectrum before and after the irradiation was measured. did. The results are shown in FIG. 3 shows a ¹ H-NMR spectrum of a sample in which the compound represented by the formula BT-OMs is dissolved in deuterated chloroform, and FIG. 4 shows a ¹ H-NMR spectrum of a sample in which propylene oxide is dissolved in deuterated chloroform. Indicates.

From the results of FIG. 2, it can be seen that the peak attributed to propylene oxide decreases after ultraviolet irradiation, and the peak attributed to oligopropylene glycol produced by the ring-opening polymerization reaction appears (see the upper spectrum in FIG. 2). . This indicates that the ring-opening reaction of propylene oxide is caused by the acid (methanesulfonic acid) generated from the compound represented by the formula BT-OMs obtained in Example 1 by irradiation with ultraviolet rays. . From these results, the compound represented by BT-OMs obtained in Example 1 is a compound capable of generating an acid upon irradiation with active energy rays, and the generated acid can cause an epoxy ring-opening reaction. That is, it is clear that the compound can be used as a cationic polymerization initiator initiator.

The compound represented by the formula (1) of the present invention has high solubility in hydrophobic cationic polymerizable compounds and solvents, and also has high acid generation quantum yield for i-line and g-line. Useful as a generator.

Claims (12)

1. Following formula (1)
   

   

   (In the formula (1), the ring Ar is a benzene ring, naphthalene ring, thiophene ring, benzothiophene ring, furan ring, benzofuran ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, imidazolidinium ring, benzoimidazolium. Represents a ring, a cyclopentene ring, a cyclohexene ring, a cyclopentene ring, an indole ring or a pyrrole ring.
   R ₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group, an alkoxysulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an arylcarbonyl group.
   R ₂ and R ₃ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl Represents a group, an acyl group or a trimethylsilyl group.
   R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue.
   X ₁ represents CR ₅ or a nitrogen atom.
   R ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an amide group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group. , R ₂ and R ₅ may be linked to form a ring.
   X ₂ represents CR ₆ or a nitrogen atom.
   R ₆ represents a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group or acyl group. , R ₃ and R ₆ may be linked to form a ring.
   Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom, a selenium atom, or CR ₇ R ₈ .
   R ₇ and R ₈ represent a hydrogen atom or an aliphatic hydrocarbon residue. )
   A compound represented by
2. Following formula (2)
   

   

   (In the formula (2), R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y ₂ are R ₁ to R ₄ , X ₁ , X ₂ , Y in the formula (1) according to claim 1. to .R 9 _~ R ₁₂ are each independently represents the same meaning as ₁ and Y _2, a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, carbonamido group, an amide group, an alkoxy group And represents an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, or an acyl group, and Y ₃ represents a sulfur atom, an oxygen atom, or a selenium atom.)
   The compound of Claim 1 represented by these.
3. The compound according to claim 2, wherein R ₁ is an alkylsulfonyl group having 1 to 4 carbon atoms.
4. The compound according to claim 2, wherein X ₁ and X ₂ are nitrogen atoms.
5. The compound according to claim 2, wherein Y ₁ to Y ₃ are each independently a sulfur atom or an oxygen atom.
6. Following formula (3)
   

   

   (In Formula (3), R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y ₂ are R ₁ to R ₄ , X ₁ , X ₂ , Y in Formula (1) according to claim 1. each independently .R 13 _~ R ₁₈ represent the same meaning as ₁ and Y _2, a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, carbonamido group, an amide group, an alkoxy group Represents an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group.)
   The compound of Claim 1 represented by these.
7. The compound according to claim 6, wherein R ₁ is an alkylsulfonyl group having 1 to 4 carbon atoms.
8. X ₁ is CR ₅ and R ₂ and R ₅ are connected to form a benzene ring, and X ₂ is CR ₆ and R ₃ and R ₆ are connected to form a benzene ring. 7. A compound according to claim 6, wherein:
9. The compound according to claim 6, wherein Y ₁ and Y ₂ are a sulfur atom or an oxygen atom.
10. The photo-acid generator containing the compound as described in any one of Claims 1 thru | or 9.
11. A photosensitive resin composition comprising the photoacid generator according to claim 10 and a compound polymerizable by the photoacid generator.
12. A cured product obtained by curing the photosensitive resin composition according to claim 11.
    

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