TWI623519B - Novel compound, photoacid generator containing the compound and photosensitive resin composition containing the photoacid generator - Google Patents

Abstract

The present invention is a compound represented by the following formula (1).

(In the formula (1), the ring Ar represents an aromatic ring or a heterocyclic ring, etc. R ₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group or an alkylcarbonyl group, an alkoxycarbonyl group or an arylcarbonyl group, etc. R ₂ and R ₃ each independently represent a hydrogen atom or an aromatic residue, etc. R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue. X ₁ and X ₂ each independently represent a nitrogen atom, etc. Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom or selenium. Atomic, etc.)

Description

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

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

The photosensitive resin composition is put into practical use in the fields of printing inks, paints, coatings, various resist inks, and the like from the viewpoints of energy saving, high production efficiency, and the like. Many of these photosensitive resin compositions are photoradical polymerization reactors using a compound having an unsaturated double bond such as an acrylate compound, but on the other hand, a photoacid generator containing an epoxy compound (resin) or the like is also used. The photocationic polymerization of the photosensitive resin composition was actively studied. A method of performing photocationic polymerization by irradiating a cationically polymerizable compound such as an epoxy compound with an active energy ray such as an ultraviolet ray or an electron beam, and a method of photoradical polymerization using an acrylate compound or the like by irradiation with an active energy ray. It has various characteristics which are advantageous in comparison with a method of hardening by photo-radical polymerization, etc., which has a small hardening shrinkage or is not affected by oxygen during hardening.

As a photoacid generator contained in the photopolymerizable photosensitive resin composition, a triarylsulfonium salt (see Patent Document 1) and a benzoquinone methyl phosphonium salt having a naphthalene skeleton (Patent Document 2) are known. Acid generator. However, due to the ionic photoacid generator The compatibility (solubility) of the hydrophobic cationically polymerizable compound or solvent used in the photosensitive resin composition is likely to be insufficient. Therefore, in order to solve this problem, a nonionic photoacid generator has also been studied. By using a nonionic photoacid generator, the above problem is not only improved, but since the nonionic photoacid generator generally absorbs in a longer wavelength region than the ion photoacid generator, it is expected to use a medium pressure, a high pressure mercury lamp or the like. When the photosensitive resin composition is cured by the i-ray or the g-ray, the sensitivity is excellent (see Patent Document 3).

However, the acid yield of the previously known nonionic photoacid generator has a quantum yield of about 0.1 to 0.3, and it is expected to develop a nonionic photoacid generator having a high sensitivity to a high acid yield quantum yield.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 50-151997

[Patent Document 2] Japanese Patent Laid-Open No. 09-118663

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-213899

It is an object of the present invention to provide a nonionic photoacid generator having a high solubility to a hydrophobic cationically polymerizable compound or solvent and having a high sensitivity to a quantum yield of a higher acid of an i-ray or a g-ray. Agent.

The present inventors have made great efforts to solve the above problems, and as a result, have found that the above problems can be solved by using a photoacid generator containing a novel compound having a specific structure, thereby completing the present invention.

That is, the present invention relates to the following: (1) A compound represented by the following formula (1), [Chemical Formula 1] (In the formula (1), the ring Ar represents a benzene ring, a naphthalene ring, a thiophene ring, a benzothiophene ring, a furan ring, a benzofuran ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, an imidazolidine. a ring, a benzimidazole ring, a cyclopentene ring, a cyclohexene ring, a cyclopentene ring, an anthracene ring or a pyrrole ring; R ₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group, an alkoxysulfonyl group, An arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group or an arylcarbonyl group; and R ₂ and R ₃ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboguanamine group, Amidino, alkoxy, aryloxy, alkoxycarbonyl, arylcarbonyl, decyl or trimethyldecyl; R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue; X ₁ represents a CR ₅ or a nitrogen atom; ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group; ₂ and R ₅ may also be linked to form a ring; _X-2 represents a CR ₆ or a nitrogen atom; R ₆ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, 2carboxamide , Acyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, acyl or arylcarbonyl group; R ₃ and R ₆ may also be linked to form a ring; Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom, a selenium Atom or CR ₇ R ₈ ; R ₇ and R ₈ represent a hydrogen atom or an aliphatic hydrocarbon residue; (2) a compound according to the above item (1), which is represented by the following formula (2), Formula _{(2), R 1 ~ R 4, X} 1, X 2, Y 1 and Y ₂ represents a front (1) of the formula R (1) in the _{1 ~ R 4, X 1,} X 2, Y 1 And Y _{2 have the} same meaning; R ₉ to R ₁₂ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, and an aromatic group. An oxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group; Y ₃ represents a sulfur atom, an oxygen atom or a selenium atom; (3) a compound according to the above item (2), wherein R ₁ is an alkyl group having 1 to 4 carbon atoms; (4) A compound according to the above item (2), wherein X ₁ and X ₂ are a nitrogen atom; (5) a compound according to the above item (2), wherein Y ₁ to Y ₃ are each independently a sulfur atom or an oxygen atom; (6) A compound according to the above item (1), which is represented by the following formula (3), [Chemical 3] (In the formula _{(3), R 1 ~ R} 4, X 1, X 2, Y 1 and Y ₂ represents a front (1) of the formula (R 1) in the _{1 ~ R 4, X 1,} X 2, Y ₁ and Y _{2 have the} same meaning; R ₁₃ to R ₁₈ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, or acyl); (7) the compound of the preceding paragraph (6) of which R ₁ is a C 1 alkylsulfonyl group 4 of; (8) the above item (6) a compound wherein X ₁ is CR ₅ , R ₂ and R _{5 are} bonded to form a benzene ring, and X ₂ is CR ₆ , and R ₃ is bonded to R _{6 to} form a benzene ring; (9) a compound according to the above item (6), wherein Y ₁ and Y ₂ are a sulfur atom or an oxygen atom; (10) A photoacid generator containing the compound according to any one of the above items (1) to (9); (11) a photosensitive resin composition containing The photoacid generator according to the above item (10) and a compound polymerizable by the photoacid generator; (12) a cured product obtained by curing the photosensitive resin composition according to the above (11).

By using the novel compound of the present invention having the specific structure represented by the formula (1), it is possible to provide a higher solubility of a cationically polymerizable compound or solvent having hydrophobicity. A nonionic photoacid generator having high sensitivity to the quantum yield of a higher acid of the active energy ray.

Figure 1 is a ¹ H-NMR spectrum of a sample of propylene oxide alone and a sample obtained by adding methanesulfonic acid to propylene oxide.

2 is a ¹ H-NMR of a sample obtained by dissolving a compound represented by the formula BT-OMs obtained in Example 1 and propylene oxide in chloroform, and irradiating the sample with a sample having ultraviolet rays having a wavelength of 365 nm. spectrum.

Fig. 3 is a ¹ H-NMR spectrum of a sample obtained by dissolving a compound represented by the formula BT-OMs in chloroform.

Fig. 4 is a ¹ H-NMR spectrum of a sample obtained by dissolving propylene oxide in chloroform.

The present invention will be described in detail below.

The compound of the present invention has a structure represented by the following formula (1). The compound represented by the formula (1) is characterized in that when the compound is irradiated with an active energy ray such as an i-ray or a g-ray, a desorption reaction of an acid induced by a substituent represented by R ₁ O in the formula occurs. The acid to be used is a function as a polymerization initiator for a cationically polymerizable compound.

In the formula (1), the ring Ar represents a benzene ring, a naphthalene ring, a thiophene ring, a benzothiophene ring, a furan ring, a benzofuran ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, an imidazol ring. a benzimidazole ring, a cyclopentene ring, a cyclohexene ring, a cyclopentene ring, an anthracene ring or a pyrrole ring.

The ring Ar may have a substituent, and specific examples of the substituent which may be included include an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxyguanamine group, a guanamine group, and an alkane group. Oxyl, aryloxy, alkoxycarbonyl, arylcarbonyl and anthracenyl. Here, the "ring Ar having a substituent" herein means a ring structure in which a hydrogen atom on the ring Ar is substituted with the above substituent. The number of substituents may be plural, and the plurality of substituents may be different from each other.

Further, the heterocyclic ring represented by the ring Ar may form a cyclic ketone or a cyclic thioketone.

The aromatic residue which may be a substituent of the ring Ar means a group which removes one hydrogen atom from an aromatic ring or a condensed ring containing an aromatic ring, and the aromatic residue may have a substituent. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a tripropylene ring, an anthracene ring, an anthracene ring, a pyridine ring, and a pyridyl group. Ring, pyrimidine ring, pyrazole ring, pyrazolidine ring, tetrahydrothiazole ring, Azolidinium ring, pyran ring, benzopyran ring, pyrrole ring, pyrrolidine ring, benzimidazole ring, imidazoline ring, imidazolidinium ring, imidazole ring, triazole ring, three Ring, diazole ring, porphyrin ring, thiophene ring, thienothiophene ring, furan ring, Oxazole ring, Diazole ring, thiazide Ring, thiazole ring, anthracene ring, benzothiazole ring, benzothiadiazole ring, naphthothiazole ring, benzo Oxazole ring, naphthalene An azole ring, a fluorene ring, a benzofluorene ring, a quinoline ring, a quinazoline ring, an anthracene ring and an oxazole ring, etc., preferably a carbon number of 4 to 20 from an aromatic ring or a condensation containing an aromatic ring The ring removes a group of one hydrogen atom.

The aliphatic hydrocarbon residue which may have a substituent of the ring Ar may, for example, be a saturated or unsaturated linear, branched or cyclic alkyl group, and the aliphatic hydrocarbon residue may have a substituent. The aliphatic hydrocarbon residue preferably has a carbon number of from 1 to 36, more preferably from 1 to 18, still more preferably from 1 to 8. Specific examples of the aliphatic hydrocarbon residue include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, and n-pentyl group. Positive Base, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-ten Hexaalkyl, n-heptadecyl, n-octadecyl, cyclohexyl, ethenyl, propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, Cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, pentynyl, hexynyl, isohexynyl, cyclohexynyl and the like. Further, examples of the cyclic alkyl group include a cycloalkyl group having 3 to 8 carbon atoms.

Examples of the halogen atom which the substituent of the ring Ar may have include an atom such as fluorine, chlorine, bromine or iodine.

Examples of the mercapto group which may have a substituent of the ring Ar include a mercaptoamine group, an ethenylamino group, and an alkylguanamine group. Specific examples thereof include a mercaptoamine group and an ethenamine group. N-methyl decylamino, N-ethyl decylamino, N-(n-propyl)decylamino, N-(n-butyl)decylamino, N-isobutylguanidinyl, N-( Second butyl decyl), N-(t-butyl) decylamino, N,N-dimethyl decylamino, N,N-diethyl decylamino, N,N-di (positive Propyl) decylamino, N,N-di(n-butyl)decylamino, N,N-diisobutylamylamine, N-methylethylammonium, N-ethylethylammonium , N-(n-propyl)acetamido, N-(n-butyl)ethylammonium, N-isobutylethylamino, N-(t-butyl)ethylammonium, N- (t-butyl) acetamidine, N,N-dimethylacetamido, N,N-diethylacetamido, N,N-di(n-propyl)acetamidamine, N,N-di(n-butyl)ethylammonium, N,N-diisobutylethylamino, phenylguanamine, naphthylamino, phenylethylamino and naphthyl Amidoxime and the like.

Examples of the alkoxy group which may have a substituent of the ring Ar include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a second butoxy group. And a third butoxy group.

Examples of the aryloxy group which may have a substituent of the ring Ar include a phenoxy group, a naphthyloxy group and the like.

The alkoxycarbonyl group which may have a substituent of the ring Ar may, for example, be an alkoxycarbonyl group having 1 to 10 carbon atoms. As a specific example, it is a methoxycarbonyl group, an ethoxycarbonyl group, or a n-propyl group. Oxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy Alkylcarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl.

The arylcarbonyl group which may be a substituent of the ring Ar, for example, represents a group in which an aryl group such as benzophenone or naphthacene is bonded to a carbonyl group.

Examples of the fluorenyl group which may have a substituent of the ring Ar include, for example, an alkylcarbonyl group having 1 to 10 carbon atoms, an arylcarbonyl group, and the like, and preferably an alkylcarbonyl group having 1 to 4 carbon atoms, and specific examples thereof include acetamidine. A group, a propyl group, a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a benzamyl group, a naphthylmethyl group, and the like.

Further, a plurality of substituents on the ring Ar may be bonded to each other to form a ring. The ring which can be formed is the same as the specific example of the aromatic ring described in the item of the aromatic residue which may have the substituent of the ring Ar of the formula (1).

The aromatic residue and the aliphatic hydrocarbon residue which may have a substituent of the ring Ar may have a substituent, and the substituent which may be the same as the ring Ar of the formula (1) may be mentioned.

The ring Ar in the formula (1) is preferably a hetero ring containing a sulfur atom, more preferably a thiophene ring. Further, a ring formed by bonding a substituent on the ring Ar to each other is preferably a benzene ring.

In the 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.

The aliphatic hydrocarbon residue represented by R ₁ may be the same as those described for the aliphatic hydrocarbon residue which may be a substituent of the ring Ar of the formula (1).

The alkylsulfonyl group represented by R _{1 of} the formula (1) and the alkyl group in the alkylcarbonyl group may be exemplified by the aliphatic hydrocarbon residue which may be a substituent which the ring Ar of the formula (1) may have. The saturated or unsaturated linear, branched or cyclic alkyl group is the same, and a halogenated alkyl group such as a fluorinated alkyl group, an alkyl iodide group, an alkyl chloride group or an alkyl iodide group is also contained in the alkyl group. The range of alkyl groups in the thiol and alkylcarbonyl groups.

The alkoxysulfonyl group represented by R _{1 of} the formula (1) and the alkoxy group in the alkoxycarbonyl group may be exemplified by the alkoxy group which may be a substituent which the ring Ar of the formula (1) may have. The same is true.

The arylsulfonyl group represented by R _{1 of} the formula (1) and the aryl group in the arylcarbonyl group may be exemplified by the term of the arylcarbonyl group which may have a substituent of the ring Ar of the formula (1). The same as the base.

R _{1 of the} formula (1) is preferably an alkylsulfonyl group, more preferably an alkylsulfonyl group having 1 to 8 carbon atoms, still more preferably an alkylsulfonyl group having 1 to 4 carbon atoms.

In the formula (1), R ₂ and R ₃ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboguanamine group, a decylamino group, an alkoxy group, or an aryloxy group. Alkyl, alkoxycarbonyl, arylcarbonyl, decyl or trimethyldecyl.

The aromatic residue represented by R ₂ and R _{3 of} the formula (1), an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group and an anthracenyl group, An aromatic residue, an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an arylcarbonyl group which may be a substituent which the ring Ar of the formula (1) may have may be mentioned. And the same as those described in the item of 醯基.

R ₂ and R ₃ in the formula (1) are preferably each independently an aromatic residue, more preferably a benzene ring residue (phenyl group). Further, as will be described later, when X ₁ and X ₂ are CR ₅ and CR ₆ , respectively, R ₂ and R _{5 are} preferably bonded to each other to form a ring, and R ₃ and R _{6 are} bonded to form a ring, and more preferably Both are benzene rings.

In the formula (1), R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue.

The aliphatic hydrocarbon residue represented by R _{4 of} the formula (1) may be the same as those described for the aliphatic hydrocarbon residue which may be a substituent of the ring Ar of the formula (1).

R ₄ in the formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula (1), X ₁ represents CR ₅ or a nitrogen atom, and R ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, a decylamino group, an alkoxy group. An aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group. Further, when X ₁ is CR ₅ , R ₂ and R ₅ may be bonded to each other to form a ring, and the ring to be formed may have a substituent.

Examples of the aromatic residue represented by R ₅ , an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group and an anthracenyl group are exemplified as the formula (1). The ring Ar may have a substituent of an aromatic residue, an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, and an anthracenyl group. The same.

In the case where X ₁ is CR ₅ , the ring formed of R ₂ and R ₅ may, for example, be an aromatic ring described in the item of an aromatic residue which may have a substituent of the ring Ar of the formula (1). In the same manner as the specific examples, the substituent which may be contained in the ring to be formed may be the same as the one which may be substituted with the ring Ar of the formula (1).

In the formula (1), X ₂ represents CR ₆ or a nitrogen atom, and R ₆ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, a decylamino group, an alkoxy group. An aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group. Further, when X ₂ is CR ₆ , R ₃ and R ₆ may be bonded to each other to form a ring, and the ring to be formed may have a substituent.

Examples of the aromatic residue, the aliphatic hydrocarbon residue, the halogen atom, the decylamino group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the arylcarbonyl group and the fluorenyl group represented by R ₆ may be mentioned as the formula (1). The ring Ar may have a substituent of an aromatic residue, an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group, and an anthracenyl group. The same.

In the case where X ₂ is CR ₆ , the ring formed of R ₃ and R ₆ may, for example, be an aromatic ring described in the item of an aromatic residue which may have a substituent of the ring Ar of the formula (1). In the same manner as the specific examples, the substituent which may be contained in the ring to be formed may be the same as the one which may be substituted with the ring Ar of the formula (1).

As X ₁ and X ₂ in the formula (1), it is preferred that both are nitrogen atoms. Further, when X ₁ and X ₂ are CR ₅ and CR _6, it is preferred that R ₂ and R _{5 are} bonded to each other to form a ring, and R ₃ and R _{6 are} bonded to each other to form a ring, and more preferably both of the ring to be formed. It is a benzene ring.

In the formula (1), Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom, a selenium atom or CR ₇ R ₈ , and R ₇ and R ₈ represent a hydrogen atom or an aliphatic hydrocarbon residue.

The aliphatic hydrocarbon residue represented by R ₇ and R ₈ may be the same as those described for the aliphatic hydrocarbon residue which may be a substituent of the ring Ar of the formula (1).

Y ₁ and Y ₂ in the formula (1) are preferably each independently a sulfur atom or an oxygen atom, and more preferably both are sulfur atoms.

The compound represented by the formula (1) is preferably a compound represented by the following formula (2).

In the formula (2), R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y _{2 are the} same as those of R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y ₂ in the formula (1). The meanings and preferred examples are also the same.

In the formula (2), R ₉ to R ₁₂ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, a decylamino group, an alkoxy group, or an aryloxy group. Alkyl, alkoxycarbonyl, arylcarbonyl or fluorenyl.

The aromatic residue represented by R ₉ to R _{12 of} the formula (2), an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group and an anthracenyl group, The aromatic residue, the aliphatic hydrocarbon residue, the halogen atom, the decylamino group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group which are specifically exemplified as the substituent which the ring Ar of the formula (1) may have may be mentioned. The same is the same for the arylcarbonyl group and the fluorenyl group.

R ₉ to R ₁₂ in the formula (2) are preferably a hydrogen atom or an aliphatic residue, more preferably independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably all hydrogen. atom.

In the formula (2), Y ₃ represents a sulfur atom, an oxygen atom or a selenium atom, preferably a sulfur atom or an oxygen atom, more preferably a sulfur atom.

The compound represented by the formula (1) is also preferably a compound represented by the following formula (3).

In the formula (3), R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y _{2 are the} same as those of R ₁ to R ₄ , X ₁ , X ₂ , Y ₁ and Y ₂ in the formula (1). The meanings and preferred examples are also the same.

In the formula (3), R ₁₃ to R ₁₈ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, a decylamino group, an alkoxy group, or an aryloxy group. Alkyl, alkoxycarbonyl, arylcarbonyl or fluorenyl.

The aromatic residue represented by R ₁₃ to R _{18 of} the formula (3), an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group and an anthracenyl group, The aromatic residue, the aliphatic hydrocarbon residue, the halogen atom, the decylamino group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group which are specifically exemplified as the substituent which the ring Ar of the formula (1) may have may be mentioned. The same is the same for the arylcarbonyl group and the fluorenyl group.

R ₁₃ to R _{18 of the} formula (3) are preferably each independently a hydrogen atom or a halogen atom, more preferably independently a halogen atom, and still more preferably a fluorine atom.

Formula (1) in the ring _{Ar, R 1 ~ R 4,} X 1 ~ X 2 1 ~ Y , and Y ₂ is preferably a combination of the above ring _{Ar, R 1 ~ R 4,} X 1 ~ X 2 and Y ₁ ~ Y _{2 is} each considered to be preferred in combination with each other, and a better combination is as follows.

That is, more preferably, it is a compound represented by the formula (2), wherein R ₁ in the formula (2) is an alkylsulfonyl group, R ₂ and R ₃ are each independently an aromatic residue, and R ₄ is a hydrogen atom or carbon. An alkyl group of 1 to 8, X ₁ and X ₂ are a nitrogen atom, Y ₁ , Y ₂ and Y ₃ are a sulfur atom or an oxygen atom, and R ₉ to R ₁₂ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a compound or a compound represented by the formula (3), wherein R ₁ in the formula (3) is an alkylsulfonyl group, R ₄ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X ₁ and X ₂ are CR ₅ and CR ₆ , which forms a ring with R ₂ and R ₅ , and forms a ring with R ₃ and R ₆ , and Y ₁ and Y ₂ are each independently a sulfur atom or an oxygen atom, and R ₁₃ to R ₁₈ are each independently a hydrogen atom or a halogen. Atom compounds.

Further, a compound represented by the formula (2), wherein R ₁ in the formula (2) is an alkylsulfonyl group having 1 to 4 carbon atoms, R ₂ and R ₃ are a benzene ring residue, and R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X ₁ and X ₂ being a nitrogen atom, Y ₁ , Y ₂ and Y ₃ being a sulfur atom, and R ₉ to R ₁₂ being a hydrogen atom or represented by the formula (3) a compound wherein R ₁ in the formula (3) is an alkylsulfonyl group having 1 to 4 carbon atoms, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ₁ and X ₂ are CR ₅ and CR ₆ A compound in which R ₂ and R ₅ form a benzene ring, and R ₃ and R ₆ form a benzene ring, Y ₁ and Y ₂ are a sulfur atom, and R ₁₃ to R ₁₈ are each independently a halogen atom.

The compound represented by the formula (1) of the present invention is preferably used as a photoacid generator.

The compound represented by the formula (1) of the present invention can be synthesized by various reactions. The following synthesis examples and examples are examples, and the method for synthesizing the compound represented by the formula (1) of the present invention is not limited to the methods described in the synthesis examples and the examples, and the combination is The raw material compound and the substituent or the partially structurally different compound used in the examples and the examples are used as a raw material to synthesize a compound of various structures contained in the formula (1).

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

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

The photosensitive resin composition of the present invention contains a compound (photoacid generator) represented by the formula (1) of the present invention and a cationically polymerizable compound.

Examples of the cationically polymerizable compound which can be used in the photosensitive resin composition of the present invention include a cyclic ether compound such as an epoxy compound (resin) or an oxetane compound (resin), and a (meth) acrylate. And ethylenically unsaturated compounds such as vinyl ethers and styrene.

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.). a polycondensate with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, benzenedialdehyde, crotonaldehyde, cinnamaldehyde, etc.); Phenols and various diene compounds (terpene, ethylene cyclohexene, lower Diene, ethylene drop a polymer of alkene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropene biphenyl, butadiene, isoprene, etc.; phenols and ketones (acetone, methyl ethyl ketone, A) Polycondensate of isobutyl ketone, acetophenone, benzophenone, etc.; polycondensate of phenol and dichloromethylbiphenyl; polycondensate of phenol and dichloromethylbenzene; a glycidyl ether epoxy compound obtained by glycidation of a phenol or a polycondensate of various aldehydes or an alcohol; 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexyl An alicyclic epoxy compound represented by methyl-3,4'-epoxycyclohexane carboxylate or the like; tetraglycidyldiaminediphenylmethane or triglycidyl-p-aminophenol The glycidylamine-based epoxy compound, the glycidyl ester-based epoxy compound, and the like are not limited thereto as long as they are compounds having an epoxy group.

Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane and (3-ethyl-3-oxetanylmethoxy)methylbenzene, 1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl)ether, different Ethoxyethyl (3-ethyl-3-oxetanylmethyl) ether, different 3-(3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, ethyldiethylene glycol (3-ethyl- 3-oxetanylmethyl)ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxa) Cyclobutylmethyl)ether, tetrahydrofuranmethyl(3-ethyl-3-oxetanylmethyl)ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tetrabromobenzene Oxyethyl (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-oxo Heterocyclic butyl methyl)ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, (3-ethyl-3-oxetanylmethyl)ether, 3,7-bis(3-oxetanyl)-5-oxa-decane, 3,3'-(1,3- (2-methylene)propane diyl bis(formaldehyde)) 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-oxetanyl) Oxy)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, tricyclodecanediyldiphenyl Methyl (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 Ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol six (3-ethyl) Base-3- Oxecyclobutylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, 3-ethyl 3-phenoxymethyloxetane, 3-ethyl-3-(4-methylphenoxy)methyloxetane, 3-ethyl-3-(4-fluorobenzene Oxy)methyloxetane, 3-ethyl-3-(1-naphthalenyloxy)methyloxetane, 3-ethyl-3-(2-naphthyloxy)methyloxy Heterocyclobutane, 3-ethyl-3-{[3-(ethoxydecyl)propoxy]methyl}oxetane, oxetanyl sesquioxetane, phenol The novolac oxetane or the like is not limited to these as long as it is a compound having an oxetane ring.

Specific examples of the (meth) acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and B. Diol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane three (meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylate glycerin Ester, bisphenol-A epoxy di(meth)acrylate, bisphenol-F epoxy di(methyl) Acrylate, bisphenol-indole type epoxy di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylic acid Ester, ethoxylated glycerol tri(meth) acrylate, ethoxylated tris (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, ethoxylate Pentaerythritol tetra(meth)acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, Kayarad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad DPCA-30 ( (Nippon Chemical Manufacturing), UA-33H (Naka Nakamura Chemical Manufacturing), UA-53H (Naka Nakamura Chemical Manufacturing), and M-8060 (East Asia Synthetic Manufacturing) and other (meth) acrylate monomers, etc. The acrylate group is not particularly limited, and any of a monomer and an oligomer may be used. Further, the (meth) acrylate of the present invention means both an acrylate and a 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, and 2-hydroxyl group. Ethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, 2-ethoxymethoxy ethyl vinyl ether, diethylene glycol monovinyl ether, 2-ethylhexyl vinyl ether, dodecyl Aliphatic monovinyl ethers such as vinyl ether, octadecyl vinyl ether, allyl vinyl ether, 2-methylpropenyloxyethyl vinyl ether, 2-propenyloxyethyl vinyl ether; 2-benzene An aromatic monovinyl ether such as oxyethyl vinyl ether, phenyl vinyl ether or p-methoxyphenyl vinyl ether; butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, 1, 4-benzenedivinyl ether, hydroquinone divinyl ether, cyclohexane dimethanol divinyl ether (1,4-bis[(vinyloxy)methyl]cyclohexane), diethylene glycol divinyl Polyfunctional vinyl ethers such as ether, dipropylene glycol divinyl ether, hexanediol divinyl ether; styrene such as styrene, α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene ;N- A cationically polymerizable nitrogen-containing monomer such as vinyl carbazole or N-vinylpyrrolidone.

The compounding ratio of the compound represented by the formula (1) in the photosensitive resin composition of the present invention is such that the solvent is removed from the compound represented by the formula (1) and the essential component of the cationically polymerizable compound, and any of the following components. The total mass of solid components, usually 0.1 to 15% by mass, preferably 0.2 to 8% by mass. By setting the compounding ratio of the compound represented by the formula (1) within the above range, a photosensitive resin composition which is economical and has excellent 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 not particularly limited as long as it is used in an organic solvent such as an ink or a paint, and the components of the photosensitive resin composition are dissolved without causing chemical reaction with the constituent components. Specific examples of the solvent include ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, and cyclopentanone; aromatic hydrocarbons such as toluene, xylene, and methoxybenzene; and dipropylene glycol Ether and glycol ethers such as dipropylene glycol diethyl ether and propylene glycol monomethyl ether, ethyl lactate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, carbitol acetate, propylene glycol monomethyl ether Esters such as acetates and γ-butyrolactone, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as octane and decane, petroleum ethers, naphtha, hydrogenated naphtha, and solvent naphtha. Wait.

These solvents may be used singly or in combination of two or more. The solvent component is added for the purpose of adjusting the film thickness or the coating property at the time of coating the substrate, and the content of the solvent for appropriately maintaining the solubility of the main component, the volatility of the component, and the liquid viscosity of the composition is relatively The total amount of the photosensitive resin composition containing a solvent is preferably 95% by mass or less, and particularly preferably 10 to 90% by mass.

Further, in the photosensitive resin composition of the present invention, in order to absorb ultraviolet rays, the absorbed light energy may be supplied to a photocationic polymerization initiator, particularly an aromatic sulfonium salt, and a sensitizer may be used. As the sensitizer, for example, 9-oxygen sulfide is preferred. An anthracene compound (9,10-dialkoxyanthracene derivative) having an alkoxy group at the 9-position and the 10-position. Examples of the alkoxy group include C1 to C4 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The 9,10-dialkoxyfluorene derivative may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a C1 to C4 alkyl group or a sulfonic acid alkyl ester group, or a carboxylic acid alkyl ester group. The alkyl group in the alkyl sulfonate group or the alkyl carboxylate may, for example, be a C1 to C4 alkyl group. The substitution position of the substituents is preferably 2 positions.

9-oxosulfur Specific examples of the class include 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-diisopropyl 9-oxosulfur And 2-isopropyl 9-oxosulfur Etc., preferably 2,4-diethyl 9-oxosulfur (Manufactured by Nippon Kayaku Co., Ltd., trade name kayacure DETX-S), 2-isopropyl 9-oxosulfur .

Examples of the 9,10-dialkoxyfluorene derivative include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10. -dibutoxyanthracene, 9,10-dimethoxy-2-ethylhydrazine, 9,10-diethoxy-2-ethylhydrazine, 9,10-dipropoxy-2-ethyl蒽, 9,10-dimethoxy-2-chloroindole, methyl 9,10-dimethoxyindole-2-sulfonate, methyl 9,10-diethoxyindole-2-sulfonate, 9,10-dimethoxyindole-2-carboxylic acid methyl ester and the like.

These may be used singly or in combination of two or more. It is most preferred to use 2,4-diethyl 9-oxosulfur Or 9,10-dimethoxy-2-ethylhydrazine. In order to exert an effect in a small amount, the sensitizer component is preferably used in an amount of 30% by mass or less, and particularly preferably 20% by mass or less based on the mass of the compound represented by the formula (1).

In the photosensitive resin composition of the present invention, various additives such as a thermoplastic resin, a colorant, a coupling agent, a tackifier, an antifoaming agent, and a leveling agent may be used as needed. Examples of the thermoplastic resin include polyether oxime, polystyrene, and polycarbonate. As the curing agent, examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, ruthenium, quinacridone red, and diketopyrrole. Pyrrole red and the like. In the case of using the above-mentioned additives, the amount of the photosensitive resin composition of the present invention in which the solvent is removed is, for example, 30% by mass or less, which is a standard, and can be used according to the purpose of use and the requirements of the cured film. Appropriate increase or decrease in function. Examples of the coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 2 -(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. As the tackifier, for example, Orben, Bentone, and montmorillonite can be cited. Examples of the antifoaming agent include antifoaming agents such as polyfluorene-based, fluoroalkyl-based, and polymeric. In the case of using such an additive or the like, the amount of the photosensitive resin composition of the present invention with respect to the solvent to be removed is, for example, 10% by mass or less, which is an approximate standard, depending on the purpose of use and the coating quality. And appropriate increase or decrease.

Further, in the photosensitive resin composition of the present invention, for example, barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum acidate, aluminum hydroxide, and Mongolian may be used. Any inorganic filler such as desilted or mica powder. The amount of use of the photosensitive resin composition of the present invention with respect to the solvent to be removed is 60% by mass or less, and can be appropriately increased or decreased depending on the purpose of use and the desired function of the cured film. Similarly, organic fillers such as polymethyl methacrylate, rubber, fluoropolymer, and polyurethane powder may be incorporated.

The photosensitive resin composition of the present invention contains a compound represented by the formula (1) and a necessary component of the cationically polymerizable compound, and optionally a solvent, a coupling agent, an ion scavenger, a thermoplastic resin, and a colorant as optional components. The tackifier, antifoaming agent, leveling agent and inorganic filler are adjusted by mixing and stirring by a usual method. For mixing and stirring, a dispersing machine such as a dispersing mixer, a homogenizer, or a three-roll mill may be used as needed. Further, after mixing, filtration may be carried out using a sieve, a membrane filter or the like.

The photosensitive resin composition of the present invention can be easily made into a cured product by irradiating an active energy ray such as an ultraviolet ray. The curing is performed by irradiating the photosensitive resin composition of the present invention to a thickness of usually about 0.01 to 1 mm, and then irradiating the active energy ray. The suitable active energy ray may be any one as long as it has the energy of decomposing the photoacid generator represented by the formula (1), and preferably includes a high pressure mercury lamp, a medium pressure mercury lamp, a xenon lamp, and a metal halogen. Light, germicidal lamp, and laser light have electromagnetic energy energy of 2000-7000 angstroms, electron beam, X-ray, ultraviolet light and other light energy lines. The irradiation time of the active energy ray is also dependent on its intensity, and is usually sufficient for about 0.1 to 10 seconds. However, it is preferable to spend the above time on the coating film having a relatively thick film thickness. Expose the active energy line for 0.1~ minutes After that, the photosensitive resin composition is cured by a photo-acid generator, and is dry to the touch. If necessary, the photosensitive resin composition is heated to about 30 to 100 ° C when irradiated with an active energy ray, thereby effectively promoting polymerization. The reaction further increases the rate of hardening. Further, the cured product obtained by irradiating the active energy ray may be subjected to heat treatment at 50 to 250 ° C for the purpose of curing due to termination of polymerization. In the case of heat treatment, in consideration of the heat resistance of the substrate to which the photosensitive resin composition is applied or the cured product obtained, when heat treatment is performed at a high temperature of 100 ° C or higher, it is preferably as short as possible. Heat treatment.

Further, by using the photosensitive resin composition of the present invention, a cured product of the resin composition can also be obtained by a method of performing a conventionally known photolithography method, that is, a method including coating, pattern irradiation, and development. Fine pattern.

Specific examples of the photocurable resin composition of the present invention include a coating material, a coating agent, an ink, a resist, a liquid resist, an adhesive, a molding material, a putty, a glass fiber impregnating agent, and a caulking. The agent, the casting agent for optical forming, etc., for example, as a base material used as a coating agent, metal, wood, rubber, plastic, glass, ceramics, etc. are mentioned.

[Examples]

Hereinafter, the present invention will be further described by way of Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, "%" means % by weight and "parts" means parts by weight unless otherwise specified.

Further, in the following examples, the following experimental apparatus and measuring apparatus were used.

‧High performance liquid chromatography [normal phase HPLC]

Analytical pump -------------------------------------HTACHI Pump L2130

Detector----------------------------------HITACHI UV Detector L-2400

Recorder----------------------------------------------HITACHI D -2500

Columns ---------------------------------------------COSMOSIL 5SL- II

‧ Medium pressure preparative liquid chromatography instrument ------- Shanshan EPCLC-W-Prep 2XY A-Type

‧ NMR device ------------------------- JEOL JNM-AL300 (300MHz)

‧ Double Convergence Mass Analysis Device (EI-HRMS)---JEOL JMS-700 MSation

‧DART quality analysis device --------------------------JEOL JMS-Q1000TD

‧Organic low molecular X-ray structure analysis device --------------Rigaku R-AXIS RAPID/S (3kW)

‧UV-visible spectrophotometer ----------------------------------JASCO V-660

‧Nerosecond time decomposition spectrometer----------------------------UNISOKU TSP-1000M

‧Fluorescence spectrophotometer ------------------------------------HITACHI H7000

‧Absolute Luminescence Quantum Yield Measuring Device----------------Hamamatsu C9920-02

‧Photoreaction quantum yield measuring device -------------------Shimadzu Manufacturing Co., Ltd. QYM-01

‧Distribution cryostat -------OXFORD INSTRUMENTS Optistat DN‧Light source

1kW Ultra High Pressure Mercury Lamp----------------------------USHIO SX-UI-501HQ

Monochromator -------------------------------------------- Shimadzu Corporation SPG -120

Nanosecond pulse Nd:YAG laser -------------------------Continuum Minilite II

High output nanosecond pulse Nd:YAG laser-----------------Continuum Surelite II

Nanosecond Optical Parameter Oscillator --------------------Continuum Panther EX OPO

‧Microwave Synthesizer ----------------------------------------Biotage Initiator

Synthesis Example 1

After dissolving 19.9 g (142 mmol) of benzo[b]thiophene in 200 mL of chloroform in a 500 mL eggplant-shaped flask, 16 mL (312 mmol) of bromine was added dropwise thereto, and the mixture was stirred at room temperature for 24 hours. After quenching with 100 mL of a 10% aqueous sodium thiosulfate solution, extraction was carried out with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was distilled off and washed with hexane to give purple The form of the color solid obtained 41.7 g (yield about 100%) of the compound represented by the following formula 1. The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 1 are as follows.

¹ H NMR (300MHz, CDCl ₃ ): δ 7.77-7.71 (m, 2H), 7.47-7.36 (m, 2H)

Synthesis Example 2

In a 500 mL eggplant-shaped flask, 5.05 g (40.3 mmol) of methyl glycinate hydrochloride was dissolved in 200 mL of dichloromethane, and then cooled to 0 ° C in an ice bath. 11.3 mL (81 mmol) of triethylamine was added, and 4.7 mL (40.5 mmol) of benzylidene chloride was added dropwise thereto over 10 minutes, and the mixture was heated to room temperature and stirred overnight. After the reaction, 100 mL of a saturated aqueous solution of sodium hydrogencarbonate was added, and the mixture was extracted with dichloromethane, and dried over anhydrous magnesium sulfate, and the solvent was distilled away to obtain 7.43 g of the compound represented by the following formula 2 as a white solid. Yield 95.5%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 2 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.84-7.81 (m, 2H), 7.56-7.46 (m, 3H), 6.67 (sl, 1H), 4.28-4.26 (d, J = 5.1Hz, 2H), 3.81(s,3H)

Synthesis Example 3

100 mL of chloroform was placed in an eggplant-shaped flask, and molecular sieve (4A) was added, and nitrogen gas was supplied for 30 minutes. On the other hand, argon gas replacement was carried out by adding 4.72 g (24.4 mmol) of the compound represented by Formula 2 obtained in Synthesis Example 2 and 8.04 g (36.2 mmol) of phosphorus pentasulfide in a four-necked flask which was dried in a frame. . 70 mL of the above chloroform was added using a syringe, and the mixture was heated at 80 ° C for 24 hours. After the reaction, 50 mL of a 5% aqueous sodium hydroxide solution was added in small portions, and the precipitate was decomposed and extracted with chloroform. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off, and the mixture was purified by using hexane-diethyl ether to the short column, and the compound represented by the following formula 3 was obtained as a brown oil. (Yield 83.5%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 3 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.82-7.73 (m, 2H), 7.44-7.36 (m, 3H), 7.13 (s, 1H), 3.97 (s, 3H)

Synthesis Example 4

To a 100 mL brown eggplant-shaped flask, 3.90 g (20.4 mmol) of the compound represented by the formula 3 obtained in Synthesis Example 3 and 5.48 g (30.8 mmol) of NBS (N-bromosuccinimide) were dissolved in chloroform 53 mL. in. After stirring at room temperature for 4 hours, 30 mL of a 10% aqueous sodium thiosulfate solution was added, and the mixture was extracted with chloroform. It was dried over anhydrous magnesium sulfate, and purified by a column chromatography (chloroform:hexane = 1:1) to obtain 3.95 g of the compound represented by the following formula 4 as a white solid (yield 71.7). %). The compound represented by the formula 4 The measured values of the nuclear magnetic resonance apparatus of the object are as follows.

¹ H NMR (300MHz, CDCl ₃ ): δ 7.84-7.80 (m, 2H), 7.42-7.40 (m, 3H), 4.04 (s, 3H)

Synthesis Example 5

In a 500 mL eggplant-shaped flask, 20.2 g (147 mmol) of thiobenzamide and 34.0 g (219 mmol) of a 50% by weight aqueous chloroacetaldehyde solution were dissolved in 100 mL of ethanol, and the mixture was heated under reflux for 3 hours. The reaction product was extracted with chloroform, dried over anhydrous magnesium sulfate, and then purified by passing through a short column of ruthenium dioxide gel (developing solvent: chloroform), whereby the product represented by the following formula 5 was obtained as a yellow oil. The compound was 25.2 g (yield about 100%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by the formula 5 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.00-7.96 (m, 2H), 7.89-7.87 (d, J = 3.3Hz, 1H), 7.48-7.44 (m, 3H), 7.35-7.34 (d, J =3.3Hz, 1H)

Synthesis Example 6

Formula 5 obtained in Synthesis Example 5 was expressed in a 300 mL brown eggplant-shaped flask. 8.36 g (51.9 mmol) of the compound and 14.0 g (78.7 mmol) of NBS were dissolved in 120 mL of chloroform, and the mixture was heated under reflux for 16 hours. 50 mL of a 10% aqueous sodium thiosulfate solution was added, and extraction was performed with chloroform. This was dried over anhydrous magnesium sulfate, and the solvent was distilled off and recrystallized from methanol, whereby 11.8 g (yield 94.4%) of the compound represented by the following formula 6 was obtained as a light brown solid. The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 6 are as follows.

¹ H NMR (300MHz, CDCl ₃ ): δ 7.89-7.85 (m, 2H), 7.74 (s, 1H), 7.46-7.44 (m, 3H)

Synthesis Example 7

After drying through a frame, 3.3 mL (23.5 mmol) of distilled diisopropylamine was added to a four-necked flask subjected to argon gas exchange, and the mixture was cooled to 0 °C. After 13.5 mL (21.6 mmol) of a n-butyllithium hexane solution was added dropwise, the mixture was heated to room temperature, and a small amount of dry THF (tetrahydrofuran) was added and diluted. The frame-dried four-necked flask was replaced with argon gas, and 1.78 g (7.41 mmol) of the compound represented by the formula 6 obtained in Synthesis Example 6 was dissolved in 35 mL of dry THF. After stirring at 0 ° C for 10 minutes, 20 mL of LDA (lithium diisopropylguanamine) was added dropwise, and the mixture was stirred at 0 ° C for 30 minutes. After the reaction, the mixture was quenched with water, extracted with diethyl ether, and dried over anhydrous magnesium sulfate, whereby 1.68 g (yield 94.4%) of the compound represented by the following formula 7 was obtained as a light brown solid. The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 7 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.96-7.93 (m, 2H), 7.47-7.44 (m, 3H), 7.22 (s, 1H)

Synthesis Example 8

In a four-necked flask which was subjected to argon gas replacement after drying in a frame, 1.69 g (6.26 mmol) of the compound of the formula 4 obtained in Synthesis Example 4 was dissolved in 26 mL of dry THF and cooled to -78 °C. 4.1 mL (6.56 mmol) of n-butyllithium hexane solution was added dropwise, and the mixture was stirred for 30 minutes while maintaining the cooling temperature. 1.8 mL of tributyltin chloride (6.64 mmol) was added and stirred at -78 ° C for 30 minutes, and the mixture was warmed to room temperature, and further stirred for 30 minutes. An aqueous solution of potassium fluoride was added, and the mixture was extracted with ethyl acetate, and dried over anhydrous magnesium sulfate, and the solvent was distilled away to obtain 3.14 g of the compound represented by the following formula 10 as a yellow oil (yield 98.7%). ). The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 10 are as follows.

¹ H NMR (300MHz, CDCl ₃ ): δ 7.86-7.83 (m, 2H), 7.38-7.35 (m, 3H), 3.94 (s, 3H), 1.65-0.87 (m, 27 H or more)

Synthesis Example 9

1.56 g (6.50 mmol) of the compound represented by the formula 7 obtained in Synthesis Example 7 and 1.65 g (6.51 mmol) of dipentafluorene dibromide and Pd ₂ (dba) ₃ chloroform adduct 0.187 g in a vial for microwave synthesis. (0.204 mmol), tricyclohexylphosphine 0.280 g (0.998 mmol) and potassium acetate 0.959 g (9.77 mmol) dissolved in 1,4-two 19 mL of alkane was stirred using a microwave at 170 ° C for 150 minutes. The reaction solution was filtered through celite with ethyl acetate, and the solvent was distilled off. The mixture was extracted with ethyl acetate and dried over anhydrous magnesium sulfate to obtain the following formula 11 as a yellow oil. The compound represented by 1.87 g (reaction rate: 100%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by the formula 11 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): 8.06-8.03 (m, 2H), 7.98 (s, 1H), 7.44-7.41 (m, 3H), 1.39 (s, 12H)

Synthesis Example 10

1.65 g (5.65 mmol) of the compound represented by Formula 1 obtained in Synthesis Example 1 and 1.52 g (5.64 mmol) of the compound represented by Formula 4 obtained in Synthesis Example 4 and 0.168 g (0.641) of triphenylphosphine were added to a four-necked flask. Mmmol), 2M tripotassium phosphate solution 11mL and 1,4-two Alkane 125 mL was passed through with nitrogen for 30 minutes. Pd(PPh ₃ ) ₄ 0.326 g (0.282 mmol) was added while flowing nitrogen gas, and the mixture was heated under reflux for 24 hours. An aqueous solution of ammonium chloride was added thereto for neutralization, and extraction was carried out with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off, and purified by silica gel column chromatography (hexane: chloroform = 1:1) to obtain 1.75 g of the compound represented by the following formula 12 as a white solid. (Yield 77.1%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 12 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.93-7.89 (m, 3H), 7.83-7.80 (m, 1H), 7.49-7.38 (m, 5H), 4.11 (s, 3H)

Synthesis Example 11

1.87 g (6.50 mmol) of the compound represented by Formula 11 obtained in Synthesis Example 9 and 2.62 g (6.50 mmol) of the compound represented by Formula 12 obtained in Synthesis Example 10 and 0.158 g of triphenylphosphine (0.602) were added to a four-necked flask. Mmmol), 2M tripotassium phosphate solution 12mL, 1,4-two 160 mL of alkane was purged with nitrogen for 30 minutes. Pd(PPh ₃ ) ₄ 0.402 g (0.348 mmol) was added while flowing nitrogen gas, and the mixture was heated under reflux for 24 hours. An aqueous solution of ammonium chloride was added thereto for neutralization, and extraction was carried out with ethyl acetate. The mixture was dried over anhydrous magnesium sulfate, and the solvent was distilled off, and purified by hydrazine column chromatography (chloroform) and normal phase HPLC (chloroform) to obtain the following formula BT-OMe (1) as a pale yellow solid. The compound represented was 1.34 g (yield 42.7%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by the formula BT-OMe (1) are shown below.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.08-8.01 (m, 3H), 7.89-7.86 (m, 1H), 7.82-7.79 (m, 2H), 7.47-7.43 (m, 3H), 7.40-7.36 (m, 5H), 7.30 (s, 1H), 3.73 (s, 3H)

EI-HRMS(m/z):calcd for C ₂₇ H ₁₈ N ₂ OS ₃ ,482.0581;found,482.0587(M+H) ⁺

[化17]

Synthesis Example 12

1.85 g (6.34 mmol) of the compound represented by Formula 1 obtained in Synthesis Example 1 and 1.80 g (6.25 mmol) of the compound represented by Formula 11 obtained in Synthesis Example 9 and 0.192 g of triphenylphosphine (0.732) were added to a four-necked flask. Mmmol), 2M tripotassium phosphate solution 12mL and 1,4-two 110 mL of alkane was purged with nitrogen for 30 minutes. Pd(PPh ₃ ) ₄ 0.548 g (0.474 mmol) was added while flowing nitrogen gas, and the mixture was heated under reflux for 24 hours. After adding an aqueous solution of ammonium chloride for neutralization, extraction was carried out with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off, and purified by silica gel column chromatography (hexane: chloroform = 1:1) to obtain the compound represented by the following formula 13 in the form of a white solid. (Yield 89.0%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by Formula 13 are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.35 (s, 1H), 8.07-8.04 (m, 2H), 7.89-7.83 (m, 2H), 7.50-7.42 (m, 5H)

Synthesis Example 13

2.00 g (5.21 mmol) of the compound represented by Formula 10 obtained in Synthesis Example 8 and 1.49 g (4.00 mmol) of the compound represented by Formula 13 obtained in Synthesis Example 12 and 1.39 g (9.17 mmol) of cesium fluoride were added to a four-necked flask. And 45 mL of toluene, and nitrogen gas was passed for 30 minutes. Pd(PPh ₃ ) ₄ 0.321 g (0.278 mmol) was added while flowing nitrogen gas, and the mixture was heated under reflux for 24 hours. 100 mL of an aqueous potassium fluoride solution was added, and extraction was performed with ethyl acetate. The mixture was dried over anhydrous magnesium sulfate, and the solvent was distilled off, and purified by silica gel column chromatography (chloroform) and normal phase HPLC (chloroform) to obtain the following formula BT-OMe (2) as a white solid. The compound represented by 1.32 g (yield 68.5%). The measured values of the nuclear magnetic resonance apparatus of the compound represented by the formula BT-OMe (2) are shown below.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 8.02-7.93 (m, 4H), 7.90-7.87 (m, 1H), 7.67-7.63 (m, 1H), 7.46-7.43 (m, 6H), 7.38-7.35 (m, 2H), 7.21 (s, 1H), 3.81 (s, 3H)

EI-HRMS(m/z):calcd for C ₂₇ H ₁₈ N ₂ OS ₃ ,482.0581;found,482.0584(M+H) ⁺

Determination of the quantum yield of photoreaction of intermediates

The hexane solution of the compound represented by the formula BT-OMe (1) obtained in Synthesis Example 11 was irradiated with ultraviolet light (365 nm), and then the photoreaction quantum yield was measured using a photoreaction quantum yield measuring apparatus (manufactured by Shimadzu Corporation, QYM-01). At the time rate, the quantum yield of the ring closure reaction was 0.33. Further, when the photoreaction quantum yield was measured by the same method as described above using the compound represented by the formula BT-OMe (2) obtained in Synthesis Example 13, the quantum yield of the ring closure reaction was 0.64.

Based on the results, the following synthesis was carried out using a compound represented by the formula BT-OMe (2) which is more excellent in quantum yield.

Synthesis Example 14

In a two-necked flask which was dried in a frame and subjected to argon gas exchange, 0.269 g (0.557 mmol) of the compound represented by the formula BT-OMe (2) obtained in Synthesis Example 13 was dissolved in about 15 mL of dichloromethane, and the system was covered with an aluminum foil. overall. 1.46 mL (2.8 mmol) of boron tribromide was added dropwise, and the mixture was stirred at room temperature for 3 days, and then extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a red solid. 0.337 g of the compound represented by the formula BT-OH (yield > 100%). On the compound represented by the formula 10 was measured ^{(1 H NMR (300MHz, CDCl} 3)) confirmed by nuclear magnetic resonance apparatus from the disappearance of the signal of the methoxy group.

Example 1

0.234 g of the compound represented by the formula BT-OH obtained in Synthesis Example 14 was placed in a frame-dried two-necked flask, and the entire system was covered with an aluminum foil. 4 mL of dichloromethane was added, and the mixture was cooled to 0 ° C with an ice bath, and 500 μL of triethylamine was added. 0.143 g (1.25 mmol) of methanesulfonium chloride was added, and the mixture was stirred at 0 ° C for 2 hours. Water was added, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. The solvent was distilled off and subjected to medium pressure gel chromatography (chloroform:hexane = 1:1) to prepare GPC (chloroform) and normal phase HPLC (chloroform). By refining, 16 mg of the compound represented by the following formula BT-OMs (corresponding to the compound 1 in Table 1) was obtained as a white solid. The measured values of the nuclear magnetic resonance apparatus of the compound represented by the formula BT-OMs are as follows.

_{^{1 H NMR (300MHz, CDCl 3}} ): δ 7.98-7.89 (m, 5H), 7.48-7.40 (m, 9H), 7.25 (s, 1H), 2.65 (s, 3H)

In order to confirm that the compound represented by the BT-OMs obtained in Example 1 is a compound which can generate an acid by irradiation with an active energy ray, the following evaluation was performed.

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

According to the result of the addition of the methanesulfonic acid, it is understood that the peak attributed to the propylene oxide disappears, and the peak attributed to the oligomeric propylene glycol formed by the ring-opening reaction appears (refer to the spectrum on the upper side in FIG. 1). . From this, it was found that the presence or absence of the ring-opening reaction of propylene oxide was confirmed based on the measurement results of the ¹ H-NMR spectrum.

Next, a sample obtained by dissolving the compound represented by the formula BT-OMs obtained in Example 1 and propylene oxide in ruthenium chloroform was irradiated with ultraviolet rays (365 nm), and the change of the ¹ H-NMR spectrum before and after the irradiation was measured. The results are shown in Figure 2. Further, Fig. 3 shows a ¹ H-NMR spectrum of a sample obtained by dissolving a compound represented by the formula BT-OMs in chloroform, and Fig. 4 shows a ¹ H-NMR sample obtained by dissolving propylene oxide in chloroform. spectrum.

From the results of Fig. 2, it is understood that the peak attributed to propylene oxide after the ultraviolet irradiation is decreased, and the peak attributed to the oligomeric propylene glycol produced by the ring-opening polymerization reaction (see the spectrum on the upper side in Fig. 2). This case indicates an acid (methanesulfonic acid) formed by the compound represented by the formula BT-OMs obtained in Example 1 by irradiation with ultraviolet rays, and a ring-opening reaction of propylene oxide occurs. Based on the results, it is clarified that the compound represented by BT-OMs obtained in Example 1 is a compound which can form an acid by irradiation with an active energy ray, and the generated acid can cause a ring-opening reaction of the epoxy, that is, it can be A compound used as a cationic polymerization initiator.

[Industrial availability]

The compound represented by the formula (1) of the present invention has a high solubility to a hydrophobic cationically polymerizable compound or a solvent, and has a higher yield of an acid for an i-ray or a g-ray, thereby being used as a quantum yield. Photoacid generator.

Claims (12)

a compound represented by the following formula (1), (In the formula (1), the ring Ar represents a benzene ring, a naphthalene ring, a thiophene ring, a benzothiophene ring, a furan ring, a benzofuran ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, an imidazolidine. a ring, a benzimidazole ring, a cyclopentene ring, a cyclohexene ring, a cyclopentene ring, an anthracene ring or a pyrrole ring; R ₁ represents an aliphatic hydrocarbon group, an alkylsulfonyl group, an alkoxysulfonyl group, An arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group or an arylcarbonyl group; and R ₂ and R ₃ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboguanamine group, Amidino, alkoxy, aryloxy, alkoxycarbonyl, arylcarbonyl, decyl or trimethyldecyl; R ₄ represents a hydrogen atom or an aliphatic hydrocarbon residue; X ₁ represents a CR ₅ or a nitrogen atom; ₅ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group; ₂ and R ₅ may also be linked to form a ring; _X-2 represents a CR ₆ or a nitrogen atom; R ₆ represents a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, 2carboxamide , Acyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, acyl or arylcarbonyl group; R ₃ and R ₆ may also be linked to form a ring; Y ₁ and Y ₂ each independently represent a sulfur atom, an oxygen atom, a selenium Atom or CR ₇ R ₈ ; R ₇ and R ₈ represent a hydrogen atom or an aliphatic hydrocarbon residue). The compound of claim 1, which is represented by the following formula (2), (In the formula _{(2), R 1 ~ R} 4, X 1, X 2, (1) in the R Y, and Y ₂ represents a requested item of formula ₁ of _{1 1 ~ R 4, X 1} , X 2, Y 1 And Y _{2 have the} same meaning; R ₉ to R ₁₂ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, and an aromatic group. An oxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group; Y ₃ represents a sulfur atom, an oxygen atom or a selenium atom). The compound of claim 2, wherein R ₁ is an alkylsulfonyl group having 1 to 4 carbon atoms. The compound of claim 2, wherein X ₁ and X ₂ are a nitrogen atom. The compound of claim 2, wherein Y ₁ to Y ₃ are each independently a sulfur atom or an oxygen atom. The compound of claim 1, which is represented by the following formula (3), (In the formula _{(3), R 1 ~ R} 4, X 1, X 2, (1) in the R Y, and Y ₂ represents a requested item of formula ₁ of _{1 1 ~ R 4, X 1} , X 2, Y 1 And Y _{2 have the} same meaning; R ₁₃ to R ₁₈ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, and an aromatic group. Oxy, alkoxycarbonyl, arylcarbonyl or fluorenyl). The compound of claim 6, wherein R ₁ is an alkylsulfonyl group having 1 to 4 carbon atoms. The compound of claim 6, wherein X ₁ is CR ₅ , R ₂ and R _{5 are} bonded to form a benzene ring, and X ₂ is CR ₆ , and R ₃ and R _{6 are} bonded to form a benzene ring. The compound of claim 6, wherein Y ₁ and Y ₂ are a sulfur atom or an oxygen atom. A photoacid generator comprising the compound of any one of claims 1 to 9. A photosensitive resin composition containing the photoacid generator of claim 10 and a compound polymerizable by a photoacid generator. A cured product obtained by hardening the photosensitive resin composition of claim 11.