JP2018118935A - Novel compound, photoacid generator containing the compound, and photosensitive resin composition containing the photoacid generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonionic photoacid generator with high acid generation quantum yield.SOLUTION: The present invention provides a compound represented by formula (2) (where, ring Ar is a benzene ring, naphthalene ring, thiophene ring or the like; Ris an aliphatic hydrocarbon or the like; Rand Rindependently represent H, an aromatic residue or the like; Ris H or an aliphatic hydrocarbon; Xis CR, N, O, S, F or P; Ris H, an aromatic residue or the like; Xis CR, N, O, S, F or P; Ris H, an aromatic residue or the like; Yis S, O, Se or CRR; Rand Rare H or an aliphatic hydrocarbon).SELECTED DRAWING: None

Description

  The present invention relates to a photoacid generator, a photosensitive resin composition containing the photoacid generator, and a compound useful as the photoacid generator, and in particular, a compound useful as a nonionic photoacid generator. About.

  The photosensitive resin composition is a composition in which the monomers and unsaturated oligomers in the composition are polymerized by irradiation with active energy rays such as ultraviolet rays and electron beams, and the entire composition is three-dimensionally crosslinked and cured. This refers to what is insolubilized and includes photoinitiators and various additives in addition to monomers and unsaturated oligomers. Photosensitive resin compositions have been widely put into practical use in fields such as printing inks, paints, coatings, and various resist inks from the viewpoints of energy saving and high production efficiency.

  Many of the photosensitive resin compositions cure and insolubilize the composition using a photo-radical polymerization reaction of a compound having an unsaturated double bond such as an acrylic ester compound. Research has also been actively conducted on the use of cationic photopolymerization of cationically polymerizable compounds. The method of curing a compound by a photocationic polymerization reaction has various advantages compared to the method of curing a compound by a photoradical polymerization reaction, such as low curing shrinkage and no influence of oxygen during curing. have.

  A photosensitive resin composition that utilizes a photocationic polymerization reaction of a compound contains a photoacid generator that generates radicals (acids) by irradiation with ultraviolet rays or electron beams, as a polymerization initiator. As photoacid generators, ionic photoacid generators such as triarylsulfonium salts (see Patent Document 1) and phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2) are known. Since the agent has low compatibility (solubility) with respect to a hydrophobic cationically polymerizable compound or a solvent, use of a nonionic photoacid generator has been studied.

Japanese Patent Laid-Open No. 50-151997 JP 09-118663 A Japanese Patent Laid-Open No. 10-213899 International Publication WO2015 / 125745 A1

  Nonionic photoacid generators are not only more compatible with hydrophobic cationically polymerizable compounds and solvents than ionic photoacid generators, but generally have an absorption wavelength greater than that of ionic photoacid generators. Are also used in the fields of printing inks, paints, coatings, various resist inks, etc., and light emission wavelengths (i-line (wavelength 365 nm), g-line ( Development of a photosensitive resin composition excellent in sensitivity to a wavelength of 436 nm) is expected (see Patent Document 3). However, the conventional nonionic photoacid generator has a low acid generation quantum yield of about 0.1 to 0.3 when irradiated with i-line or g-line, and has a high acid generation quantum yield. Development of a photoacid generator has been desired.

  The problem to be solved by the present invention is a nonionic system having a high acid generation quantum yield while maintaining the properties of high compatibility with hydrophobic cationically polymerizable compounds and solvents and excellent sensitivity to i-line and g-line. It is to provide a photoacid generator.

This invention made | formed in order to solve the said subject is a compound represented by following General formula (1).
In the above 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, imidazolidium ring, benzoimidazolium Represents a ring, a cyclopentene ring, a cyclohexene ring, a cyclopentene ring or a maleimide;
R ₁ is an aliphatic hydrocarbon group, alkylsulfonyl group, alkoxysulfonyl group, arylsulfonyl group, alkylcarbonyl group, alkoxycarbonyl group, arylcarbonyl group, halogenated alkylsulfonyl group, halogenated alkoxysulfonyl group, halogenated arylsulfonyl group Represents a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated 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,
When X ₁ represents CR ₅ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and X ₁ represents CR ₅ , 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, or R ₂ and R ₅ may be linked to form a ring. ,
When X ₂ represents CR ₆ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and X ₂ represents CR ₆ , 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, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group, or R ₃ and R ₆ may be linked to form a ring. ,
When Y ₁ represents a sulfur atom, an oxygen atom, a selenium atom or CR ₇ R ₈ , and Y ₁ represents CR ₇ R ₈ , R ₇ and R ₈ represent a hydrogen atom or an aliphatic hydrocarbon residue.

In the process leading to the present invention, the present inventor has characteristics such as high compatibility with hydrophobic cationically polymerizable compounds and solvents, excellent sensitivity to i-line and g-line, and zero acid generation quantum yield. And another compound having a high acid generation quantum yield compared to conventional nonionic photoacid generators (see Patent Document 4), the major difference between this compound and the compound according to the present invention is , R ₁ can be a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group. At this time, the acid generated when the compound represented by formula (1) is irradiated with light is a strong acid. In particular, when R ₁ is a perfluoroalkylsulfonyl group, a perfluoroalkoxysulfonyl group, a perfluoroarylsulfonyl group, a perfluoroalkylcarbonyl group, a perfluoroalkoxycarbonyl group, or a perfluoroarylcarbonyl group, Since the acid generated when the compound represented is irradiated with light becomes a super strong acid that exhibits very strong acidity, the compound is useful as a photoacid generator as a polymerization initiator of the photosensitive resin composition.

For example, when R ₁ is a trifluoromethylsulfonyl group, an acid generated when the compound represented by the formula (1) is irradiated with light is known to exhibit a very strong acidity. It becomes an acid.
On the other hand, the structure in which R ₁ of the compound described in Patent Document 4 is a trifluoromethylsulfonyl group is unstable, and the trifluoromethylsulfonate ion (CF ₃ SO ₃ ⁻ ) is liberated. In practice, synthesis and isolation are impossible, or use as a photoacid generator is difficult.
Thus, the compound of the present invention represented by the formula (1) is described in Patent Document 4 in that it is highly compatible with a hydrophobic cationically polymerizable compound and a solvent and excellent in sensitivity to i-line and g-line. Although it is equivalent to the compound described, it is superior to the compound described in Patent Document 4 in that a structure capable of generating a super strong acid by light irradiation can be taken. The reason is that in the compound described in Patent Document 4, an atom or atomic group such as a sulfur atom having a high electron donating property is directly connected to a carbon atom to which R ₁ O corresponding to an acid unit is bonded. The activity is high and the bond between R ₁ O and the carbon atom is easily cleaved, whereas the compound of the present invention represented by the formula (1) uses a 6-membered ring such as a stable benzene ring. It is in.

Moreover, this invention is a compound represented by following formula (2).
Wherein _{(2), R 2 ~R 4} , X 1, X 2, and _{Y 1 R} 2 _{to R} 4 in the formula (1) according to claim _{1, X 1,} X _2, and the same as _{Y 1} Express meaning,
R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
R ₉ 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. ,
X ₃ represents CR ₁₀ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and when X ₃ represents CR ₁₀ , R ₁₀ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue Represents 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, or R ₉ and R ₁₀ may be linked to form a ring. ,
Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom.

Furthermore, this invention is a compound represented by following formula (3).
In formula (3), R _{2 to} R ₄ , X ₁ and Y ₁ represent the same meaning as R _{2 to} R ₄ , X ₁ and Y ₁ in formula (1) according to claim 1,
R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
X ₄ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
R _{11 to} R ₁₇ 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 or an acyl group.

Furthermore, this invention is a compound represented by following formula (4).
In formula (4), R _{2 to} R ₄ , X ₁ , and Y ₁ represent the same meaning as R _{2 to} R ₄ , X ₁ , and Y ₁ in formula (1) according to claim 1,
R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
X ₃ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
X ₄ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
R _{15 to} R ₂₂ 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 or an acyl group.

In the compounds represented by the above formulas (2) to (4), a combination of an oxygen atom and a sulfur atom, a combination of a nitrogen atom and a sulfur atom that expresses an attractive interaction between X ₁ and Y ₂ , It is preferable to select a combination of X ₁ and Y ₂ from a combination of CH unit and nitrogen atom, a combination of CH unit and oxygen atom, a combination of CH unit and fluorine, a combination of phosphorus atom and nitrogen atom, and the like.
In the compound represented by the above formula (2), a combination of an oxygen atom and a sulfur atom, a combination of a nitrogen atom and a sulfur atom, a CH unit that expresses an attractive interaction between X ₂ and X ₃ It is preferable to select a combination of X ₂ and X ₃ from a combination of nitrogen and nitrogen atoms, a combination of CH units and oxygen atoms, a combination of CH units and fluorine, a combination of phosphorus atoms and nitrogen atoms, and the like.
Furthermore, in the compound represented by the above formula (3), a combination of an oxygen atom and a sulfur atom, a combination of a nitrogen atom and a sulfur atom, a CH unit, which exhibits an attractive interaction between X ₄ and R ₁₄ It is preferable to select a combination of X ₄ and R ₁₄ from a combination of nitrogen and nitrogen, a combination of CH and oxygen, a combination of CH and fluorine, a combination of phosphorus and nitrogen, and the like.
Furthermore, in the compound represented by the above formula (4), a combination of an oxygen atom and a sulfur atom, a combination of a nitrogen atom and a sulfur atom that expresses an attractive interaction between X ₃ and X ₄ , CH It is preferable to select a combination of X ₃ and X ₄ from a combination of a unit and a nitrogen atom, a combination of a CH unit and an oxygen atom, a combination of a CH unit and a fluorine, a combination of a phosphorus atom and a nitrogen atom, and the like.
From the above, rotation of a single bond between the central five-membered ring and the left five-membered ring in the compounds represented by formulas (2) to (4), between the central five-membered ring and the right six-membered ring The rotation of each single bond can be controlled.

The photoacid generator according to the present invention contains any of the compounds represented by the formulas (1) to (4) described above.
In this case, it is preferable that the photoacid generator according to the present invention contains any one of the compounds represented by the above formulas (2) to (4). With this configuration, the compound contained in the photoacid generator A strong acid can be generated by a photoelectron cyclic reaction. In particular, in the compounds represented by the above formulas (2) to (4), R ₁ is a perfluoroalkylsulfonyl group, a perfluoroalkoxysulfonyl group, a perfluoroarylsulfonyl group, a perfluoroalkylcarbonyl group, a perfluoroalkoxycarbonyl group. Or a perfluoroarylcarbonyl group, it is possible to generate a super strong acid exhibiting very strong acidity by the photoelectron cyclic reaction of the compound contained in the photo acid generator,

The photosensitive resin composition which concerns on this invention contains the photoacid generator containing the compound represented by either of the formula (1)-(4) mentioned above, and the compound which can be polymerized by this photoacid generator. .
Further, the cured product according to the present invention is a photosensitizer containing a photoacid generator containing a compound represented by any one of the above formulas (1) to (4) and a compound polymerizable by the photoacid generator. It is obtained by curing the functional resin composition.

  According to the present invention, it has high solubility compatibility with hydrophobic cationically polymerizable compounds and solvents, and excellent sensitivity to i-line and g-line, and also has high acid generation quantum with respect to active energy rays. A nonionic photoacid generator having a yield can be obtained.

¹ H-NMR spectrum of the compound DS-0102 according to Example 1 of the present invention. ¹ H-NMR spectrum of the compound DS-01. ¹ H-NMR spectrum of the compound DS-0202. ¹ H-NMR spectrum of the compound DS-0201. ¹ H-NMR spectrum of the compound DS-02. 2 shows an absorption spectrum of Compound DS-01 after irradiation with ultraviolet light, (a) shows an absorption spectrum of Compound DS-01 with an irradiation time of 0 to 30 seconds, and (b) shows an irradiation time of 30 seconds to 240. The absorption spectrum of compound DS-01 after 1 second is shown. ¹ H-NMR spectrum of the compound DS-01-A. ¹ H-NMR spectrum (a) and ¹³ C-NMR spectrum (b) of compound RL-0102 according to Example 2 of the present invention. ¹ H-NMR spectrum (a) and ¹³ C-NMR spectrum (b) of Compound RL-0100. Absorption spectrum of Compound RL-0102 when irradiated with ultraviolet light for 0 to 30 seconds. Absorption spectrum of Compound RL-0102 when irradiated with ultraviolet light for 30 to 240 seconds. Absorption spectrum of Compound RL-0100-A when irradiated with ultraviolet light for 0 to 360 seconds. Absorption spectrum of Compound RL-0100-C when irradiated with ultraviolet light for 0 to 240 seconds. The structure of the compound RL-100-A obtained from the results of X-ray structural analysis. Compound RL-0100 and propylene oxide were mixed and irradiated with ultraviolet rays for 10 minutes, and then the mass analysis result (mass spectrometry chart) of the obtained polymer substance. The electron microscope observation image of the residue part which removed the soluble part after irradiating an ultraviolet-ray to the spin coat film | membrane which formed the resin curable composition containing the compound RL-0100 on the glass substrate, and heat-processing. The figure which shows the synthetic | combination procedure of compound AM-06 concerning Example 3 of this invention. Absorption spectra of Compound AM-04 and Compound AM-06 before and after UV irradiation.

Hereinafter, the present invention will be described in detail.
The compound according to the present invention has a structure represented by the following formula (1). The feature of the compound represented by the formula (1) is that the acid is desorbed from the substituent represented by R1O when the compound is irradiated with active energy rays such as i-line and g-line. Since the separation reaction occurs, the detached acid can function as a polymerization initiator for the cationically polymerizable compound.

  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 ring. , Cyclopentene ring, cyclohexene ring, cyclopentene ring or maleimide.

  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 ring. Represents a cyclopentene ring, a cyclohexene ring, a cyclopentene ring or a maleimide ring. The ring Ar may be a heterocyclic ring, and the heterocyclic ring may form a cyclic ketone or a cyclic thioketone.

  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. A plurality of substituents may be used, or a plurality of substituents may be different.

  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, a fluorene ring and a carbazole ring, and the like, 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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, 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. Moreover, as a cyclic | annular alkyl group, a C3-C8 cycloalkyl group etc. are mentioned, for example.

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, and specific examples thereof include an amide group, an acetamide group, an N-methylamide group, and an N-ethylamide group. Group, N- (n-propyl) amide group, N- (n-butyl) amide group, N-isobutyramide 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 a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, and an n-pen. 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 an alkylcarbonyl group having 1 to 10 carbon atoms, an arylcarbonyl group and the like, 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 group represented by R ₁ include the same as those described in the section 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. , Alkylsulfonyl group and alkylcarbonyl group are included in the category of alkyl 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. Examples thereof include halogenated alkoxy groups such as fluorinated alkoxy groups, iodinated alkoxy groups, chlorinated alkoxy groups, and iodinated alkoxy groups, and are also included in the category of alkoxy groups in the alkoxysulfonyl group and alkoxycarbonyl group.
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 In addition, halogenated aryl groups such as a fluorinated aryl group, an aryl iodide group, an aryl chloride group and an aryl iodide group are also included in the category of the aryl group in the arylsulfonyl group and the 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, and R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue.
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).

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 Formula (1), X ₁ represents CR ₅ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and R ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, or a cyano group. Represents 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. When X ₁ is CR ₅ , R ₂ and R ₅ may 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 that may be formed by R ₂ and R ₅ is described in the section of the aromatic residue as a substituent that the ring Ar of formula (1) may have. The same thing as the specific example of an aromatic ring is mentioned, Moreover, as a substituent which this ring formed may have, it is a term of the substituent which ring Ar of Formula (1) may have. The same as mentioned.

In Formula (1), X ₂ represents CR ₆ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus 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, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group is represented. 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.
Moreover, as X < ₁ > and X < ₂ > in Formula (1), it is preferable that both are nitrogen. When X ₁ and X ₂ are CR ₅ and CR _6, it is preferable that R ₂ and R ₅ form a ring, and R ₃ and R ₆ form a ring. More preferably, both are benzene rings.

In formula (1), Y ₁ represents a sulfur atom, an oxygen atom, a selenium atom or CR ₇ R ₈ , and R ₇ and R ₈ 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 a compound represented by Formula (1), the compound represented by following formula (2) is preferable.

Wherein _{(2), R 2 ~R 4} , X 1, X 2, and _{Y 1} are as defined _{R 2 ~R 4, X 1,} X 2, and _{Y 1} in the formula (1), preferred examples The same is true.
In the formula (2), R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group.

In the formula (2), R ₉ is 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, Represents an arylcarbonyl group or an acyl group.
Aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group or acyl represented by R _{9 in} formula (2) As the group, an aromatic residue, aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group as a substituent that the ring Ar of formula (1) may have , Arylcarbonyl group and acyl group, and the same as those described in the section of acyl group.

R ₉ in formula (2) is preferably a hydrogen atom or an aliphatic residue, more preferably an alkyl group having 1 to 4 carbon atoms.
In formula (2), Y3 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.

In the formula (2), X ₃ represents CR ₁₀ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and R ₁₀ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, or a cyano group. Represents 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. In addition, when X ₃ is CR ₁₀ , R ₉ and R ₁₀ may be linked to form a ring, and the formed ring may have a substituent. As the aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group or acyl group represented by R ₁₀ , 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 (1) may have and Examples thereof are the same as those described in the item of the acyl group.

Wherein (2), _{Y 2} represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom.

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

In formula (3), R _{2 to} R ₄ , X ₁ , and Y ₁ represent the same meaning as R _{2 to} R ₄ , X ₁ , and Y ₁ in formula (1) according to claim ₁ and are preferred. The same is true.
In Formula (3), R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group.
In Formula (3), X ₄ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or phosphorus Represents an atom.
In formula (3), R _{11 to} R ₁₇ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy Represents a group, 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 _{11 to} R _{17 in the} formula (3), 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.

  Moreover, as a compound represented by Formula (1), the compound represented by following formula (4) is also preferable.

In formula (4), R _{2 to} R ₄ , X ₁ , and Y ₁ represent the same meanings as R _{2 to} R ₄ , X ₁ , and Y ₁ in formula (1) according to claim ₁ and are preferred. The same is true.
In formula (4), R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
In formula (4), X ₃ , X ₄ , and Y ₃ each represent CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom.
Furthermore, in formula (4), R _{15 to} R ₂₂ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy Represents a group, 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 _{15 to} R _{22 in} Formula (4), 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.

In the above formulas (2) to the compound represented by the formula (4), to express a suction interaction between X ₁ and Y _2, it is preferable to select a combination of X ₁ and Y _2. In the compound represented by the formula (2), to express a suction interaction between X ₂ and X _3, it is preferable to select a combination of X ₂ and X _3. Furthermore, in the compound represented by the formula (3), to express a suction interaction between X ₄ and R _14, it is preferable to select a combination of X ₄ and R _14. Furthermore, in the compound represented by the formula (4), to express a suction interaction between X ₃ and X _4, it is preferable to select a combination of X ₃ and X _4. Combinations that express attractive interactions include combinations of oxygen and sulfur atoms, combinations of nitrogen and sulfur atoms, combinations of CH units and nitrogen atoms, combinations of CH units and oxygen atoms, combinations of CH units and fluorine And combinations of phosphorus atom and nitrogen atom. This controls the rotation of the single bond between the central five-membered ring and the left five-membered ring and the single bond between the central five-membered ring and the right six-membered ring in formulas (2) to (4). be able to. As a result, the structure in which the distance between the carbon atoms to which R ₄ and R ₁ O are bonded in Formulas (2) to (4) is preferentially stabilized, photoreactivity is improved, and high photosensitivity is possible. It becomes.

In the compounds represented by the above formulas (2) to (4), R ₁ is a perfluoroalkylsulfonyl group, a perfluoroalkoxysulfonyl group, a perfluoroarylsulfonyl group, a perfluoroalkylcarbonyl group, a perfluoroarylcarbonyl group, or A perfluoroalkylarylcarbonyl group is preferred. Thereby, when the compound represented by the formulas (2) to (4) is irradiated with light, a super strong acid that exhibits very strong acidity is generated. Therefore, the compound serves as a polymerization initiator of the photosensitive resin composition. Useful as a photoacid generator.

  The compounds represented by the formulas (1) to (4) of the present invention can be synthesized using various reactions. The synthesis examples and examples described later are examples thereof, and the synthesis methods of the compounds represented by the formulas (1) to (4) of the present invention are not limited to the methods described in the synthesis examples and examples. In addition, it is possible to synthesize compounds of various structures included in the formulas (1) to (4) by using, as a raw material, compounds having different substituents and partial structures from the raw material compounds used in these synthesis examples and examples. It is.

The photosensitive resin composition according to the present invention includes a photoacid generator containing a compound represented by any one of the above-described formulas (1) to (4), and a cation that is a compound polymerizable by the photoacid generator. Contains a polymerizable compound.
Examples of the cationically polymerizable compound that can be used in the photosensitive resin composition according to the present invention include cyclic ether compounds such as epoxy compounds (resins) and oxetane compounds (resins), (meth) acrylates, vinyl ethers, and ethylene such as styrene. Unsaturated 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, diisopropenylbi Polymers such as phenyl, butadiene and isoprene), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of phenols and 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 Min-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 the oxetane compound 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, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3- Oxeta Rumethyl) 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 Nyl (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-3 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-oxetanyl) Methyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxe) Tanylmethyl) 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 limited to these as long as the compound has an oxetane ring. In what There.

  Specific examples of (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, triethyleneglycol (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, bis Enol-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, cayarad RP-1040 (Nippon Kayaku Co., Ltd.), Kayrad DPCA-30 (Nippon Kayaku Co., Ltd.), UA-33H (Shin Nakamura Chemical Co., Ltd.), UA-53H (Shin Nakamura Chemical Co., Ltd.) (Meth) acrylate monomers such as Migyo Co., Ltd. and M-8060 (manufactured by Toagosei Co., Ltd.), etc., but there is no particular limitation as long as it has a (meth) acrylate group, and any of monomers and oligomers Can also be used. 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-methoxy Aromatic monovinyl ethers such as siphenyl 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; Cationic polymerizable nitrogen-containing monomers such as N-vinylcarbazole and N-vinylpyrrolidone.

  The compounding ratio of the compounds represented by the formulas (1) to (4) in the photosensitive resin composition of the present invention is the essential components of the compounds represented by the formulas (1) to (4) and the cationically polymerizable compound, as 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 excluding the solvent, such as optional components to be used. By setting the blending ratio of the compounds represented by the formulas (1) to (4) 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 in order to lower the viscosity of the resin composition and improve the coating property. 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 and 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 amount used is preferably 95% by mass or less, particularly preferably 10 to 90% by mass in the photosensitive resin composition containing the solvent.

  In the photosensitive resin composition of the present invention, a sensitizer may be further used in order to absorb ultraviolet rays and provide the absorbed light energy to the photocationic polymerization initiator. As the sensitizer, for example, thioxanthones and anthracene compounds having an alkoxy group at the 9th and 10th positions (9,10-dialkoxyanthracene derivative) 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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a C1-C4 alkyl group, a sulfonic acid alkyl ester group, a 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 thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc., and 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) Manufactured by trade name KAYACURE DETX-S) and 2-isopropylthioxanthone are preferable.

  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 exhibits 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 compounds represented by the formulas (1) to (4). It is.

  Various additives, such as a thermoplastic resin, a coloring agent, a coupling agent, a thickener, an antifoamer, and a leveling agent, can be used for the photosensitive resin composition of this invention as needed. 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 increased or decreased as appropriate.

  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 the compounds represented by the formulas (1) to (4) and the essential components of the cationically polymerizable compound, and if necessary, optional solvents, coupling agents, ion catchers, heat It adjusts by mixing and stirring a plastic resin, a coloring agent, a thickener, an antifoamer, a leveling agent, an inorganic filler, etc. by a normal method. When 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. Curing is performed by irradiating the photosensitive resin composition of the present invention with an active energy ray after having a thickness of about 0.01 to 1 mm. 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, and electromagnetic energy having a wavelength of 2000 to 7000 angstroms composed of laser light, electron energy, X-rays, and light energy rays such as 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 of the photosensitive resin compositions are cured with a photoacid generator and dried by touching, but if necessary, the photosensitive resin composition is irradiated with active energy rays. By sometimes heating to about 30 to 100 ° C., it is possible to effectively accelerate the polymerization reaction and further improve the curing rate. Moreover, you may heat-process the cured | curing material obtained by irradiating an active energy ray at 50-250 degreeC in order to complete the hardening by superposition | 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, the fine pattern of the hardened | cured material of a resin composition is given by using the photosensitive resin composition which concerns on this invention, and applying the technique of a conventionally well-known photolithophie, ie, the method including a coating, pattern irradiation, and a development process. It is also possible to obtain When X-rays are used as active energy rays, powders or fine particles of X-ray emitting materials such as BaFCl: Eu, which have the property of absorbing X-rays and emitting ultraviolet rays, may be combined for high sensitivity. Conceivable.

  Specific uses of the photocurable resin composition according to the present invention include paints, coating agents, inks, resists, liquid resists, adhesives, molding materials, putty, glass fiber impregnating agents, sealants, 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, specific examples of the present invention will be described, but the present invention is not limited thereto. Unless otherwise specified, “%” indicates wt% and “parts” indicates parts by weight.

In the following examples, the following experimental apparatus and measuring apparatus were used.
・ High performance liquid chromatography
[Normal phase HPLC]
Analysis pump: HITACHI Pump L2130 (Hitachi High-Tech Science Corporation)
Detector: HITACHI UV Detector L-2400 (Hitachi High-Tech Science Co., Ltd.)
Recorder: HITACHI D-2500 (Hitachi High-Tech Science Co., Ltd.)
Column: COSMOSIL 5SL-II
・ Medium pressure preparative liquid chromatography: EPCLC-W-Prep 2XY A-Type (Yamazen Corporation)
・ Nuclear magnetic resonance system: JNM-AL300 (300MHz) (JEOL Ltd.)
・ Double convergence mass spectrometer (EI-HRMS): JMS-700 MStation (JEOL Ltd.)
・ MALDI-TOF mass spectrometer: JMS-S3000 (JEOL Ltd.)
・ DART mass spectrometer: JMS-Q1000TD (JEOL Ltd.)
・ Organic small molecule X-ray structural analyzer: R-AXIS RAPID / S (3kW) (Rigaku Corporation)
・ Ultraviolet visible spectrophotometer: V-660 (JASCO Corporation)
・ Nanosecond time-resolved spectrometer: TSP-1000M (Unisoku Corporation)
・ Fluorescence spectrophotometer: HITACHI H7000 (Hitachi High-Tech Science Co., Ltd.)
・ Absolute luminescence quantum yield measurement system: C9920-02 (Hamamatsu Photonics)
・ Photoreaction quantum yield measurement system: QYM-01 (Shimadzu Corporation)
・ Spectros cryostat: OXFORD INSTRUMENTS OptistatDN (Oxford Instruments Inc.)
·light source
1kW ultra high pressure mercury lamp: SX-UI-501HQ (USHIO Inc.)
Monochromator: SPG-120 (Shimadzu Corporation)
Nanosecond pulsed Nd: YAG laser: Minilite II (Continuum, USA)
High-power nanosecond pulse Nd: YAG laser: Surelite II (Continuum, USA)
Nanosecond optical parametric oscillator: Panther EX OPO (Continuum, USA)
・ Microwave synthesizer: Initiator + (Biotage Japan KK)

[Example 1]
(1) Synthesis of 5-bromo-2-phenylthiazole (DS-0106) In a 300 mL brown eggplant flask, 8.36 g of 2-phenylthiazole and 14 g of N-bromosuccinimide (NBS) were dissolved in 120 mL of chloroform. And refluxed for 16 hours. Then, sodium thiosulfate aqueous solution was added and extracted with chloroform. The organic layer is recovered, dried over anhydrous magnesium sulfate, the solvent is removed, recrystallized from methanol, and purified to obtain a light brown solid compound represented by DS-0106 in the following formula (5). 0 g was obtained (yield 72.4%). The measured values of the sample obtained by dissolving the compound DS-0106 in deuterated chloroform (CDCl ₃ ) by the nuclear magnetic resonance apparatus (NMR) were as follows.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ7.44-7.46 (m, 3H)), 7.74 (s, 1H), 7.85-7.89 (m, 2H)

(2) Synthesis of 4-bromo-2-phenylthiazole (DS-0105) A 300 mL four-necked flask was purged with argon, distilled diisopropylamine (14.5 mL) was added, and the mixture was cooled to 0 ° C. A 1.6M n-butyllithium / hexane solution (40 mL) was added dropwise to warm to room temperature, and a small amount of tetrahydrofuran (THF) was added to dilute to prepare a THF solution of lithium diisopropylamide (LDA). The four-necked flask was purged with argon, and DS-0106 (4.80 g) was dissolved in THF (50 mL). After stirring at 0 ° C. for 10 minutes, the LDA solution was added dropwise and allowed to stir at 0 ° C. for 30 minutes. After the reaction, extraction was performed with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 4.3 g of a light brown solid compound represented by DS-0105 in the above formula (5). (Yield 90.9%). NMR measurement values of a sample in which compound DS-0105 was dissolved in deuterated chloroform were as follows.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ7.22 (s, 1H), 7.44-7.47 (m, 3H), 7.93-7.96 (m, 2H)

(3) Synthesis of DS-0104 DS-0105 (1.56 g), bispinacolatodiboron (1.65 g), tricyclohexylphosphine (0.28 g), potassium acetate (0.96 g) in a vial for microwave synthesis ) Was dissolved in 1,4-dioxane (19 mL). After deaeration, a catalytic amount (4 mol%) of tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) chloroform adduct was added, and the mixture was stirred at 170 ° C. for 150 minutes using a microwave. After completion of the reaction, water was added and extracted with a water / ethyl acetate system. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain a yellow oily compound (crude product) represented by DS-0104 in the above formula (5). DS-0104 was used in the next reaction as it was. NMR measurement values of a sample prepared by dissolving DS-0104 in deuterated chloroform were as follows.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 1.39 (s, 12H), 7.41-7.44 (m, 3H), 7.98 (s 1H), 8.03-8.06 (m, 2H)

(4) Synthesis of 4,5-dibromo-2-phenylthiazole (DS-0103) In a 300 mL eggplant-shaped flask, DS-0105 (2.52 g) and NBS (2.32 g) were dissolved in chloroform (100 mL). And refluxed for 16 hours. A sodium thiosulfate aqueous solution was added, and the mixture was extracted with chloroform. The organic layer was recovered, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography to obtain 1.8 g of a light brown needle-like solid compound represented by DS-0103 in the following formula (6). (Yield 58.6%). NMR measurement values of a sample in which compound DS-0103 was dissolved in deuterated chloroform were as follows.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ7.22 (s, 1H), 7.44-7.46 (m, 3H), 7.84-7.87 (m, 2H)

(5) Synthesis of DS-0101 In a 300 mL four-necked flask, DS-0103 (1.19 g, 3.74 mmol), DS-0104 (1.24 g), triphenylphosphine (0.21 g, 0.641 mmol) 25 mL of 2M tripotassium phosphate aqueous solution and 50 mL of 1,4-dioxane were added. After deaeration, a catalytic amount (8 mol%) of Pd (PPh ₃ ) ₄ was added and heated to reflux for 24 hours. Aqueous ammonium chloride solution was added and extraction was performed with a water / ethyl acetate system. The organic layer was recovered, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography to obtain 0.33 g of a white solid compound represented by DS-0101 in the above formula (6) (yield). (Rate 22.1%). The NMR measurement values of the sample in which DS-0101 was dissolved in deuterated chloroform and the results of analysis using a DART mass spectrometer were as follows.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 7.45-7.49 (m, 6H), 7.97-8.02 (m, 4H), 8.16 (s, 1H)
DART mass spectrometry: m / z [M + H] ⁺ = calculated value for C ₁₈ H ₁₁ BrN ₂ S ₂ 399; found 399

(6) Synthesis of DS-0102 In a microwave synthesis vial, 1-bromo-2-methoxynaphthalene (0.52 g), bispinacolatodiboron (0.65 g), tricyclohexylphosphine (0.11 g,. 40 mmol) and potassium acetate (0.41 g) were dissolved in 1,4-dioxane (19 mL). A catalytic amount (4 mol%) of Pd ₂ (dba) ₃ chloroform adduct was added, and the mixture was stirred at 170 ° C. for 150 minutes using a microwave. After completion of the reaction, extraction was performed with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography to obtain 0.25 g of a light yellow solid compound represented by DS-0102 in the following formula (7) (yield). (Rate 41.1%). NMR measurement values of a sample in which DS-0102 was dissolved in deuterated chloroform were as follows. FIG. 1 shows the ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 1.47 (s, 12H), 3.91 (s, 3H), 7.19-7.22 (d, 1H, J = 9Hz), 7.27-7.32 (t, 1H , J = 15Hz), 7.39-7.44 (t, 1H, J = 15Hz), 7.73-7.76 (d, 1H, J = 9Hz), 7.83-7.86 (d, 1H, J = 9Hz), 7.89-7.92 (d , 1H, J = 9Hz)
Moreover, the result of having analyzed compound DS-0102 with the DART mass spectrometer was as follows.
DART mass spectrometry: m / z [M + H] ⁺ = C ₁₈ H ₁₁ Calculated value of BrN ₂ S ₂ 399, measured value 398.9653

(7) Synthesis of DS-01 In a 200 mL four-necked flask, DS-0101 (0.11 g), DS-0102 (0.09 g), triphenylphosphine (0.01 g), 2M tripotassium phosphate aqueous solution ( 5 mL) and 1,4-dioxane (5 mL). A catalytic amount (8 mol%) of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) was added, and the mixture was heated to reflux for 24 hours. Aqueous ammonium chloride solution was added and extraction was performed with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography to obtain 0.05 g of a white solid compound represented by DS-01 in the above formula (7) (yield 41). .1%). NMR measurement values of a sample in which DS-01 was dissolved in deuterated chloroform were as follows. FIG. 2 shows the ¹ H-NMR spectrum.
¹ H-NMR (600 MHz, TMS, CDCl ₃ ): δ 3.840 (s, 3H), 6.290 (s, 1H), 7.342-7.365 (m, 2H), 7.415-7.467 (m, 7H), 7.493- 7.509 (m, 2H), 7.852-7.871 (m, 1H), 7.924-7.940 (d, d 2H, J = 9.6Hz, J = 1.8Hz), 8.007-8.023 (d, 2H, J = 9.6Hz), 8.081-8.097 (d, d 2H, J = 9.6Hz, J = 1.8Hz)

In addition, the results of analysis of Compound DS-01 with a MALDI-TOF mass spectrometer were as follows.
HRMS (MALDI-TOF): m / z [M + H] ⁺ = C ₇₂ H ₄₇ N ₄ O ₂ S ₄ ⁺ calculated 477.1118, measured 477.1095

(8) Synthesis of DS-0202 A 300 mL four-necked flask was replaced with argon, 70 mL of DMF was added and cooled to 0 ° C., and 1.61 g of sodium hydride (50% to 72%) was added. The dried 100 mL four-necked flask was purged with argon, and 1-bromo-2-naphthol (2.51 g) was dissolved in 20 mL of DMF and added dropwise to another four-necked flask. After stirring at 0 ° C. for 30 minutes, 1 mL of methoxymethyl chloride diluted with 10 mL of DMF was added dropwise, and after stirring at 0 ° C. for 30 minutes, the temperature was raised to room temperature. After the reaction, extraction was performed with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography to obtain 2.9 g of a colorless oily compound represented by DS-0202 in the following formula (8) (yield) 96.6%). NMR measurement values of a sample in which DS-0202 was dissolved in deuterated chloroform were as follows. FIG. 3 shows the ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ3.61 (s, 3H), 5.39 (s, 2H), 7.40-7.43 (m, 2H), 7.75-7.78 (d, 2H, J = 9Hz ), 8.22-8.25 (d, 1H, J = 9Hz)

(9) Synthesis of DS-0201 A 300 mL four-necked flask was replaced with argon, 1.7 g of DS-0202 was added, diluted by adding a small amount of THF, and cooled to -78 ° C. Thereto, 4 mL of a 1.6 M n-butyllithium hexane solution was added dropwise and stirred for 30 minutes while maintaining the temperature. After adding tributyltin chloride (1.7 mL), the temperature was raised from −78 ° C. to room temperature with stirring for 30 minutes. After the reaction, an aqueous potassium fluoride solution was added and the mixture was extracted with a water / ethyl acetate system. The organic layer was recovered, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography to obtain 1.8 g of a light yellow oily compound represented by DS-0201 in the above formula (8) (yield) 58.2%). NMR measurement values of a sample in which DS-0201 was dissolved in deuterated chloroform were as follows. FIG. 4 shows the ¹ H-NMR spectrum.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ0.84-1.64 (m, 27H or higher), 3.51 (s, 3H), 5.22 (s, 2H), 7.26-7.32 (t, 1H, J = 18Hz), 7.39-7.43 (m, 2H), 7.78-7.81 (d, 3H, J = 9Hz)

(10) Synthesis of DS-02 DS-0101 (0.11 g), DS-0201 (0.15 g), cesium fluoride (0.09 g), and toluene (50 mL) were placed in a 200 mL four-necked flask. After deaeration, a catalytic amount (8 mol%) of Pd (PPh ₃ ) ₄ was added and heated to reflux for 24 hours. An aqueous potassium fluoride solution was added, and the mixture was extracted with a water / ethyl acetate system. The organic layer was recovered, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 0.04 g of a white solid compound represented by DS-02 in the following formula (9) (yield) 28.6%). NMR measurement values of a sample in which DS-02 was dissolved in deuterated chloroform were as follows. FIG. 5 shows the ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, TMS, CDCl ₃ ): δ 3.26 (s, 3H), 5.08-5.10 (d, 1H, J = 8Hz)), 5.20-5.22 (d, 1H, J = 8Hz), 6.31 (s, 1H), 7.35-7.39 (t, 2H, J = 16Hz), 7.40-7.47 (m, 7H), 7.54-7.56 (d, 1H, J = 8Hz), 7.86-7.88 (d, 1H, J = 8Hz), 7.91-7.93 (d, d 2H, J = 8Hz, J = 1.6Hz), 7.97-7.99 (d, 2H, J = 8Hz), 8.07-8.09 (d, d 2H, J = 8Hz, (J = 1.6Hz)

The results of mass spectrometry of DS-0101 using a MALDI-TOF mass spectrometer were as follows.
HRMS (MALDI-TOF): m / z [M + H] ⁺ = C ₃₀ H ₂₂ N ₂ O ₂ S ₂ calculated 507.1209, measured 507.1201

(11) Synthesis of DS-03 and synthesis of DS-04 100 mg of DS-02 was placed in a 300 ml flask, and 15 ml of methanol and 0.1 ml of 35% hydrochloric acid were further added, followed by stirring at 50 ° C. for 12 hours. After completion of the reaction, the mixture was neutralized with sodium hydrogen carbonate, extracted with ethyl acetate, and the solvent was distilled off to obtain a compound represented by DS-03 in the following formula (10). About 28 mg of this DS-03 was placed in a flask of 100 ml, dissolved in 4 ml of dichloromethane, 30 μL of trifluoroacetic anhydride and 60 μL of triethylamine were added and stirred for 2 hours while cooling in an ice bath. After completion of the reaction, 5 mL of water and 5 mL of ethyl acetate were added for extraction, and then the ethyl acetate layer was collected and the solvent was distilled off to obtain a compound represented by DS-04 in the following formula (10).
The results of analyzing DS-04 with a DART mass spectrometer were as follows.
DART mass spectrometry: m / z [M + H] + = calculated for C30H18O2N2F3S2 559, measured 559

(12) Spectral change accompanying light irradiation of DS-01
A sample in which DS-01 was dissolved in hexane was irradiated with ultraviolet light (365 nm), and it was confirmed that DS-01 exhibited a photochromic reaction that colored blue.
Moreover, the change of the absorption spectrum of the sample when ultraviolet light was irradiated for 0 to 240 seconds was examined. An ultraviolet-visible spectrophotometer (JASCO V-660) was used to measure the absorption spectrum. The result is shown in FIG.
FIG. 6A shows the change in the absorption spectrum when the ultraviolet light irradiation time is 0 to 30 seconds. As is clear from this figure, the absorption spectrum of the sample showed a characteristic absorption band at a wavelength of 550 nm by irradiation with ultraviolet light. Since this is similar to the change in absorption spectrum observed in many dimethyl derivatives, it is attributed to DS-01-C represented by the following formula (11).

  On the other hand, FIG. 6B shows a change in the absorption spectrum when the ultraviolet light irradiation time is 30 seconds to 240 seconds. As is clear from this figure, it was found that when the irradiation time of ultraviolet light exceeds 30 seconds, the absorption band at a wavelength of 550 nm gradually decreases.

Next, after irradiating a sample obtained by dissolving compound DS-01 in deuterated chloroform with ultraviolet light (365 nm) and confirming that the compound DS-01 exhibits a photochromic reaction that turns blue, the blue color disappears. When the compound contained in the sample was identified by NMR and mass spectrometry, the following results were obtained. FIG. 7 shows the ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, TMS, CDCl ₃ ): σ7.55-7.64 (m, 6H), 7.70-7.74 (t, 1H, J = 16Hz), 7.89-7.93 (t, 1H, J = 16Hz) , 8.02-8.09 (m, 3H), 8.25-8.27 (d, 2H, J = 8Hz), 8.36-8.38 (d 2H, J = 8Hz), 10.98-11.00 (d, 1H, J = 8Hz)
DART mass spectrometry: m / z [M + H] ⁺ = C ₂₈ H ₁₆ N ₂ S ₂ calculated 445, measured 445.1

From the above results, it was confirmed that DS-01-C was obtained from DS-01 by the reaction caused by ultraviolet light irradiation, and DS-01-A was obtained by the subsequent reaction.
In addition, with respect to DS-02 described above, the same result was obtained when a sample dissolved in deuterated chloroform was irradiated with ultraviolet light (365 nm) and the same experiment as DS-01 was performed. From this, as shown in the following formula (12), it is confirmed that DS-02-C can be obtained from DS-02 by the reaction caused by ultraviolet irradiation, and DS-01-A can be obtained by the subsequent reaction. It was done.

[Example 2]
(1) Synthesis of 7-methoxyquinoline (RL-0107) Sodium nitrobenzenesulfonic acid (3.9 g, 17.3 mmol) and 10 ml of methanesulfonic acid were placed in a 100 ml three-necked flask and stirred. Iron (II) sulfate 0.2 g, 0.8 mmol and 3-methoxyaniline (3.09 mL) were added dropwise and heated to about 120 ° C. Glycerol (6.3 g) was added and reacted at 135 ° C. for 16 hours. After completion of the reaction, about 100 mL of 10M NaOH aqueous solution was added and extracted with ethyl acetate. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 4.2 g of RL-0107 (yield: about 48%). The structure of RL-0107 was identified by NMR and mass spectrometry, and the following results were obtained.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 3.96 (s, 3H), 7.19-7.29 (m, 2H), 7.43 (sd, 1H), 7.68-7.71 (d, 1H, J = 9Hz) , 8.06-8.09 (d, 1H, J = 9Hz), 8.83-8.85 (d, 1H, J = 9Hz)
ESI-HRMS: m / z [M + H] ⁺ = C ₁₀ H ₁₀ NO ⁺ calculated value 160.07624, measured value 160.07621
From the above results, it was confirmed that RL-0107 is a compound having a structure represented by the following formula (13).

(2) Synthesis of 8-bromo-7-methoxyquinoline (RL-0106) 4.2 g of RL-0107 was placed in a 100 mL three-necked flask, and 5.7 g of N-bromosuccinimide (NBS) was added. Furthermore, 60 mL of dichloromethane was added, and argon gas substitution was performed at 0 ° C. The reaction was allowed to proceed for an additional 12 hours at room temperature. After completion of the reaction, sodium thiosulfate (Na ₂ S ₂ O ₃ ) was added and extracted with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 5.9 g of RL-0106 (yield: about 93.1%). The structure of RL-0106 was identified by NMR and mass spectrometry, and the following results were obtained.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 4.09 (s, 3H), 7.33-7.39 (m, 2H), 7.81-7.84 (d, 1H, J = 9Hz), 8.12-8.15 (d, 1H, J = 9Hz), 9.03-9.04 (d, 1H, J = 3Hz).
EI-HRMS: m / z [M] ⁺ = C ₁₀ H ₈ BrNO ⁺ calculated value 236.97893, actual value 236.97833
From the above results, it was confirmed that RL-0106 is a compound having a structure represented by the above formula (13).

(3) Synthesis of RL-0104 1.64 g of benzothiopheneboronic acid (RL-0105), 1.46 g of RL-0106, 0.98 g of sodium carbonate, 75 mL of water, 150 mL of dimethoxyethane in a 500 mL three-necked flask I put it in. After deaeration, a catalytic amount (5 mol%) of Pd (PPh ₃ ) ₄ was added and reacted at 75 ° C. to 85 ° C. for 24 hours. After completion of the reaction, water was added and extracted with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 1.6 g of brown solid RL-0104 (yield: about 90%). The structure of RL-0104 was identified by NMR and mass spectrometry, and the following results were obtained.
₁ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 3.85 (s, 3H), 7.23-7.34 (m, 4H), 7.48 (s, 1H), 7.50-7.51 (d, 1H, J = 3Hz ), 7.91-7.94 (d, 2H, J = 9Hz), 8.14-8.18 (d, 1H, J = 12Hz), 8.80-8.82 (d, 1H, J = 6Hz).
EI-HRMS: m / z [M] ⁺ = C ₁₈ H ₁₃ NOS ⁺ calculated value 291.0718, actual value 291.0705
From the above results, it was confirmed that RL-0104 is a compound having a structure represented by the following formula (14).

(4) Synthesis of RL-0103 1.45 g of compound RL-0104 and 2.3 g of N-bromosuccinimide were each placed in 30 mL of a water / tetrahydrofuran mixed solution and reacted at room temperature and in a nitrogen atmosphere for 12 hours. After completion of the reaction, water was added and extracted with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 1.3 g of brown solid RL-0103 (yield: about 71%). The structure of RL-0103 was identified by NMR and mass spectrometry, and the following results were obtained.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 3.89 (s, 3H), 7.05-7.08 (d, 1H, J = 9 Hz), 7.15-7.21 (t, 1H, J = 9 Hz), 7.26-7.32 (m, 2H), 7.49-7.52 (d, 2H, J = 9Hz), 7.77-7.80 (d, 1H, J = 9Hz), 7.96-7.99 (d, 1H, J = 9Hz), 8.16- 8.19 (d, 1H, J = 9Hz), 8.80-8.82 (d, 1H, J = 6Hz).
ESI-HRMS: m / z [M + H] ⁺ = C ₁₈ H ₁₃ BrNOS ⁺ calculated value 369.99012, actual value 369.99044
From the above results, it was confirmed that RL-0103 is a compound having a structure represented by the above formula (14).

(5) Synthesis and NMR spectrum of RL-0102 In a 300 mL three-necked flask, 1.3 g of RL-0103, 1.88 g of DS-0104, 0.47 g of triphenylphosphine, 30 mL of 2M aqueous potassium phosphate solution, 1, 80 mL of 4-dioxane was added. After deaeration, a catalytic amount (5 mol%) of Pd (PPh ₃ ) ₄ was added and reacted at 110 ° C. for 24 hours. After completion of the reaction, water was added and the mixture was extracted with a water / ethyl acetate system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed, and the residue was purified by column chromatography to obtain 0.66 g of yellow solid RL-0102 (yield: about 42%). The structure of RL-0102 was identified by NMR and mass spectrometry, and the following results were obtained. FIG. 8A shows the ¹ H-NMR spectrum of RL-0102, and FIG. 8B shows the ¹³ C-NMR spectrum of RL-0102.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ 3.76 (s, 3H), 6.35 (s, 1H), 7.04-7.07 (d, 1H, J = 9Hz), 7.16-7.22 (t, 1H, J = 18Hz), 7.22-7.34 (m, 4H), 7.39-7.42 (m, 3H), 7.51-7.54 (d, 1H, J = 9Hz), 7.88-7.93 (m, 1H), 8.00-8.03 (d , 1H, J = 9Hz), 8.18-8.21 (d, 1H, J = 9Hz), 8.75-8.77 (d, 1H, J = 6Hz).
¹³ C-NMR (300 MHz, TMS, CDCl ₃ ): δ166.42, 158.45, 151.81, 150.78, 148.42, 141.75, 139.27, 136.11, 135.37, 133.56, 130.16, 129.94, 129.00, 127.70, 126.78, 124.61, 124.17, 124.00, 123.38, 122.52, 120.40, 119.45, 114.70, 113.50, 56.81.
ESI-HRMS: m / z [M + H] ⁺ = C ₂₇ H ₁₈ N ₂ OS ₂ ⁺ calculated value 451.09388, actual value 451.09339
From the above results, it was confirmed that RL-0102 is a compound having a structure represented by the above formula (14).

(6) Synthesis of RL-0101 In a 20 mL two-necked flask, 150 mg of RL-0102 and 8 mL of dichloromethane were placed, and an argon atmosphere was established. 1.7 mL of boron tribromide (BBr ₃ ) was added dropwise and reacted at room temperature for 3 days. After completion of the reaction, water was added and extracted with a water / dichloromethane system. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain a crude product represented by the following formula (15) as RL-0101. The RL-0101 crude product was used in the next reaction as it was.

(7) Synthesis and NMR spectrum of RL-0100 In a 20 mL two-necked flask, 10 mL of dichloromethane and the above-mentioned RL-0101 crude product were placed in an argon atmosphere. After cooling to 0 ° C., 0.5 mL of triethylamine and 0.26 mL of trifluoromethanesulfonic acid chloride were added and reacted at 0 ° C. for 3 hours. After completion of the reaction, water was added and extracted with a water / dichloromethane system. The organic layer was collected, dried over anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography, and further purified by reverse phase HPLC (mobile phase; acetonitrile) to obtain 50 mg of yellow solid RL-0100 (recovery). The rate is about 71%). The structure of RL-0100 was identified by NMR and mass spectrometry, and the following results were obtained. FIG. 9A shows the ¹ H-NMR spectrum of RL-0100, and FIG. 9B shows the ¹³ C-NMR spectrum of RL-0100.
¹ H-NMR (300 MHz, TMS, CDCl ₃ ): δ6.22 (s, 1H), 6.67 (s, 1H), 7.04-7.07 (d, 1H, J = 9Hz), 7.20-7.23 (t, 1H , J = 9Hz), 7.35-7.38 (d, 1H, J = 9Hz), 7.42-7.47 (m, 4H), 7. 91-7.96 (m, 4H), 8.17-8.20 (d, 1H, J = 9Hz ), 8.73-8.75 (d, 1H, J = 6Hz).
¹³ C-NMR (300 MHz, TMS, CDCl ₃ ): δ 167.51, 155.29, 151.37, 149.45, 148.53, 141.08, 139.65, 136.28, 133.17, 130.61, 130.14, 129.15, 126.83, 125.42, 124.78, 124.10, 123.80, 122.62, 119.41, 119.32, 116.89, 115.31.
ESI-HRMS: m / z [M + Na] ⁺ = C ₂₇ H ₁₈ N ₂ OS ₂ Na ⁺ calculated value 591.00946, actual value 591.00920
From the above results, it was confirmed that RL-0100 is a compound having a structure represented by the above formula (15).

(8) Spectral change accompanying light irradiation of RL-0102
A sample in which RL-0102 was dissolved in hexane was irradiated with ultraviolet light (365 nm), and it was confirmed that RL-0102 exhibited a photochromic reaction that colored blue.
Moreover, the change of the absorption spectrum of the sample when ultraviolet light was irradiated for 0 to 25 seconds was examined. An ultraviolet-visible spectrophotometer (JASCO V-660) was used to measure the absorption spectrum. The result is shown in FIG. As is apparent from this figure, the absorption spectrum of the sample showed a characteristic absorption band at 550 nm by irradiation with ultraviolet light. Since this is similar to the absorption spectrum change observed in many dimethyl derivatives, it is attributed to RL-0102-C represented by the following formula (16).

  On the other hand, when a sample in which RL-0102 was dissolved in methanol was irradiated with ultraviolet light for 0 to 10 minutes, a photochromic reaction showing a new absorption band in the ultraviolet region was observed as shown in FIG. In this absorption spectrum, the absorbance near the wavelength of 300 nm is enhanced, and this is attributed to RL-0102-A in which methanol is desorbed from RL-0102-C shown in the above formula (16).

(9) Spectral changes associated with light irradiation of RL-0100 When a sample in which RL-0100 is dissolved in methanol is irradiated with ultraviolet light for 0 to 360 seconds, a photochromic reaction showing a new absorption band in the ultraviolet region occurs. It was seen (FIG. 12). In this absorption spectrum, the absorbance near 300 nm is enhanced, which is attributed to RL-0100-A from which methanol is eliminated from RL-0100. Further, in this absorption spectrum, a weak absorption band was observed at 550 nm, which was similar to the absorption spectrum change observed in many of the dimethyl derivatives, and is attributed to RL-0100-C (the following formula: (See (17)).

  Furthermore, when a sample in which RL-0100 was dissolved in chloroform was irradiated with ultraviolet light for 0 to 240 seconds, a photochromic reaction showing a new absorption band in the ultraviolet region was observed (FIG. 13). In this absorption spectrum, the absorbance near 300 nm is enhanced, which is attributed to RL-0100-A from which methanol has been eliminated. Further, in this absorption spectrum, a weak absorption band is observed at 550 nm, which is similar to the absorption spectrum change seen in many of the dimethyl derivatives, and is attributed to RL-0100-C (the above formula (16 )reference).

(10) X-ray structural analysis of RL-0100-A
The sample after light irradiation of RL-0100 in methanol was separated by column chromatography to obtain a yellow powder after removing the solvent. The results of X-ray structural analysis of RL-0100-A obtained after recrystallization of this yellow powder are shown in FIG. 14 and Table 1 below.

(11) Absorption maximum wavelength, molar extinction coefficient, and photoreaction quantum yield
The absorption maximum wavelength, molar extinction coefficient, and photoreaction quantum yield of RL-0102, RL-0100, and RL-0100-A were measured, and the results shown in Table 2 below were obtained. The photoreaction quantum yield was measured using QYM-01 manufactured by Shimadzu Corporation.

(11) Resin composition containing RL-0100 Propylene oxide and RL-0100 (0.2 mol%) were mixed and irradiated with ultraviolet rays (313 nm) for 10 minutes. Thereafter, the obtained polymer substance was identified by mass spectrometry. As a result, the mass spectrometry chart shown in FIG. 15 was obtained, and the progress of photopolymerization was confirmed.

(12) Pattern formation In diethyl glycol diethyl ether (DGDE), 25 wt% of SU-8 monomer and 10 wt% of RL-0100 are dissolved with respect to the solvent weight, and a spin coat film is formed on the glass substrate. The sample which formed was produced (rotation speed 1500rpm, 30 seconds). This sample was heated at 65 ° C. for 3 minutes and further heated at 100 ° C. for 7 minutes to remove the solvent. Thereafter, the mask was brought into close contact, and irradiation with ultraviolet light (365 m) was performed (22 mW / cm ² , 20 minutes). After the irradiation, a heat treatment was further performed at 65 ° C. for 3 minutes and at 100 ° C. for 2 minutes, and then soluble components were removed with isopropyl alcohol. As shown in FIG. 16, as a result of observing the sample with an electron microscope, pattern formation was confirmed.

[Example 3]
(1) Synthesis of AM-06
The compound AM-06 was obtained from 4-bromo-2-phenylthiazole (AM-01) through the five steps shown in the following formula (18) (total yield 67%).

(2) Comparison of AM-04 and AM-06 structures
The results of X-ray structural analysis of AM-04 and AM-06 are shown in FIG. FIG. 17A shows the result of AM-04, and FIG. 17B shows the result of AM-06.

(3) Spectral changes accompanying light irradiation of AM-04 and AM-06
Samples obtained by dissolving AM-04 and AM-06 in methanol were each irradiated with ultraviolet rays (365 nm), and the absorption spectra of the resulting samples were measured. The result is shown in FIG. The upper part of FIG. 18 shows the results for AM-04, and the lower part shows the results for AM-06. In any compound, the absorbance at a wavelength of 250 to 400 nm was enhanced by ultraviolet irradiation. Since this is similar to the change in absorption spectrum observed in many dimethyl derivatives, it was inferred that AM-04 and AM-06 were changed to ring-closed AM-04a and AM-06a, respectively.

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

Claims (16)

A compound represented by 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 ring Represents a cyclopentene ring, a cyclohexene ring, a cyclopentene ring or a maleimide,
R ₁ is an aliphatic hydrocarbon group, alkylsulfonyl group, alkoxysulfonyl group, arylsulfonyl group, alkylcarbonyl group, alkoxycarbonyl group, arylcarbonyl group, halogenated alkylsulfonyl group, halogenated alkoxysulfonyl group, halogenated arylsulfonyl group Represents a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated 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,
When X ₁ represents CR ₅ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and X ₁ represents CR ₅ , 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, or R ₂ and R ₅ may be linked to form a ring. ,
When X ₂ represents CR ₆ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and X ₂ represents CR ₆ , 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, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group, or R ₃ and R ₆ may be linked to form a ring. ,
Y ₁ is a sulfur atom, an oxygen atom, a selenium atom or a _CR 7 _{R 8, when Y 1} represents _CR 7 _{R 8, R 7} and _{R 8} represents a hydrogen atom or an aliphatic hydrocarbon residue, compound. A compound represented by the following formula (2),
Equation _{(2) R 2 ~R 4,} X 1, X 2, and _{Y 1} is _{R 2 ~R 4, X 1,} X 2 in the formula (1) according to claim 1, and the same meaning as _{Y 1} Represent,
R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
R ₉ 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. ,
X ₃ represents CR ₁₀ , a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom, and when X ₃ represents CR ₁₀ , R ₁₀ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue Represents 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, or R ₉ and R ₁₀ may be linked to form a ring. ,
The compound according to claim 1, wherein Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom. A compound represented by the following formula (3),
In formula (3), R _{2 to} R ₄ , X ₁ and Y ₁ represent the same meaning as R _{2 to} R ₄ , X ₁ and Y ₁ in formula (1) according to claim 1,
R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
X ₄ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
R _{11 to} R ₁₇ 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 The compound according to claim 1, which represents a group or an acyl group. A compound represented by the following formula (4),
In formula (4), R _{2 to} R ₄ , X ₁ , and Y ₁ represent the same meaning as R _{2 to} R ₄ , X ₁ , and Y ₁ in formula (1) according to claim 1,
R ₁ represents a halogenated alkylsulfonyl group, a halogenated alkoxysulfonyl group, a halogenated arylsulfonyl group, a halogenated alkylcarbonyl group, a halogenated alkoxycarbonyl group, or a halogenated arylcarbonyl group,
X ₃ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
X ₄ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
Y ₂ represents CH, a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, or a phosphorus atom,
R _{15 to} R ₂₂ 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 The compound according to claim 1, which represents a group or an acyl group. In the compound according to any one of claims 2 to 4,
A compound wherein R ₁ is a perfluoroalkylsulfonyl group, a perfluoroalkoxysulfonyl group, a perfluoroarylsulfonyl group, a perfluoroalkylcarbonyl group, a perfluoroalkoxycarbonyl group or a perfluoroarylcarbonyl group. In the compound according to any one of claims 2 to 4,
The combination of X ₁ and Y ₂ are selected from a combination of groups or atoms expressing suction interaction between X ₁ and Y _2, compound. The compound of claim 2, wherein
The combination of X ₂ and X ₃ are selected from a combination of groups or atoms expressing suction interaction between X ₂ and X _3, compound. The compound of claim 3, wherein
The combination of X ₄ and R ₁₄ are selected from a combination of expressing group or atom suction interaction between X ₄ and R _14, compound. 5. A compound according to claim 4,
The combination of X ₃ and X ₄ are selected from the combinations of groups or atoms expressing suction interaction between X ₃ and X _4, compound. In the compound according to any one of claims 6 to 9,
A group or atom combination that exhibits an attractive interaction is a combination of an oxygen atom and a sulfur atom, a combination of a nitrogen atom and a sulfur atom, a combination of CH and a nitrogen atom, a combination of CH and an oxygen atom, a combination of CH and fluorine Or a combination of a phosphorus atom and a nitrogen atom.   A photoacid generator containing the compound according to claim 1. .   The photo-acid generator containing the compound in any one of Claims 2-10.   A photosensitive resin composition comprising the photoacid generator according to claim 11 and a compound polymerizable by the photoacid generator.   A photosensitive resin composition comprising the photoacid generator according to claim 12 and a compound polymerizable by the photoacid generator.   A cured product obtained by curing the photosensitive resin composition according to claim 13.   A cured product obtained by curing the photosensitive resin composition according to claim 14.