JP5940259B2 - Photosensitive composition - Google Patents

Description

  The present invention relates to a composition that is cured by light irradiation.

So-called UV coating, which is cured by light irradiation and coats the surface, is expanding its application range such as coating agents, paints and printing inks from the viewpoint of workability (fast curing) and low VOC.
In general, a photocurable coating agent comprises a photopolymerization initiator, a radical polymerizable monomer, an oligomer or a polymer, and a colorant and an additive depending on applications. Colorants are roughly divided into pigments and dyes, and are blended to color the coating film. The colorant has a light absorption characteristic according to its color and absorbs a part of the irradiated light to attenuate the light or shield the irradiated light. The light may not reach. In order to solve this problem, it has been proposed to use a specific photopolymerization initiator (see, for example, Patent Document 1).

  However, the invention described in Patent Document 1 is a combination of a photopolymerization initiator and a sensitizer having a specific structure, and can be cured with a smaller amount of energy irradiation than conventionally used photopolymerization initiator systems. Is improved, but there is a problem that the curability is insufficient when the colorant concentration in the ink composition is increased or the film thickness is increased.

JP 2009-19142 A

  The present invention has been made in view of the above problems, and the object of the present invention is small even when a substance such as a colorant that attenuates or shields irradiated light is present in a high concentration or has a large film thickness. It is providing the photosensitive composition which can be hardened | cured with the amount of energy.

As a result of intensive studies to achieve the above object, the present inventors have found that a photosensitive composition containing a substance that attenuates or blocks light, such as a radical initiator, a polymerizable substance, and a colorant, contains an acid. It has been found that by making both the generator and the base generator coexist, excellent curability is exhibited even in a portion where light is attenuated or shielded, and the present invention has been achieved.
That is, this invention is a photosensitive composition containing the following (1)-(5), Comprising: At least 1 of a radical initiator (A), an acid generator (B), and a base generator (C). One generates active species (H) upon irradiation with actinic rays, and the active species (H) reacts with the radical initiator (A), acid generator (B) or base generator (C) to form new active species. (I) is generated and the polymerization reaction of the polymerizable substance (D) by the new active species (I) proceeds, and the active species (H) or the new active species (I) is an acid or a base. The radical initiator (A) is a radical initiator (A1) that generates radicals with actinic rays and / or a radical initiator (A2) that generates radicals with acid and / or base, and the acid generator (B ) Is an acid generator (B1) which generates an acid by actinic rays and / or radicals, acids and An acid generator (B2) that generates an acid by at least one selected from the group consisting of a base, wherein the base generator (C) generates a base by actinic rays and / or a radical; A base generator (C2) that generates a base by at least one selected from the group consisting of acids and bases, an acid generator (B1) that generates an acid by actinic rays, and / or a group consisting of radicals, acids and bases The acid generator (B2) that generates an acid by at least one selected from the group consisting of a sulfonium salt derivative (B121) having a phosphine anion as an anion and / or an iodonium salt derivative (B122) having a phosphine anion as an anion. A base generator (C1) which generates a base by actinic rays and / or a group consisting of a radical, an acid and a base Base generator generating a base by at least one selected Luo (C2), a quaternary amidine salt derivatives (C123), polymerizable substance (D) a radical polymerizable compound (D1) der Rukoto It is the photosensitive composition characterized.
(1) Radical initiator (A)
(2) Acid generator (B)
(3) Base generator (C)
(4) Polymerizable substance (D)
(5) Colorant (E), metal oxide powder (F) or metal powder (G).
In the present invention, an actinic ray is a ray having a wavelength of 360 nm to 830 nm.

By using the photosensitive composition of the present invention, a thick film can be cured with a small amount of energy even if a substance such as a colorant that attenuates or blocks irradiated light is present in a high concentration.
In addition, by using metal oxide powder or metal powder as a substance that attenuates or shields irradiated light, green sheet formation and electrode layer formation of ceramic electronic components can be performed in a short time by light irradiation. Become. Furthermore, the negative resist pattern formation containing a metal oxide powder or metal powder, a hydrophilic epoxy resin and a crosslinking agent can be performed in a short time by light irradiation.

The photosensitive composition of the present invention contains the following (1) to (5);
(1) Radical initiator (A)
(2) Acid generator (B)
(3) Base generator (C)
(4) Polymerizable substance (D)
(5) Colorant (E), metal oxide powder (F) or metal powder (G).

  In the photosensitive composition of the present invention, at least one of the radical initiator (A), the acid generator (B) and the base generator (C) generates an active species (H) by irradiation with actinic rays, The active species (H) reacts with a radical initiator (A) other than the source of (H), an acid generator (B) and a base generator (C) to produce a new active species (I). Thus, the polymerization reaction of the polymerizable substance (D) by the new active species (I) proceeds. Here, examples of the active species (H) and (I) include radicals, acids, and bases. In the above reaction, either the active species (H) or (I) is an acid and / or a base. It is necessary. By diffusing the active species (H), it is possible to cure a portion where the active ray is attenuated or a portion where the light does not reach, which is difficult to photocur with a general photopolymerization initiator. In order for the active species (H) to diffuse, it is preferable to use a polymerizable substance (D) that does not react with the active species (H).

  In general cationic polymerization using an acid generator alone or anionic polymerization using a base generator alone, it is difficult to use a wavelength at which the generator does not absorb. However, in the present invention, a photoacid generator or a photobase is used. A wavelength at which the generator does not have absorption can be used in combination with a radical generator having absorption at that wavelength.

  In addition, an acid generator (B) and a base generator are contained in a photosensitive composition containing a substance that attenuates or blocks light, such as a radical initiator (A), a polymerizable substance (D), and a colorant (E). By coexisting both of (C), the curability at the portion where the light is attenuated or shielded is greatly improved as compared with the case where (B) and (C) are not contained, and (B) or ( Compared with the case where any one of C) is present, the curability at the portion where the light is attenuated or shielded is greatly improved.

In the present invention, the radical initiator (A) means a compound that generates radicals with actinic rays, acids or bases, and radical initiators (A1) that generate radicals with actinic rays, radicals with acids and / or bases. A known compound such as a radical initiator (A2) that generates hydrogen can be used.
For example, acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124). The benzoin derivative polymerization initiator (A125), the oxime ester derivative polymerization initiator (A126), the titanocene derivative polymerization initiator (A127), etc. can generate radicals by any of actinic rays, acids or bases. It can be applied as (A1) or (A2).
The organic peroxide polymerization initiator (A21), the azo compound polymerization initiator (A22), the other radical initiator (A23), and the like can generate radicals with an acid or base. ).
(A) may be used individually by 1 type, and may use 2 or more types together.
In addition, (A121) shows that it is the 1st example of a compound applicable as any of (A1) and (A2). Similarly, (A21) indicates the first example of a compound applicable as (A2).

  As the acylphosphine oxide derivative polymerization initiator (A121), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by Ciba Japan (DAROCUR TPO)] and bis (2,4,6-trimethylbenzoyl)- And phenylphosphine oxide [manufactured by Ciba Japan (IRGACURE 819)].

  As the α-aminoacetophenone derivative-based polymerization initiator (A122), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by Ciba Japan (IRGACURE 907)], 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by Ciba Japan (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone [manufactured by Ciba Japan (IRGACURE 379)] and the like.

  Examples of the benzyl ketal derivative polymerization initiator (A123) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by Ciba Japan (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (A124), 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by Ciba Japan (IRGACURE 184)], 2-hydroxy-2-methyl-1-phenyl-propane-1 -ON [Ciba Japan (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [Ciba Japan (IRGACURE) 2959)] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [IRGACURE 127 )] And the like.

  Examples of the benzoin derivative polymerization initiator (A125) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (A126), 1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] [manufactured by Ciba Japan (IRGACURE OXE 01)] and Etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by Ciba Japan (IRGACURE OXE 02)] .

  As the titanocene derivative polymerization initiator (A127), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) is used. Examples thereof include titanium [manufactured by Ciba Japan (IRGACURE 784)] and the like.

  Examples of the organic peroxide polymerization initiator (A21) include benzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butyl peroxybenzoate, and n-butyl. 4,4-di- (t-butylperoxy) valerate, di- (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5, -dimethyl-2 , 5, -di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydro Over oxide and t- butyl trimethylsilyl peroxide.

  As the azo compound-based polymerization initiator (A22), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).

  Examples of the other polymerization initiator (A23) include 2,3-dimethyl-2,3-diphenylbutane.

  As the radical initiator (A2) that generates a radical by an acid and / or a base, an organic peroxide polymerization initiator (A21) and / or an azo compound polymerization initiator (A22) are preferable.

  The addition amount of the radical polymerization initiator (A) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight based on the weight of the polymerizable substance (D), from the viewpoint of photocurability. More preferably, it is 0.1 to 20% by weight.

In the present invention, the acid generator (B) means a compound that generates an acid by actinic rays, radicals or acids, and an acid generator (B1) that generates an acid by actinic rays and a group consisting of radicals, acids and bases. Well-known compounds, such as an acid generator (B2) which generate | occur | produces an acid by at least 1 sort (s) chosen from, are mentioned.
For example, the sulfonium salt derivative (B121), the iodonium salt derivative (B122), and the like can generate an acid by any of actinic rays, radicals, acids, or bases, and can be applied as (B1) or (B2).
In addition, the sulfonic acid ester derivative (B21), the acetic acid ester derivative (B22), the phosphonic acid ester (B23) and the like can generate an acid by any of radicals, acids, and bases, and can be applied as (B2). .
(B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the sulfonium salt derivative (B121) in the present invention include compounds represented by the following general formula (1) or the following general formula (2).

In the general formula (1) or (2), A ¹ is a divalent or trivalent group represented by any ^one of the general formulas (3) to (10), and Ar ^{1 to} Ar ⁷ are each independently benzene. Having at least one ring skeleton, halogen atom, C1-C20 acyl group, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, carbon number 1 to 20 alkylsilyl groups, nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, cyano groups, phenyl groups, naphthyl groups, phenoxy groups and phenylthio groups, at least one atom or substituent An aromatic hydrocarbon group or a heterocyclic group which may be substituted with Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, Ar ⁵ is a divalent group, and (X ¹ ) ^- and (X ^{2) -} is an anion And, a is an integer of 0 to 2, b is an integer from 1 to 3, and a + b is an integer equal the valence of A ¹ in 2 or 3.

R ^{1 to} R ⁷ in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or 1 to carbon atoms. 20 alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, at least one atom or optionally substituted phenyl group which is substituted with a group selected from the group consisting of a phenoxy group and a phenylthio group, R ¹ And R ² , R ⁴ and R ⁵ , and R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

As A ¹ in the general formula (2), groups represented by the general formulas (5) and (7) to (10) are preferable from the viewpoint of acid generation efficiency, and the general formulas (5) and (8) The group represented by (10) is more preferable.

Ar ^{1 to} Ar ⁷ in the general formulas (1) and (2) are groups having absorption in the ultraviolet to visible light region.
The number of benzene ring skeletons in Ar ^{1 to} Ar ⁷ is preferably 1 to 5, and more preferably 1 to 4.
As an example in the case of having one benzene ring skeleton, a residue obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline, coumarin, and the like can be given.
Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
As an example in the case of having three benzene ring skeletons, for example, one or two hydrogen atoms were removed from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
Examples of the case of having four benzene ring skeletons include residues obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

  Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio group. , Heptylthio group, octylthio group and the like.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

As the atoms or substituents substituted for Ar ^{1 to} Ar ⁷ , halogen acid, cyano group, phenyl group, naphthyl group, phenoxy group, phenylthio group, alkyl group having 1 to 20 carbon atoms are preferable from the viewpoint of acid generation efficiency. , An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms, more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, They are an alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Ar ^{1 to} Ar ⁴ , Ar ⁶ and Ar ⁷ are preferably a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group, 2,4, from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthylmercapto) phenyl group and m-chlorophenyl group.

Ar ⁵ is preferably a phenylene group, a 2- or 3-methylphenylene group, a 2- or 3-methoxyphenylene group, a 2- or 3-butylphenylene group, and a 2- or 3-chloro group from the viewpoint of acid generation efficiency. A phenylene group.

Examples of the anion represented by (X ¹ ) ⁻ or (X ² ) ⁻ in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, and those having 1 to 4 carbon atoms. Dialkyldithiocarbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.) , An aliphatic or aromatic sulfoxy anion (trifluoromethanesulfonic acid anion, etc.) optionally substituted with halogen, hexafluoroantimonate anion (SbF ₆ ⁻ ), phosphine anion [hexafluorophosphine anion (PF ₆ ⁻ And tris (perfluoroethyl) trifluoride Fin anion _{(PF 3 (C 2 F 5} ) 3 -) , etc.] and borate anion (tetraphenyl borate and butyl triphenyl borate anion), and the like, from the viewpoint of acid generation efficiency, phosphine anion, substituted by halogen Aliphatic sulfoxy ions and borate anions are preferred.

  As the sulfonium salt derivative (B121), a compound having a triphenylsulfonium cation, a tri-p-tolylsulfonium cation, or a [p- (phenylmercapto) phenyl] diphenylsulfonium cation as a cation skeleton is preferable from the viewpoint of acid generation efficiency. Compounds represented by the following general formulas (11) to (14) are preferable, and compounds represented by the following general formulas (11) to (14) are more preferable.

(X ³ ) ⁻ to (X ⁶ ) ⁻ in the general formulas (11) to (14) represent anions, specifically, (X ¹ ) ⁻ or (X ² ) in the general formula (1) or (2). ) ^- it includes the same ones as exemplified as, preferable ones are also same.

  The iodonium salt derivative (B122) in the present invention is represented by the following general formula (15) or the following general formula (16).

In the formula, A ² is a divalent or trivalent group represented by any one of the general formulas (3) to (10), and Ar ^{8 to} Ar ¹² each independently have at least one benzene ring skeleton. A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. , Aromatic group optionally substituted with at least one substituent selected from the group consisting of nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, phenoxy group and phenylthio group A hydrocarbon group or a heterocyclic group, wherein Ar ^{8 to} Ar ¹⁰ and Ar ¹² are monovalent groups, Ar ¹¹ is a divalent group, and (X ⁷ ) ⁻ and (X ⁸ ) ⁻ are anions. C is an integer of 0-2, d is 1-3 An integer, and c + d is an integer equal the valence of A ² in 2 or 3.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

As A ² in the general formula (16), the groups represented by the general formulas (5) and (7) to (10) are preferable from the viewpoint of the efficiency of generating an acid. Groups represented by (8) to (10) are more preferable.

Ar ^{8 to} Ar ¹² in the general formula (15) or the general formula (16) are groups in which the compound represented by the general formula (15) or the general formula (16) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{8 to} Ar ¹² is preferably 1 to 5, and more preferably 1 to 4. Specific examples of Ar ^{8 to} Ar ¹² include general formula (1) or general formula (2). The thing similar to what was illustrated as Ar < ¹ > -Ar < ⁷ > of these is mentioned, A preferable thing is also the same.

Examples of (X ⁷ ) ⁻ and (X ⁸ ) ⁻ include the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ⁻ in the general formula (1) or (2), and preferable ones are also included. It is the same.

  As the iodonium salt derivative (B122), (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium cation, [bis (4-t-butylphenyl)] iodonium are preferable from the viewpoint of acid generation efficiency. Cation, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium cation, [bis (4-methoxyphenyl)] iodonium cation and [bis (4-methoxyphenyl)] iodonium cation. Compounds having a cation skeleton and compounds represented by the following general formulas (17) to (20) are more preferable, and compounds represented by the following general formulas (17) to (20) are more preferable.

In the general formulas (17) to (20), R ^{8 to} R ¹³ are a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An atom or substitution selected from the group consisting of an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group And (X ⁹ ) ⁻ to (X ¹² ) ⁻ represents an anion.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

R ^{8 to} R ¹³ are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, A phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms. An alkoxy group and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Examples of (X ⁹ ) ⁻ to (X ¹² ) ^{− in the} general formulas (17) to (20) include those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in} the general formula (1) or (2). The same thing is mentioned, A preferable thing is also the same.

  In general, the photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) absorbs visible light, and the initiator itself is colored, which adversely affects the hue of the cured film. However, by using the compound represented by the general formula (2) or the general formula (16), an adverse effect on the hue of the cured film can be suppressed.

  Examples of the sulfonic acid ester derivative (B21) include methanesulfonic acid cyclohexyl ester, ethanesulfonic acid isopropyl ester, benzenesulfonic acid-t-butyl ester, p-toluenesulfonic acid cyclohexyl ester, and naphthalenesulfonic acid cyclohexyl ester.

  Examples of the acetate derivative (B22) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.

  Examples of the phosphonic acid ester (B23) include triphenylphosphonic acid cyclohexyl ester.

  The addition amount of the acid generator (B) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight with respect to the weight of the polymerizable substance (D) from the viewpoint of photocurability, and further Preferably it is 0.1-20 weight%.

In the present invention, the base generator (C) means a compound that generates a base by actinic rays, radicals or bases, a group consisting of a base generator (C1) that generates a base by actinic rays and radicals, acids and bases. A known compound such as a base generator (C2) that generates a base with at least one selected from the group consisting of:
For example, the oxime derivative (C121), the quaternary ammonium salt derivative (C122), the quaternary amidine salt derivative (C123), and the like can generate a base by any of actinic rays, radicals, acids, or bases (C1 ) Or (C2).
Further, the carbamate derivative (C21) can generate a base by any of a radical, an acid, and a base, and can be applied as (C2).
(C) may be used individually by 1 type, and may use 2 or more types together.

Examples of the oxime derivative (C121) include o-acyloxime.
Examples of the carbamate derivative (C21) include 1-Fmoc-4-piperidone and o-nitrobenzoyl carbamate.

  Examples of the quaternary ammonium salt derivative (C122) and the quaternary amidine salt derivative (C123) include compounds represented by the following general formulas (21) to (23).

R ^{14 to} R ⁴¹ in the general formulas (21) to (23) are each a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkylthio group, C1-C20 alkylsilyl group, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, represented by general formula (24) An atom or a substituent selected from the group consisting of the substituent represented by formula (25) and the substituent represented by formula (25), wherein any one of R ^{14 to} R ²³ is represented by formula (24) or formula (25 And any one of R ^{24 to} R ³¹ is a substituent represented by the general formula (24) or the general formula (25), and any one of R ^{32 to} R ^41. Is a substitution represented by the general formula (24) or the general formula (25) It is a group.

R ^{42 to} R ⁴⁵ in the general formulas (24) and (25) are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{46 to} R ⁴⁸ are each having 1 to 20 carbon atoms which may be substituted with a hydroxyl group. It is an alkyl group, (X ¹³ ) ⁻ and (X ¹⁴ ) ⁻ represent an anion, and e is an integer of 2 to 4.

  In general formulas (21) to (23), a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon Examples of the alkylsilyl group having 1 to 20 are the same as those described in the description of the general formula (1) and the general formula (2).

The compound represented by the general formula (21) is an anthracene skeleton, the compound represented by the general formula (22) is a thioxanthone skeleton, and the compound represented by the general formula (23) is a compound having a benzophenone skeleton, i-line (365 nm). It is an example of a compound having a maximum absorption wavelength in the vicinity. R ^{14 to} R ²³ are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc., and include a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, Nitro group, carboxyl group, hydroxyl group, mercapto group, alkyl silyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, alkyl group having 1 to 20 carbon atoms, phenyl group, naphthyl group The atom or substituent selected from the group consisting of is modified according to the purpose. However, any one of R < ¹⁴ > -R < ²³ > is a substituent represented by General formula (24) or General formula (25).

R ^{14 to} R ²³ are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, A phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms. An alkoxy group and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Specific examples of the above R ^{14 to} R ²³ include the compounds described in the description of R ^{8 to} R ^{13 in} the general formulas (17) to (19).

The substituent represented by the general formula (24) is a substituent having a cationized amidine skeleton, and e is an integer of 2 to 4. Examples of the substituent include a substituent having a cationized structure of 1,8-diazabicyclo [5.4.0] -7-undecene in which e is 4, and 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure. R ⁴² and R ⁴³ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. It is.

General formula (25) has a quaternary ammonium structure, R ⁴⁴ and R ⁴⁵ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, More preferably, they are a hydrogen atom or a C1-C5 alkyl group. R ^{46 to} R ⁴⁸ represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic. R ^{46 to} R ⁴⁸ are preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

(X ¹³ ) ⁻ and (X ¹⁴ ) ⁻ in the general formulas (24) and (25) represent anions, specifically, (X ¹ ) ⁻ or (X ² ) in the general formula (1) or (2). ) ^- it includes the same as those exemplified as. Of these, aliphatic or aromatic carboxy ions and borate anions are preferred from the viewpoint of photodegradability.

When the compound represented by the general formula (24) is irradiated with actinic rays, the bond between carbon and nitrogen to which R ⁴² and R ⁴³ are bonded is cleaved to produce a basic compound having an amidine skeleton. In the compound represented by 25), upon irradiation with actinic rays, a bond between carbon and nitrogen to which R ⁴⁴ and R ⁴⁵ are bonded is cleaved to produce a tertiary amine.

  Of these base generators (C1) that generate bases by actinic rays, compounds represented by the following general formula (26) are preferred from the viewpoint of photodegradability.

(X ¹⁵ ) ⁻ in the general formula (26) represents an anion, specifically, the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in the} general formula (1) or (2). Things. Of these, aliphatic or aromatic carboxy ions and borate anions are preferred from the viewpoint of photodegradability.

  Examples of the carbamate derivative (C21) include 1-Z-4-piperidone.

  The addition amount of the base generator (C) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight with respect to the weight of the polymerizable substance (D) from the viewpoint of photocurability, and further Preferably it is 0.1-20 weight%.

In the present invention, it is preferable to contain (A1), (A2), (B1), (B2), (C1) and (C2) in any combination of the following (1) to (4).
(1) Contains (A1), (B2) and (C2).
(2) Contains (B1), (A2) and (C2).
(3) Contains (C1), (A2) and (B2).
(4) A combination of two or more of (1) to (3) above.

  As the polymerizable substance (D) in the present invention, known compounds such as a radical polymerizable compound (D1) and an ionic polymerizable compound (D2) can be used. (D) may be used alone or in combination of two or more. Further, if necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be used in combination.

Examples of the radical polymerizable compound (D1) include an acrylamide compound (D11) having 3 to 35 carbon atoms, a (meth) acrylate compound (D12) having 4 to 35 carbon atoms, and an aromatic vinyl compound (D13) having 6 to 35 carbon atoms. And a C3-C20 vinyl ether compound (D14) and other radical polymerizable compounds (D15).
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.

  Examples of the (meth) acrylamide compound (D11) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- n-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide, N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholine.

Examples of the (meth) acrylate compound (D12) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates.
Monofunctional (meth) acrylates include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( (Meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate Relate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexyl carbitol ( (Meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meta) ) Acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxy Propyl (meth) acrylate, diethylene glycol monovinyl ether monoacrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate Rate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene Oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether ( (Meth) acrylate, dipropylene glycol (meth) acrelane , Polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2- Hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO Modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, PO modified nonylphenol (meth) acrylate and EO modified-2- Ethylhexyl (meth) acrylate.

  As the bifunctional (meth) acrylate, 1,4-butanedi (meth) acrylate, 1,6-hexanediacrylate, polypropylene diacrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanedioldi (Meth) acrylate, neopentyl diacrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) a Relate, hydroxypivalate neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate and tri And cyclodecanedi (meth) acrylate.

  Trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate , Propoxylated trimethylolpropane tri (meth) acrylate and ethoxylated glycerol triacrylate, and the like.

  Tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionate dipentaerythritol tetra (meth) acrylate and ethoxylated pentaerythritol tetra. (Meth) acrylate etc. are mentioned.

  Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate, dipenta Examples thereof include carboxylic acid-containing penta (meth) acrylate, which is a reaction product of erythritol penta (meth) acrylate and a polyvalent carboxylic acid or polyvalent carboxylic acid anhydride.

  Examples of the aromatic vinyl compound having 6 to 35 carbon atoms (D13) include vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro. Styrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, Seo propenyl styrene, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

As a C3-C35 vinyl ether compound (D14), the following monofunctional or polyfunctional vinyl ether is mentioned, for example.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

  Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added penta Examples include erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  Other radical polymerizable compounds (D15) include acrylonitrile, vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), allyl ester compounds (such as allyl acetate), and halogen-containing monomers (vinylidene chloride and chloride). Vinyl) and olefin compounds (ethylene and propylene, etc.).

  Among these, from the viewpoint of curing speed, the acrylamide compound (D11) having 3 to 35 carbon atoms, the (meth) acrylate compound (D12) having 4 to 35 carbon atoms, and the aromatic vinyl compound having 6 to 35 carbon atoms are preferable. (D13) and a C3-C20 vinyl ether compound (D14), more preferably a C3-C35 acrylamide compound (D11) and a C4-C35 (meth) acrylate compound (D12). .

  Examples of the ion polymerizable compound (D2) include an epoxy compound (D21) having 3 to 20 carbon atoms and an oxetane compound having 4 to 20 carbon atoms (D22).

As a C3-C20 epoxy compound (D21), the following monofunctional or polyfunctional epoxy compounds are mentioned, for example.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide. 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide and 3-vinylcyclohexene oxide. .

  Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether. Epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) Til) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Serine triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-di Examples include epoxy octane and 1,2,5,6-diepoxycyclooctane.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of curing speed, and alicyclic epoxides are particularly preferable.

  Examples of the oxetane compound (D22) having 4 to 20 carbon atoms include compounds having 1 to 6 oxetane rings.

  Examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4 -Fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3 -Oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanyl) Methyl) ether, 2-ethylhexyl (3-ethyl-3-o Cetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxy Ethyl (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, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether and bornyl (3-ethyl-3-oxetanylmethyl) ether.

  Examples of the compound having 2 to 6 oxetane rings include 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-oxetanyl) Methyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4 -Bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis ( 3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO Modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A Bis (3-ethyl-3-oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether are mentioned.

  Of these, compounds having 1 to 2 oxetane rings are preferred from the viewpoint of curing speed.

  As the colorant (E) in the present invention, pigments and dyes such as inorganic pigments and organic pigments conventionally used in paints and inks can be used.

  Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

  Organic pigments include β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone and other soluble azo pigments, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetanilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as cinderdinone-based, quinacridone-based, dioxazine-based, perinone-based, and perylene-based compounds. For example, in the color index (CI; published by The Society of Dyersand Colorists) Compounds that are classified into placement (Pigment), specifically, there may be mentioned those color index (C.I.) numbers are assigned as follows.

  C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180 and C.I. I. Pigment yellow 185;

  C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71 and C.I. I. Pigment orange 73; C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36 and C.I. I. Pigment violet 38;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1 and C.I. I. Pigment red 97,

  C. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264 and C.I. I. Pigment red 265;

C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60; C.I. I. Pigment green 7, C.I. I. Pigment green 36; C.I. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment black 1 and C.I. I. Pigment Black 7.
These organic pigments can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

  Specific examples of dyes include yellow dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones or open-chain active methylene compounds as coupling components, open-chain activity as coupling components Examples thereof include azomethine dyes having a methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes.

  For magenta dyes, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes, azomethine dyes having a pyrazolone or pyrazolotriazole as a coupling component, arylidene dyes, styryl dyes, merocyanine dyes such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples thereof include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of the coupling component include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives, aryl or heteryl azo dyes (such as CI Direct Blue 14), and indigo / thioindigo dyes.

  The particle diameter of the colorant (E) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm, as an average particle diameter, from the viewpoint of the sharpness of the coating film.

  Although the addition amount of a coloring agent (E) is not specifically limited, It is preferable to add in the range of 1-60 weight% in the photosensitive composition of this invention.

In the photosensitive composition of the present invention, when a pigment is used, a pigment dispersant is preferably added to improve the dispersibility and the storage stability of the photosensitive composition.
Pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184, 2020, etc.) ), Pigment dispersants manufactured by Ajinomoto Fine Techno Co. (Ajisper PB711, PB821, PB814, PN411, PA111, BP-831, etc.), pigment dispersants manufactured by Lubrizol (Solspers 5000, 12000, 32000, 33000, 39000, etc.). It is done. These pigment dispersants may be used alone or in combination of two or more. Although the addition amount of a pigment dispersant is not specifically limited, It is preferable to use in the range of 0.1 to 10 weight% in the photosensitive composition.

  By containing the metal oxide powder (F) or the metal powder (G), the photosensitive composition of the present invention can be used for green sheet formation and electrode layer formation of ceramic electronic components.

  The metal oxide powder (F) is used when forming the dielectric layer. Examples of (F) include titanium oxide, aluminum oxide, barium titanate, calcium zirconate, niobium oxide, and lead zirconate titanate, with barium titanate being preferred.

  The particle diameter of (F) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm as an average particle diameter from the viewpoint of dielectric constant.

  The addition amount in the photosensitive composition when using the metal oxide powder (F) is preferably 1 to 80% by weight, more preferably, based on the weight of the polymerizable substance (D) from the viewpoint of sharpness. 5 to 60% by weight.

The metal powder (G) is a noble metal and a base metal used when forming the conductor layer, and specifically includes palladium, nickel, copper, silver, gold, etc., preferably palladium, nickel, and copper. It is.
The average particle size of (G) is preferably 0.01 μm to 10 μm.

  The addition amount in the photosensitive composition when using the metal powder (G) is preferably 1 to 80% by weight, more preferably 5 to 5%, based on the weight of the polymerizable substance (D), from the viewpoint of sharpness. 60% by weight.

  The photosensitive composition of this invention can be used for formation of a negative resist pattern by containing a hydrophilic epoxy resin (J) and a crosslinking agent (K) further.

The hydrophilic epoxy resin (J) is an epoxy resin containing a hydrophilic functional group such as a hydroxyl group, a carboxyl group, or an oxyethylene group in the molecule, and more preferably has a carboxyl group from the viewpoint of developability.
The carboxyl group content is indicated by an acid value.
The acid value of (J) is preferably 10 to 500 mgKOH / g. If it is 10 mgKOH / g or more, the developability is more likely to be exhibited, and if it is 500 mgKOH / g or less, the water resistance of the cured product can be further improved.

The acid value in the present invention can be measured by an indicator titration method using an alkaline titration solution. The method is as follows.
(I) About 0.1 to 10 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then a neutral methanol / acetone solution [a mixture of acetone and methanol at 1: 1 (volume ratio)] is added and dissolved.
(Ii) Add several drops of phenolphthalein indicator and titrate with 0.1 mol / L potassium hydroxide titration solution. The end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.
(Iii) Determine using the following equation.
Acid value (mgKOH / g) = (A × f × 5.61) / S
Where, A: number of mL of 0.1 mol / L potassium hydroxide titration solution f: titer of 0.1 mol / L potassium hydroxide titration solution S: sampling amount (g)

  The hydrophilic epoxy resin (J) particularly preferably has an acryloyl group and / or a methacryloyl group in the molecule from the viewpoint of photocuring reactivity.

A preferred method for producing the hydrophilic epoxy resin (J) is to add all or part of the epoxy groups in the raw material epoxy resin (J ₀ ) (hereinafter sometimes simply referred to as (J ₀ )) to (meta ) Reacting acryloyl group-containing monocarboxylic acid (j) to open an epoxy group to form a hydroxyl group, and reacting polyvalent carboxylic acid and / or polyvalent carboxylic acid anhydride (z) with a part of this hydroxyl group It is a method to make it.

Examples of the raw material epoxy resin (J ₀ ) include aliphatic epoxy resins [for example, sorbitol polyglycidyl ether (Denacol EX-611), glycerol triglycidyl ether (Denacol EX-313), 1,6-hexanediol diglycidyl ether (Denacol). EX-212) (both manufactured by Nagase Kasei Kogyo Co., Ltd.)] and alicyclic epoxy resins [for example, diglycidyl ether of hydrogenated bisphenol A (Denacol EX-252) (manufactured by Nagase Kasei Kogyo Co., Ltd.)] and aromatic epoxy Resin [for example, phenol novolac epoxy resin, cresol novolac epoxy resin {for example, EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.)}, bisphenol A epoxy resin, biphenyl type epoxy resin, glycidyl modified polyvinylphenol, etc.) It is.
Among (J ₀ ), an aromatic epoxy resin is preferable from the viewpoint of the hardness of the cured product.

  Examples of the (meth) acryloyl group-containing monocarboxylic acid (j) used for the production of (J) include acrylic acid, methacrylic acid, and 2-acryloyloxyethyl succinic acid.

The polyvalent carboxylic acid and polyvalent carboxylic acid anhydride (z) used in the production of (J) are unsaturated polyvalent carboxylic acid, saturated polyvalent (2-6 valent) carboxylic acid, and anhydrides thereof. Is mentioned.
Examples of polycarboxylic acids include aliphatic saturated polycarboxylic acids such as oxalic acid, succinic acid, adipic acid, dodecanedioic acid and hexahydrophthalic acid; dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl Aliphatic unsaturated polycarboxylic acids such as succinic acid, tetrahydrophthalic acid and methyltetrahydrophthalic acid; aromatic polycarboxylic acids such as phthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid and naphthalenetetracarboxylic acid Is mentioned.
Examples of polyhydric carboxylic anhydrides include aliphatic saturated polycarboxylic anhydrides such as succinic anhydride and hexahydrophthalic anhydride; dodecenyl succinic anhydride, pentadecenyl succinic anhydride, octadecenyl succinic anhydride, tetrahydrophthalic anhydride and Aliphatic unsaturated polyvalent carboxylic acid anhydrides such as methyltetrahydrophthalic anhydride; aromatic polyhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, biphenyltetracarboxylic anhydride and naphthalenetetracarboxylic anhydride Carboxylic acid anhydrides.
Of these, saturated polyvalent carboxylic acid anhydrides are preferable from the viewpoints of sensitivity and developability.

In the production of (J), the charged weight ratio of (meth) acryloyl group-containing monocarboxylic acid (j) / (J ⁰ ) is preferably such that the concentration of the (meth) acryloyl group in (J) is 1.0 mmol / g or more. The weight ratio is such that

The reaction temperature in the reaction of the raw material epoxy resin (J ⁰ ) and the (meth) acryloyl group-containing monocarboxylic acid (j) is not particularly limited, but is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 5 to 30 hours. Further, if necessary, a catalyst (for example, triphenylphosphine) and a radical polymerization inhibitor (hydroquinone, p-methoxyphenol, etc.) may be used.

The charge equivalent of the polyvalent carboxylic acid and / or polyvalent carboxylic acid anhydride (z) relative to the weight of the (meth) acryloyl group-containing monocarboxylic acid (j) adduct of (J ⁰ ) is the acid value of (J) However, the equivalent / g which becomes 10-500 mgKOH / g is preferable. For example, when (z) is a divalent carboxylic acid or an anhydride thereof, the charge equivalent of (z) / (J ⁰ ) (meth) acrylic acid adduct is preferably 0 from the above viewpoint. .18 to 8.9 meq / g, more preferably 0.53 to 7.1 meq / g.

The reaction temperature in the reaction of the (meth) acryloyl group-containing monocarboxylic acid adduct of (J ⁰ ) with the polyvalent carboxylic acid and / or polyvalent carboxylic anhydride (z) is not particularly limited, but preferably 70 ~ 110 ° C. The reaction time is not particularly limited, but is preferably 3 to 10 hours.

  The number average molecular weight (hereinafter sometimes abbreviated as “Mn”) of (J) is preferably 500 to 3,000, more preferably 1, from the viewpoint of sensitivity and developability as a photosensitive composition. 000-2,800.

  Mn is a value in terms of polystyrene measured by the GPC method using a GPC measuring device (HLC-8120GPC, manufactured by Tosoh Corporation) and a column (2 TSKgel GMHXL + TSKgel Multipore HXL-M, manufactured by Tosoh Corporation). As sought.

  As the hydrophilic epoxy resin (J) in the present invention, known compounds such as a cresol novolac type acid-modified epoxy acrylate resin can be used, and examples thereof include CCR-1218H, CCR-1159H, CCR-1222H, CCR-1314H, PCR-1191H, TCR-1335H, ZAR-2001H, and ZCR-1569H [all are all manufactured by Nippon Kayaku Co., Ltd.].

  The addition amount of the hydrophilic epoxy resin (J) in the photosensitive composition of the present invention is preferably 90% by weight or less, more preferably 5%, based on the weight of the polymerizable substance (D), from the viewpoint of developability. ~ 80% by weight.

  Examples of the crosslinking agent (K) in the present invention include polysiloxane (K1) or melamine resin (K2) having two or more hydrolyzable alkoxy groups.

The polysiloxane (K1) having two or more hydrolyzable alkoxy groups has a silane compound (p1) represented by the following general formula (27) as an essential constituent monomer, and the alkoxy group [general formula (27) A portion of OR ⁵¹ ] in the middle is a condensate obtained by polymerizing through a condensation reaction.

In the formula, R ⁴⁹ is one or more organic groups selected from the group consisting of (meth) acryloyloxyalkyl groups having 1 to 6 carbon atoms in the alkylene group, glycidyl alkyl groups, mercaptoalkyl groups and aminoalkyl groups. It is.
R ⁵⁰ is an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
R ⁵¹ is an alkyl group having 1 to 4 carbon atoms. m is 0 or 1.

R ⁴⁹ does not react in the condensation reaction step of the silane compound (p1), and remains in the polysiloxane (K1) after the condensation reaction, so that it undergoes the thermosetting reaction when the photosensitive composition of the present invention is thermally cured. It is a functional group that contributes.
R ⁴⁹ is preferably a (meth) acryloyloxyalkyl group or a glycidoxyalkyl group from the viewpoint of curability.

Among R ⁵⁰ , examples of the alkyl group having 1 to 12 carbon atoms include a linear alkyl group and a branched alkyl group.
Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-octyl and n-dodecyl groups. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl and 2-ethylhexyl groups. Can be mentioned.

Among R ⁵⁰ , examples of the alicyclic hydrocarbon group include a cyclohexyl group, a cyclooctyl group, a cyclohexylmethyl group, and a methylcyclohexyl group.

Among R ⁵⁰ , examples of the 6-12 aromatic hydrocarbon group include an aryl group, an aralkyl group, and an alkylaryl group.
Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group; examples of the aralkyl group include a tolyl group, xylyl group, and mesityl group; and examples of the alkylaryl group include a methylphenyl group and an ethylphenyl group.

Among R ⁵⁰ , a linear alkyl group, a branched alkyl group and an aryl group are preferable from the viewpoint of curing reactivity, and a linear alkyl group and an aryl group are more preferable.
Preferred are a methyl group, an ethyl group, a phenyl group, and combinations thereof.

Examples of R ⁵¹ which is an alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec-butyl group, and a thermosetting reaction is preferable. From the viewpoint of properties, they are methyl group and ethyl group.

In the general formula (27), examples of the silane compound (p1) having a (meth) acryloyloxyalkyl group as R ⁴⁹ include the following compounds.
Examples of trifunctional silane compounds in which m is 0, that is, three alkoxy groups include 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3 -Acryloyloxypropyltriethoxysilane and the like.

  Examples of the trifunctional silane compound in which m is 1, that is, two alkoxy groups include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3 -Acryloyloxypropylmethyldiethoxysilane and the like.

Examples of the silane compound having a glycidoxyalkyl group as R ⁴⁹ include the following compounds.
Examples of the trifunctional silane compound in which m is 0, that is, three alkoxy groups include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

  Examples of the trifunctional silane compound in which m is 1, that is, two alkoxy groups include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like.

Examples of the silane compound having a mercaptoalkyl group as R ⁴⁹ include the following compounds.
Examples of the trifunctional silane compound in which m is 0, that is, three alkoxy groups include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like. Examples of the trifunctional silane compound in which m is 1, that is, two alkoxy groups include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and the like.

The silane compound having an aminoalkyl group as R ^49, include compounds such as the following.
Examples of trifunctional silane compounds in which m is 0, that is, three alkoxy groups include N-2 aminoethyl γ-aminopropyltrimethoxysilane, N-2 aminoethyl γ-aminopropyltriethoxysilane, and 3-aminopropyltrimethoxy. Silane, 3-aminopropyltriethoxysilane, etc. are mentioned.
Examples of trifunctional silane compounds having m of 1, that is, two alkoxy groups include N-2 aminoethyl γ-aminopropylmethyldimethoxysilane, N-2 aminoethyl γ-aminopropylmethyldiethoxysilane, and 3-aminopropylmethyl. Examples include dimethoxysilane and 3-aminopropylmethyldiethoxysilane.

Among (p1) represented by the general formula (27), R ⁴⁹ in the general formula (27) is preferably a (meth) acryloyloxyalkyl group or a glycidoxyalkyl group from the viewpoint of curing reactivity. It is a silane compound having
More preferred are (meth) acryloyloxyalkyl group-containing trifunctional silane compounds having 3 alkoxy groups, and glycidoxyalkyl group-containing trifunctional silane compounds having 3 alkoxy groups. Particularly preferred are 3-acryloyloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.

As (K1), a homocondensation polymer consisting only of the silane compound (p1) represented by the general formula (27), and other silane compounds (p2) and (p1) capable of cocondensing with (p1) These cocondensates are mentioned.
Examples of the silane compound (p2) that can be co-condensed with (p1) include silane compounds represented by the following general formula (28).

In formula (28), R ⁵² is an alkyl group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ⁵³ is an alkyl group having 1 to 4 carbon atoms, and n is 0 to 0. It is an integer of 2.

Examples of R ⁵² and R ^{53 in} formula (28) include those exemplified for R ⁵⁰ and R ⁵¹ in formula (27).
Of R ^52, a linear alkyl group, a branched alkyl group, and an aryl group are preferable, and a linear alkyl group and an aryl group are more preferable. Particularly preferred are a methyl group, an ethyl group, a phenyl group and a combination thereof.
R ⁵³ is preferably a methyl group or an ethyl group.

In the general formula (28), examples of the tetrafunctional silane compound having n = 0, that is, four alkoxy groups include tetramethoxysilane and tetraethoxysilane.
Examples of the trifunctional silane compound in which n is 1, that is, three alkoxy groups include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
Examples of the bifunctional silane compound in which n is 2, that is, two alkoxy groups include diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldimethoxysilane, and phenylmethyldiethoxysilane. .
From the viewpoint of forming a uniform network of polysiloxane (K1), n is 1, that is, a trifunctional silane compound is preferable.

  The charge ratio (p1) / (p2) of the total amount of the silane compound (p1) and the other silane compound (p2) is preferably 1 / 0.1 to 1 / 6.0 mol from the viewpoint of curing reactivity. More preferably, 1 / 0.2 to 1 / 4.0 mol is good.

  The polysiloxane (K1) is, for example, 20 to 100 ° C. in a dry atmosphere with stirring a predetermined amount of water and, if necessary, a catalyst in the silane compound (p1) and other silane compound (p2) used as necessary. In about 10 minutes to 60 minutes, and then aged for 1 to 12 hours at a temperature below the boiling point of the by-produced alcohol (for example, 0 to 150 ° C.) to obtain a condensation reaction.

When the amount of water added in the condensation reaction is Y mol and the number of moles of alkoxy groups in the silane compound (p1) and the other silane compound (p2) is W, if Y / W is too small, the yield of the condensate The molecular weight decreases. On the other hand, when Y / W is too large, the molecular weight becomes too large and the storage stability tends to decrease.
From this, it is preferable to carry out in the range of 0.1 <Y / W <5, more preferably in the range of 0.3 <Y / W <3.
As the water to be added, ion exchange water or distilled water is usually used.

  In addition, a silane compound having one alkoxy group can be co-condensed for the purpose of adjusting the molecular weight. Examples of the silane compound having one alkoxy group include triphenylmethoxysilane and trimethylmethoxysilane.

Examples of the catalyst for the condensation reaction include organic acids, inorganic acids, alkali metal hydroxides, alkaline earth hydroxides, quaternary alkyl ammonium hydroxides, quaternary alkyl ammonium halides, sodium hypochlorite, Examples thereof include metal alkoxides and chelate complexes thereof. Of these, acidic catalysts such as organic acids, inorganic acids, metal alkoxides, and metal alkoxide chelate compounds are preferred, and organic acids are particularly preferred.
The addition amount of the catalyst is preferably 0.0001 to 10 parts by weight, and more preferably 0.001 to 1 part by weight with respect to the total of 100 parts by weight of (p1) and (p2).

  Examples of (K1) include KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, X-22-164, X-22-164AS, and X-22 manufactured by Shin-Etsu Chemical Co., Ltd. -164A, X-22-164B, X-22-164C, X-22-164E, X-22-174DX, X-22-2426 and X-22-2475, and BYK-3500 manufactured by Big Chemie, Examples include BYK-3510 and BYK-3530.

  As the melamine resin (K2) in the present invention, a known compound can be used. For example, a complete alkyl group type (Cymel 300, Cymel 350 etc.), a methylol group type (Cymel 370 etc.) and an imino group type (Cymel 204). , Cymel 325, etc.) [all above, all manufactured by Mitsui Cyanamid Co., Ltd.].

  The addition amount of the crosslinking agent (K) in the photosensitive composition of the present invention is preferably 90% by weight or less, more preferably 5 to 80%, based on the weight of the polymerizable substance (D), from the viewpoint of developability. % By weight.

  The photosensitive composition of the present invention can contain a solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent) and the like as necessary.

Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, limonene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (Tetrahydrofuran and 1,8-cineole etc.). These may be used alone or in combination of two or more.
The content of the solvent in the photosensitive composition is preferably 0 to 99% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight.

  Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive composition.

  Adhesion imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. The content of the adhesion-imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive composition.

  The photosensitive composition of the present invention further comprises inorganic fine particles, a dispersant, an antifoaming agent, a leveling agent, a thixotropic agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant and an ultraviolet ray in accordance with the purpose of use. An absorbent or the like can be contained.

  The photosensitive composition of the present invention comprises a radical initiator (A), an acid generator (B), a base generator (C), a polymerizable substance (D), a colorant (E), a metal oxide. Ball mill with powder (F) or metal powder (G) and, if necessary, hydrophilic epoxy resin (J), cross-linking agent (K) [polysiloxane (K1), melamine resin (K2), etc.], solvent and other components Alternatively, it can be obtained by kneading with a three roll mill or the like. The kneading temperature is preferably 10 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.

  Since the photosensitive composition of the present invention can be photocured by irradiation with actinic rays of 360 to 830 nm, in addition to commonly used high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, high-power metal halide lamps and the like (UV · The latest trends in EB curing technology, edited by Radtech Research Association, CMC Publishing, 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Heating may be performed for the purpose of diffusing the base generated from the photobase generator during and / or after irradiation with actinic rays. The heating temperature is preferably 30 ° C to 200 ° C, more preferably 35 ° C to 150 ° C, and particularly preferably 40 ° C to 120 ° C.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”. In addition, Examples 1-4, 12, 14, 15, 17, 19-25, 33, 35, 36, 38, and 40-41 in the following are reference examples.

  The photosensitive composition of the present invention is also suitable for a color filter containing a pattern formed by alkali development to form a pattern and further post-baking.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

[Production of acid generator (B)]
Production Example 1
[Synthesis of Acid Generator (B121-1) {Compound Represented by Chemical Formula (29)}]

(1) Synthesis of 2- (phenylthio) thioxanthone [intermediate (B121-1-1)]:
11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. The product was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. Purification by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) yielded 3.1 parts of intermediate (B121-1-1) (yellow solid).

(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (B121-1-2)]:
While stirring 11.2 parts of the intermediate (B121-1-1), 215 parts of acetonitrile, and 0.02 part of sulfuric acid at 40 ° C., 4.0 parts of 30% aqueous hydrogen peroxide was gradually added dropwise thereto. After reacting at ˜45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to obtain 13.2 parts of intermediate (B121-1-2) (yellow solid).

(3) Synthesis of acid generator (B121-1):
While stirring 4.3 parts of the intermediate (B121-1-2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise thereto, After reacting at ˜45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and washed with water until the pH of the aqueous phase becomes neutral. Washed. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed, and the residue was dried under reduced pressure. This residue was dissolved in 212 parts of dichloromethane, charged into 65 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing with water three times, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of an acid generator (B121-1) (yellow solid).

Production Example 2
[Synthesis of Acid Generator (B121-2) {Compound Represented by Chemical Formula (30)}]

  In a reaction vessel, IRGACURE 819 [Ciba Japan Co., Ltd.] 4.2 parts, p-tolyl sulfoxide [Tokyo Chemical Industry Co., Ltd.] 2.8 parts, nonafluoro-1-butanesulfonate potassium [Tokyo Chemical Industry Co., Ltd.] 4 .1 part, 1.2 parts of sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd.] and 100 parts of acetonitrile were charged and dissolved, and stirred at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the solvent was distilled off from the organic layer under reduced pressure to obtain 6.7 parts of an acid generator (B121-2) (yellow solid). .

Production Example 3
[Synthesis of Acid Generator (B121-3) {Compound Represented by Chemical Formula (31)}]

  In a reaction vessel, 3.5 parts of DAROCUR TPO [Ciba Japan Co., Ltd.], 2.4 parts of diphenyl sulfoxide [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.2 parts of potassium hexafluorophosphate [manufactured by Tokyo Chemical Industry Co., Ltd.], sulfuric acid [Wako Pure Chemical Industries, Ltd.] 1.2 parts and 100 parts of acetonitrile were charged and dissolved, followed by stirring at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the solvent was distilled off from the organic layer under reduced pressure to obtain 5.4 parts of an acid generator (B121-3) (yellow solid). .

Production Example 4
[Synthesis of Acid Generator (B121-4) {Compound Represented by Chemical Formula (32)}]

  In a reaction vessel, 2.8 parts of IRGACURE 907 [Ciba Japan Co., Ltd.], 1.7 parts of bromobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.3 parts of silver tetrafluoroborate [manufactured by Tokyo Chemical Industry Co., Ltd.] and tetrahydrofuran 100 parts were charged and dissolved, and stirred at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the solvent was distilled off from the organic layer under reduced pressure to obtain 3.3 parts of an acid generator (B121-4) (light yellow solid). It was.

Production Example 5
[Synthesis of Acid Generator (B122-1) {Compound Represented by Chemical Formula (33)}]

  8.1 parts of t-butylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 5.35 parts of potassium iodide [manufactured by Tokyo Chemical Industry Co., Ltd.] and 20 parts of acetic anhydride are dissolved in 70 parts of acetic acid and cooled to 10 ° C. While maintaining the temperature at 10 ± 2 ° C., a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed 3 times with water, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the target acid generator (B122-1) (light yellow liquid). It was.

Production Example 6
[Synthesis of Acid Generator (B122-2) {Compound Represented by Chemical Formula (34)}]

  “8.1 parts” of “t-butylbenzene” is added to 7.5 parts of “p-methoxybenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]” and “118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate}” Except for changing to “potassium hexafluorophosphate [manufactured by Tokyo Chemical Industry Co., Ltd.] 80 parts”, 12.1 parts of an acid generator (B122-2) (light yellow liquid) was obtained in the same manner as in Production Example 5.

Production Example 7
[Synthesis of Acid Generator (B122-3) {Compound Represented by Chemical Formula (35)}]

  “8.1 parts of t-butylbenzene” was replaced with “9.2 parts of methyl phenoxyacetate [Tokyo Kasei Co., Ltd.]” and “118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} 13.3 parts of an acid generator (B122-3) (light yellow liquid) were obtained in the same manner as in Production Example 5 except that it was changed to 140 parts of tetrakis (perfluorophenyl) borate [manufactured by Tokyo Chemical Industry Co., Ltd.]. .

Production Example 8
[Synthesis of Acid Generator (B122-4) {Compound Represented by Chemical Formula (36)}]

  In a reaction vessel, IRGACURE 651 [Ciba Japan Co., Ltd.] 2.4 parts, potassium iodide [Tokyo Kasei Co., Ltd.] 4.0 parts, hexafluoroantimonate silver [Tokyo Kasei Co., Ltd.] 8.2 parts, 2.4 parts of sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd.], 5.0 parts of benzene and 100 parts of acetonitrile were charged and dissolved, followed by stirring at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the organic solvent was distilled off under reduced pressure to obtain 10.7 parts (light yellow solid) of an acid generator (B122-4).

[Production of base generator (C)]
Production Example 9
[Synthesis of Base Generator (C122-1) {Compound represented by Formula (37)}]

  Dissolve 2.0 parts of 9-chloromethylanthracene (manufactured by Aldrich) in chloroform and add 3.1 parts of trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] little by little (slightly exothermic after addition) The mixture was stirred at room temperature (about 25 ° C.) for 1 hour to obtain a reaction solution. The reaction solution is dropped little by little into an aqueous solution consisting of 4.0 parts of sodium tetraphenylborate salt and 40 parts of water, and the mixture is further stirred for 1 hour at room temperature (about 25 ° C.). The layer was washed 3 times with water. The organic solvent was distilled off under reduced pressure to obtain 7.1 parts of a white solid. This white solid was recrystallized from acetonitrile to obtain 6.2 parts of a base generator (C122-1) (white solid).

Production Example 10
[Synthesis of Base Generator (C122-2) {Compound Represented by Chemical Formula (38)}]

(1) Synthesis of methylthioxanthone [intermediate (C122-2-1)]:
10 parts of dithiosalicylic acid [manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved in 139 parts of sulfuric acid, stirred for 1 hour at room temperature (about 25 ° C.), and then cooled in an ice bath to obtain a cooled solution. Next, 25 parts of toluene was dropped little by little while keeping the liquid temperature of this cooling solution at 20 ° C. or lower, and then returned to room temperature (about 25 ° C.) and further stirred for 2 hours to obtain a reaction solution. The reaction solution was added little by little to 815 parts of water, and the precipitated yellow solid was filtered off. This yellow solid is dissolved in 260 parts of dichloromethane, 150 parts of water is added, 6.7 parts of 24% KOH aqueous solution is further added to make the aqueous layer alkaline, and the mixture is stirred for 1 hour, and then the aqueous layer is removed by a liquid separation operation. The organic layer was washed 3 times with 130 parts of water. Then, the organic layer was dried over anhydrous sodium sulfate, and then the organic solvent was distilled off under reduced pressure to obtain 8.7 parts of intermediate (C122-2-1) (yellow solid). The intermediate (C122-2-1) is a mixture of 2-methylthioxanthone and 3-methylthioxanthone.

(2) Synthesis of 2-bromomethylthioxanthone [intermediate (C122-2-2)]:
An intermediate (C122-2-1) (2.1 parts) was dissolved in cyclohexane (120 parts), and N-bromosuccinimide [Wako Pure Chemical Industries, Ltd.] 8.3 parts and benzoyl peroxide [Wako Pure Chemical Industries, Ltd.] Made by Co., Ltd.] After adding 0.1 part and reacting under reflux for 4 hours (3-methylthioxanthone does not react), the solvent (cyclohexane) was distilled off, and then 50 parts of chloroform was added to the residue. Redissolved to obtain a chloroform solution. The chloroform solution was washed with 30 parts of water three times, and the aqueous layer was removed by a liquid separation operation. Then, the organic solvent was distilled off under reduced pressure to obtain 1.7 parts of a brown solid. This was recrystallized from ethyl acetate (3-methylthioxanthone was removed here) to obtain 1.5 parts of intermediate (C122-2-2) (yellow solid).

(3) Synthesis of N- (9-oxo-9H-thioxanthen-2-yl) methyl-N, N, N-tris (2-hydroxyethyl) ammonium bromide [intermediate (C122-2-3)]
After dissolving 1.0 part of intermediate (C122-2-2) (2-bromomethylthioxanthone) in 85 g of dichloromethane, 0.5 part of triethanolamine [manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise thereto. The mixture was stirred at room temperature (about 25 ° C.) for 1 hour, and the organic solvent was distilled off under reduced pressure to obtain 2.2 parts of a white solid. This white solid was recrystallized with a tetrahydrofuran / dichloromethane mixed solution to obtain 1.0 part of an intermediate (C122-2-3) (brown solid).

(4) Synthesis of base generator (C122-2):
Sodium tetraphenylborate salt [manufactured by Nacalai Tesque Co., Ltd.] 0.8 parts of an intermediate (C122-2-3) was dissolved in 50 parts of chloroform in an aqueous solution in which 17 parts of water was dissolved. After the solution was added dropwise little by little, the mixture was stirred for 1 hour at room temperature (about 25 ° C.), the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with 30 parts of water three times. The organic solvent was distilled off under reduced pressure to obtain a yellow solid. This yellow solid was recrystallized with an acetonitrile / ether mixed solution to obtain 1.3 parts of a base generator (C122-2) (slightly yellow powder).

Production Example 11
[Synthesis of Base Generator (C122-3) {Compound Represented by Chemical Formula (39)}]

(1) Synthesis of N- (9-oxo-9H-thioxanthen-2-yl) methyl-N, N-dimethyl-N- (2-hydroxyethyl) ammonium bromide [intermediate (C122-3-3)] :
Except for changing “triethanolamine [Wako Pure Chemical Industries, Ltd.] 0.5 parts” to “dimethylethanolamine [Wako Pure Chemical Industries, Ltd.] 0.3 parts”], (1 ) To (3), 0.8 part of an intermediate (C122-3-3) (brown solid) was obtained.

(2) Synthesis of base generator (C122-3):
A base generator in the same manner as in (4) of Production Example 10 except that 1.0 part of “intermediate (C122-2-3)” was changed to 0.8 part of “intermediate (C122-3-3)” 1.0 part of (C122-3) (white powder) was obtained.

Production Example 12
[Synthesis of Base Generator (C122-4) {Compound Represented by Chemical Formula (40)}]

  Except that “trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” was changed to “1-azabicyclo [2.2.2] octane 1.0 part”, in the same manner as in Production Example 9. , 4.4 parts of a base generator (C122-4) (white solid) were obtained.

Production Example 13
[Synthesis of Base Generator (C123-1) {Compound Represented by Chemical Formula (41)}]

  “Trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” is replaced with “1,8-diazabicyclo [5.4.0] -7-undecene [San Apro Co., Ltd.“ DBU ”] 1.3. 4.7 parts of a base generator (C123-1) (white solid) was obtained in the same manner as in Production Example 9 except that it was changed to “parts”.

Production Example 14
[Synthesis of Base Generator (C123-2) {Compound Represented by Chemical Formula (42)}]

  “Trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” was replaced with “1,5-diazabicyclo [4.3.0] -5-nonene [San Apro Co., Ltd.“ DBN ”] 1.1. In the same manner as in Production Example 9, except for changing to "parts", 4.6 parts of a base generator (C123-2) (white solid) was obtained.

Production Example 15
[Synthesis of Base Generator (C123-3) {Compound Represented by Chemical Formula (43)}]

(1) Preparation of silver phenylglyoxylate:
3.9 parts of phenylglyoxylic acid (manufactured by Aldrich) is dissolved in 20 parts of methanol, and 0.9 part of sodium hydroxide [manufactured by Wako Pure Chemical Industries, Ltd.] is added little by little (the heat generation due to neutralization is observed). The mixture was stirred for 1 hour, and after adding 10.4 parts of a 1 mol / L aqueous silver nitrate solution [manufactured by Wako Pure Chemical Industries, Ltd.], the precipitated gray solid was filtered off, washed with methanol, and dried. As a result, 4.4 parts of silver phenylglyoxylate (gray solid) was obtained.

(2) Synthesis of base generator (C123-3):
2.0 parts of 9-chloromethylanthracene (manufactured by Aldrich) was dissolved in 40 g of methanol, and 1,8-diazabicyclo [5.4.0] -7-undecene ["DBU" manufactured by San Apro Co., Ltd.] 1 .3 parts were added little by little (a slight exotherm was observed after the addition), and the mixture was stirred at room temperature (about 25 ° C.) for 1 hour to obtain a reaction solution. The reaction solution was added dropwise to a dispersion composed of 3.0 parts of silver phenylglyoxylate and 20 parts of methanol, and the mixture was further stirred for 1 hour at room temperature (about 25 ° C.), and then the resulting gray solid was removed by filtration. Was distilled off under reduced pressure to obtain 4.5 parts of a brown solid. This brown solid was recrystallized with an ether / hexane mixed solution to obtain 2.6 parts of a base generator (C123-3) (yellow solid).

Production Example 16
[Synthesis of Base Generator (C123-4) {Compound Represented by Chemical Formula (44)}]

(1) 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (C123-4-3) ]:
Manufactured except that “Triethanolamine [Wako Pure Chemical Industries, Ltd.]” was changed to “1,8-diazabicyclo [5.4.0] -7-undecene [San Apro Co., Ltd.“ DBU ”]”. In the same manner as in Example 10, (1) to (3), 2.2 parts of intermediate (C123-4-3) (white solid) was obtained.

(2) Synthesis of base generator (C123-4):
A base generator (C123-4) (light yellowish white) was prepared in the same manner as in Production Example 10 (4) except that “Intermediate (C122-2-3)” was changed to “Intermediate (C123-4-3)”. 1.3 parts of powder) was obtained.

Production Example 17
[Synthesis of Base Generator (C123-5) {Compound Represented by Chemical Formula (45)}]

(1) Synthesis of 2,4-di-tert-butyl-7-methylthioxanthone [intermediate (C123-5-1)]:
Intermediate (C122-2-1) (2.1 parts) is dissolved in dichloromethane (85 parts), and aluminum (III) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 parts) and 2-chloro-2-methylpropane are added thereto. [Wako Pure Chemical Industries, Ltd.] 1.9 parts was added and stirred at room temperature (about 25 ° C.) for 23 hours. The aqueous layer was removed by a liquid separation operation, and the organic layer was washed 3 times with 30 parts of water. The organic solvent was distilled off under reduced pressure to obtain a pale yellow solid. This pale yellow solid was recrystallized with an ethyl acetate / hexane mixed solution to obtain 0.5 part of an intermediate (C123-5-1) (yellow powder).

(2) Synthesis of 2,4-di-tert-butyl-7-bromomethylthioxanthone [intermediate (C123-5-2)]:
In the same manner as in (2) of Production Example 10, except that 2.1 parts of “Intermediate (C122-2-1)” was changed to 1.0 part of “Intermediate (C123-5-1)” C123-5-2) (yellow powder) 1.2 parts were obtained.

(3) 8- (2,4-Di-tert-butyl-9-oxo-9H-thioxanthen-7-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide Synthesis of [Intermediate (C123-5-3)]:
Intermediate (C123-5-3) (Fine) was prepared in the same manner as in (3) of Production Example 10 except that “Intermediate (C122-2-2)” was changed to “Intermediate (C123-5-2)”. 1.3 parts of a yellow powder) were obtained.

(4) Synthesis of base generator (C123-5):
A base generator in the same manner as in (4) of Production Example 10 except that 1.0 part of “intermediate (C122-2-3)” was changed to 0.8 part of “intermediate (C123-5-3)” 1.0 part of (C123-5) (slightly yellow powder) was obtained.

Production Example 18
[Synthesis of Base Generator (C123-6) {Compound Represented by Chemical Formula (46)}]

(1) Synthesis of 4-bromomethylbenzophenone [intermediate (C123-6-1)]:
4-methylbenzophenone (manufactured by Aldrich) 25.1 parts, N-bromosuccinimide [Wako Pure Chemical Industries, Ltd.] 22.8 parts, benzoyl peroxide [20% water content: Wako Pure Chemical Industries, Ltd.] 0.54 parts and 80 parts of acetonitrile were added, heated to 80 ° C., reacted under reflux for 2 hours, cooled, the organic solvent was distilled off under reduced pressure, and recrystallized from 160 parts of methanol to obtain an intermediate (C123 -6-1) 26 parts (white crystals) were obtained.

(2) Synthesis of 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (C123-6-2)]:
25.8 parts of the intermediate (C123-6-1) was dissolved in 100 parts of acetonitrile, and 1,8-diazabicyclo [5.4.0] -7-undecene [“DBU” manufactured by San Apro Co., Ltd.] 14 After dropwise addition of 6 parts (heat generation after dropping), the mixture was stirred at room temperature (about 25 ° C.) for 18 hours, and the organic solvent was distilled off under reduced pressure to obtain a brown solid. This brown solid was recrystallized from acetonitrile to obtain 28.2 parts of intermediate (C123-6-2) (white solid).

(3) Synthesis of base generator (C123-6):
A solution of 0.8 parts of sodium tetraphenylborate salt [manufactured by Nacalai Tesque Co., Ltd.] dissolved in 17 parts of water and 6.8 parts of intermediate (C123-6-2) dissolved in 50 parts of chloroform in advance After dropwise addition, the reaction solution was obtained by stirring at room temperature (about 25 ° C.) for 2 hours. The reaction solution was filtered, and the yellow liquid obtained by evaporating the filtrate under reduced pressure was dissolved in acetonitrile and recrystallized to obtain 7.6 parts of a base generator (C123-6) (white solid).

Production Example 19
[Synthesis of Base Generator (C123-7) {Compound Represented by Chemical Formula (47)}]

(1) Synthesis of 8- (9-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide [(C123-7-1)]
Except having changed "intermediate (C123-6-1) 25.8 parts" into "2-bromomethylnaphthalene [product made from Tokyo Chemical Industry Co., Ltd.] 1.1 parts", it carried out similarly to manufacture example 18 (2). Intermediate part (C123-7-1) (white powder) was obtained.

(2) Synthesis of base generator (C123-7):
A base generator in the same manner as in Production Example 18 (3) except that "6.8 parts of intermediate (C123-6-2)" was changed to "0.8 parts of intermediate (C123-7-1)" 1.3 parts of (C123-7) (slightly yellow powder) were obtained.

Examples 1 to 21 (Examples of radical polymerization using pigments)
[Preparation of photosensitive composition]
<Preparation of high concentration dispersion>
Titanium oxide as a pigment (“Taipek R-930” manufactured by Ishihara Sangyo Co., Ltd.), 4 parts of a pigment dispersant (“Solspers 32000” manufactured by Lubrizol Co., Ltd.) and polyethylene glycol diacrylate as a radical polymerizable compound [Kyoeisha Chemical ( A mixture of 53 parts “Light Acrylate 14EG-A”] was kneaded for 3 hours using a ball mill to prepare a pigment dispersant solution having a pigment concentration of 43%.

<Preparation of photosensitive composition>
47 parts of the above high-concentration pigment dispersant liquid, 46 parts of polyethylene glycol diacrylate as a radically polymerizable compound [“Light Acrylate 14EG-A” manufactured by Kyoeisha Chemical Co., Ltd.], diethylthioxanthone [Nippon Kayaku as a sensitizer] "Kayacure DETX-S"] 2 parts and 3 parts of radical generator (A), 1 part of acid generator (B) and 1 part of base generator (C) shown in Table 1 using a ball mill at 25 ° C And kneaded for 3 hours to produce photosensitive compositions (Q-1) to (Q-21) of the present invention.

Examples 22 to 42 (Examples of ion polymerization using a dye)
Other than changing “titanium oxide” to “CI Direct Blue 14” (manufactured by Tokyo Chemical Industry Co., Ltd.) and “PEG 600 diacrylate as radical polymerizable compound” to “cyclohexene oxide as ion polymerizable compound” Produced photosensitive compositions (Q-22) to (Q-42) of the present invention in the same manner as in Examples 1 to 21.

Comparative Example 1 [When neither acid generator (B) nor base generator (C) is used]
Comparative Example 1 was used in the same manner as in Example 1 except that the acid generator (B) and the base generator (C) in Example 1 were not used and the amount of the radical generator (A) used was changed to 5 parts. A photosensitive composition (Q′-1) was produced.

  In addition, regarding the compounds shown in Table 1, DAROCUR TPO as (A121) is manufactured by Ciba Japan, 1-Fmoc-piperidone as (C21) is manufactured by ALDRICH, and BPO (benzoyl peroxide) as (A21) is NOF “Nyper BW” manufactured by Tokyo Chemical Industry Co., Ltd. was used as p-toluenesulfonic acid cyclohexyl ester as (B21).

[Evaluation of coating curability]
Each photosensitive composition obtained in Examples 1-42 and Comparative Example 1 was subjected to surface treatment on a 100 μm thick PET (polyethylene terephthalate) film [Toyobo Co., Ltd. Cosmo Shine A4300] using an applicator. It apply | coated so that it might become a film thickness of 20 micrometers. About the exposure, it implemented using the following 2 types of irradiation apparatuses.
(1) The exposure was performed using a belt conveyor type UV irradiation device ("EICS" Corporation "ECS-151U"). The exposure amount was 150 mJ / cm ² at 365 nm.
(2) Exposure was performed using a spot type LED irradiation device (“RX FireFlex” manufactured by Foseon Technology). The exposure amount was 150 mJ / cm ² .
Table 2 shows the results of evaluating the curability of the coated film immediately after light irradiation with a finger touch and nail, according to the following evaluation criteria.
A: There is no tack on the surface and it is not damaged by the nail.
○: There is no tack on the surface, but the nail is damaged.
Δ: There is tack on the surface and it is damaged by the nail.
X: Uncured.

[Production of ceramic green sheets]
Example 43 [Example using metal oxide powder (F)]
<Preparation of photosensitive composition>
80 parts of barium titanate powder [“BT-03” manufactured by Sakai Chemical Industry Co., Ltd.], 13 parts of polyethylene glycol diacrylate [“NK Ester A-600” manufactured by Shin-Nakamura Chemical Co., Ltd.] as a radical polymerizable compound, 1 part diethylthioxanthone [Nippon Kayaku Co., Ltd. “Kayacure DETX-S”] as a sensitizer, 1 part Ionette DO-1000 [manufactured by Sanyo Chemical Industries, Ltd.] as a dispersant, used in Example 1 3 parts of the radical generator (A), 1 part of the acid generator (B) and 1 part of the base generator (C) were kneaded at 25 ° C. for 3 hours using a ball mill, and the photosensitive composition (Q- 43) was produced.

[Create electrode layer]
Example 44 [Example using metal powder (G)]
A photosensitive composition (Q-44) was produced in the same manner as in Example 43 except that “barium titanate powder” was changed to “palladium powder [“ SFP-030 ”manufactured by Sumitomo Metal Mining Co., Ltd.]”. .

Comparative Example 2 [When neither acid generator (B) nor base generator (C) is used]
A comparative example was used in the same manner as in Example 44 except that the acid generator (B) and the base generator (C) in Example 44 were not used, and the amount of the radical generator (A) was changed to 5 parts. A photosensitive composition (Q′-2) was produced.

[Evaluation of coating film curability (ceramic green sheet and electrode layer)]
Each photosensitive composition obtained in Examples 43 to 44 and Comparative Example 2 was subjected to surface treatment on a 100 μm thick PET (polyethylene terephthalate) film [Toyobo Co., Ltd. Cosmo Shine A4300] using an applicator. It apply | coated so that it might become a film thickness of 20 micrometers. About the exposure, it implemented using the following 2 types of irradiation apparatuses.
(1) The exposure was performed using a belt conveyor type UV irradiation device ("EICS" Corporation "ECS-151U"). The exposure amount was 150 mJ / cm 2 at 365 nm.
(2) Exposure was performed using a spot type LED irradiation device (“RX FireFlex” manufactured by Foseon Technology). The exposure amount was 150 mJ / cm ² .
Table 3 shows the results of evaluating the curability immediately after light irradiation of the coated film after curing with the following evaluation criteria by scratching with finger touch and nails.
A: There is no tack on the surface and it is not damaged by the nail.
○: There is no tack on the surface, but the nail is damaged.
Δ: There is tack on the surface and it is damaged by the nail.
X: Uncured.

[Evaluation of multilayer ceramic capacitors]
The photosensitive composition described in Example 43 was applied by the doctor blade method, exposed and cured to produce a green sheet. Next, the photosensitive composition described in Example 44 was printed by screen printing, exposed and cured. 30 layers of this were stacked and pressure-bonded at 49 MPa. Thereafter, the laminate was cut into a predetermined size to obtain a chip. This was degreased at 350 ° C. for 4 hours and then sintered at 1320 ° C. for 2 hours. Further, an external electrode was formed on the sintered body to obtain a multilayer ceramic capacitor. The obtained capacitor was measured based on JIS C 5101-1-1998 to confirm that there was no problem. Further, as a result of checking the appearance and the inside with an optical microscope, no abnormality was found.

Example 45 [Preparation of photosensitive resist composition for negative resist]
50 parts of palladium powder [“SFP-030” manufactured by Sumitomo Metal Mining Co., Ltd.], 22.5 parts of dipentaerythritol hexaacrylate [“Neomer DA-600” manufactured by Sanyo Chemical Co., Ltd.] as a radical polymerizable compound, radical generation Etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [Ciba Japan Co., Ltd. (IRGACURE OXE 02) as the agent (A12) ] 2.15 parts and 2-hydroxy-2-methyl-1-phenyl-propan-1-one [manufactured by Ciba Japan (DAROCUR 1173)], B122-1 [chemical formula as acid generator (B12)] Compound represented by (33)] 1.1 parts, C123-4 [compound represented by chemical formula (44) as base generator (C12) 0.35 parts, diethylthioxanthone as a sensitizer [“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.], 1.8 parts as hydrophilic epoxy resin (J), CCR-1314H [Nippon Kayaku Co., Ltd. )] 17.15 parts, Cymel 506 [Mitsui Cyanamid Co., Ltd.] 3.55 parts as a crosslinking agent (K2), and diethylene glycol monoethyl ether acetate [Tokyo Chemical Industry Co., Ltd.] 25 as a solvent using a ball mill. The photosensitive composition (Q-45) of the present invention was produced by kneading at 3 ° C. for 3 hours.

Example 46 [Preparation of photosensitive composition for color filter (red)]
"KBM-5103 [manufactured by Shin-Etsu Chemical Co., Ltd.] 10 parts" as a polysiloxane and "Ajisper BP-831 [manufactured by Ajinomoto Fine Techno Co., Ltd.] 10 parts" as a pigment dispersant were newly added, A photosensitive composition (Q-46) of the present invention was produced in the same manner as in Example 45 except that “palladium powder” was changed to “Pigment Red 254”.

Example 47 [Preparation of photosensitive composition for color filter (green)]
“KBE-503 [manufactured by Shin-Etsu Chemical Co., Ltd.] 10 parts” as polysiloxane and “Ajisper BP-831 [manufactured by Ajinomoto Fine Techno Co., Ltd.] 10 parts” as a pigment dispersant were newly added, A photosensitive composition (Q-47) of the present invention was produced in the same manner as in Example 45 except that “palladium powder” was changed to “Pigment Green 36”.

Example 48 [Preparation of photosensitive composition for color filter (green)]
“BYK-3500 [manufactured by Big Chemie Co., Ltd.] 10 parts” as polysiloxane and “Ajisper BP-831 [manufactured by Ajinomoto Fine Techno Co., Ltd.] 10 parts” as a pigment dispersant were newly added, and “palladium powder” ”Was changed to“ Pigment Blue 15: 6 ”in the same manner as in Example 45 to prepare a photosensitive composition (Q-48) of the present invention.

Example 49 [Preparation of photosensitive composition for color filter (black matrix)]
"KBM-5103 [manufactured by Shin-Etsu Chemical Co., Ltd.] 10 parts" as a polysiloxane and "Ajisper BP-831 [manufactured by Ajinomoto Fine Techno Co., Ltd.] 10 parts" as a pigment dispersant were newly added, A photosensitive composition (Q-49) of the present invention was produced in the same manner as in Example 45 except that “palladium powder” was changed to “Pigment Black 1”.

Comparative Example 3 [Negative Resist Photosensitive Composition Using No Acid Generator (B) or Base Generator (C)]
A comparison was made in the same manner as in Example 45 except that the acid generator (B) and the base generator (C) in Example 45 were not used, and the amount of the radical generator (A) used was changed to 3.6 parts. A photosensitive composition (Q′-3) was prepared.

Comparative Example 4 [Photosensitive composition for color filter using neither acid generator (B) nor base generator (C)]
A comparison was made in the same manner as in Example 46 except that the acid generator (B) and the base generator (C) in Example 46 were not used and the amount of the radical generator (A) was changed to 3.6 parts. A photosensitive composition (Q′-4) was prepared.

[Evaluation of coating film developability]
Each photosensitive composition obtained in Examples 45 to 49 and Comparative Examples 3 to 4 was subjected to surface treatment on a 100 μm thick PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.], and an applicator. The film was applied to a thickness of 20 μm. Subsequently, under reduced pressure (30 mmHg), pre-baking was performed at 80 ° C. for 3 minutes to dry the solvent. Next, a linear mask having a width of 15 nm was set and then exposed. For the exposure, a belt conveyor type UV irradiation device (“Egraphics Co., Ltd.“ ECS-151U ”) was used. The exposure amount was 150 mJ / cm ² at 365 nm.
The test specimen after exposure was immersed in a 1% NaCO ₂ aqueous solution for 100 seconds, and then alkali development was performed by spraying ion exchange water. Subsequently, post-baking was performed under reduced pressure (30 mmHg) at 80 ° C. for 3 minutes.
Table 4 shows the results of visual observation of the developability of the coating film after development with an optical microscope and evaluation based on the following evaluation criteria.
○: Patterning can be performed without chipping.
Δ: Partially missing but patterned.
X: Patterning is not possible.

  Since the photosensitive composition of the present invention can be cured with a thick film at a high colorant concentration even with a small amount of energy, coating agents, inks (such as UV printing inks and UV inkjet printing inks), paints, adhesives, and production of ceramic electronic components Or as a material for forming a negative resist pattern (particularly for color filter applications).

Claims (19)

A photosensitive composition containing the following (1) to (5), wherein at least one of the radical initiator (A), the acid generator (B) and the base generator (C) is irradiated with actinic rays. The active species (H) is generated, and the active species (H) reacts with the radical initiator (A), the acid generator (B) or the base generator (C) to generate a new active species (I). The polymerization reaction of the polymerizable substance (D) by the new active species (I) proceeds, and the active species (H) or the new active species (I) is an acid or a base, and a radical initiator (A ) Is a radical initiator (A1) that generates radicals by actinic rays and / or a radical initiator (A2) that generates radicals by acids and / or bases, and the acid generator (B) generates an acid by actinic rays. Group of acid generator (B1) generated and / or radical, acid and base An acid generator (B2) that generates an acid by at least one selected from the group consisting of a base generator (C1) that generates a base by actinic rays and / or a radical, an acid, and a base. A base generator (C2) that generates a base by at least one selected from the group consisting of: an acid generator (B1) that generates an acid by actinic rays; and / or at least selected from the group consisting of radicals, acids and bases The acid generator (B2) that generates an acid by one kind is a sulfonium salt derivative (B121) and / or an iodonium salt derivative (B122), and a base generator (C1) that generates a base by actinic rays and / or A base generator (C2) that generates a base by at least one selected from the group consisting of a radical, an acid, and a base is a quaternary amidine salt derivative (C12 ) Comprising a photosensitive composition polymerizable substance (D) is characterized in that it is a radically polymerizable compound (D1);
(1) Radical initiator (A)
(2) Acid generator (B)
(3) Base generator (C)
(4) Polymerizable substance (D)
(5) Colorant (E), metal oxide powder (F) or metal powder (G). Radical initiator (A1) that generates radicals by actinic rays, radical initiator (A2) that generates radicals by acids and / or bases, acid generator (B1) that generates acids by actinic rays, radicals, acids and bases An acid generator (B2) that generates an acid by at least one selected from the group consisting of: a base generator (C1) that generates a base by actinic rays; and at least one selected from the group consisting of a radical, an acid and a base The photosensitive composition of Claim 1 which contains the base generator (C2) which generate | occur | produces a base in the combination in any one of the following (1)-(4).
(1) Contains (A1), (B2) and (C2).
(2) Contains (B1), (A2) and (C2).
(3) Contains (C1), (A2) and (B2).
(4) A combination of two or more of (1) to (3) above. The photosensitive composition according to claim 1, wherein the sulfonium salt derivative (B121) is a compound represented by the general formula (1) or the general formula (2).
[Wherein, A ¹ is a divalent or trivalent group represented by any ^one of the general formulas (3) to (10); Ar ^{1 to} Ar ⁷ each independently has at least one benzene ring skeleton. A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. , A nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group and a phenylthio group, may be substituted with at least one atom or substituent. An aromatic hydrocarbon group or a heterocyclic group, Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, and Ar ⁵ is a divalent group; (X ¹ ) ⁻ and (X ² ) ⁻ Are respectively phosphines. A represents an integer of 0 to 2, b is an integer of 1 to 3, and a + b is 2 or 3, which is the same integer as the valence of A ¹ . ]
[Wherein, R ^{1 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, amino Represents a phenyl group optionally substituted by at least one atom or substituent selected from the group consisting of a group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group, and R ¹ , R ² , R ⁴ And R ⁵ , and R ⁶ and R ⁷ may be bonded to each other to form a ring structure. ] The photosensitive composition according to claim 1 , wherein the sulfonium salt derivative (B121) is a compound represented by the general formulas (11) to (14).
[Wherein (X ³ ) ⁻ to (X ⁶ ) ⁻ each represents an anion. ] The photosensitive composition according to claim 1, wherein the iodonium salt derivative (B122) is a compound represented by the general formula (15) or the general formula (16).
[In the formula, A ² is a divalent or trivalent group represented by any one of the general formulas (3) to (10); Ar ^{8 to} Ar ¹² each independently have at least one benzene ring skeleton. A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. , A nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group and a phenylthio group, may be substituted with at least one atom or substituent. An aromatic hydrocarbon group or a heterocyclic group, wherein Ar ^{8 to} Ar ¹⁰ and Ar ¹² are monovalent groups, Ar ¹¹ is a divalent group; (X ⁷ ) ⁻ and (X ⁸ ) ⁻ are Phosphi each Represents an anion; c is an integer of 0 to 2, d is an integer from 1 to 3, and c + d is an integer equal valence of A2 2 or 3. ] The photosensitive composition according to any one of claims 1 to 5, wherein the iodonium salt derivative (B122) is a compound represented by any one of the general formulas (17) to (20).
[Wherein, R ^{8 to} R ¹³ are each a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An atom or a substituent selected from the group consisting of an alkylthio group, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group; ⁹ ) ⁻ to (X ¹² ) ⁻ each represents a phosphine anion. ] The photosensitive composition according to any one of claims 1 to 6, wherein the quaternary amidine salt derivative (C123) is a compound represented by any one of the general formulas (21) to (23).
[Wherein, R ^{14 to} R ⁴¹ are each a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. A group consisting of an alkylthio group, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, and a substituent represented by the general formula (24) Any one of R ^{14 to} R ²³ is a substituent represented by the general formula (24); any one of R ^{24 to} R ³¹ is a general formula ( 24); any one of R ^{32 to} R ⁴¹ is a substituent represented by the general formula (24). ]
[Wherein, R ^{42 to} R ⁴⁵ are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R ^{46 to} R ⁴⁸ are each an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group. And (X ¹³ ) ⁻ and (X ¹⁴ ) ⁻ each represents an anion; e is an integer of 2 to 4; ] The photosensitive composition according to any one of claims 1 to 7, wherein the quaternary amidine salt derivative (C123) is a compound represented by the general formula (26).
[Wherein (X ¹⁵ ) ⁻ represents an anion. ]   The radical initiator (A1) that generates radicals by the actinic ray and / or the radical initiator (A2) that generates radicals by the acid and / or base is an acylphosphine oxide derivative-based polymerization initiator (A121), α- Aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124), benzoin derivative polymerization initiator (A125), oxime ester derivative polymerization The photosensitive composition according to any one of claims 1 to 8, which is at least one radical polymerization initiator selected from the group consisting of an initiator (A126) and a titanocene derivative-based polymerization initiator (A127).   The radical initiator (A2) that generates radicals by the acid and / or base is an organic peroxide polymerization initiator (A21) and / or an azo compound polymerization initiator (A22). The photosensitive composition in any one.   The radical polymerizable substance (D1) is an acrylamide compound (D11) having 3 to 35 carbon atoms, a (meth) acrylate compound (D12) having 4 to 35 carbon atoms, and an aromatic vinyl compound (D13) having 6 to 35 carbon atoms. The photosensitive composition according to any one of claims 1 to 10, which is at least one polymerizable substance selected from the group consisting of a vinyl ether compound (D14) having 3 to 20 carbon atoms.   The photosensitive composition according to any one of claims 1 to 11, which is used for coating agents, inks, paints, adhesives or ceramic electronic parts.   Furthermore, the photosensitive composition in any one of Claims 1-12 containing a hydrophilic epoxy resin (J) and a crosslinking agent (K).   The photosensitive composition according to claim 13, wherein the hydrophilic epoxy resin (J) is a resin having a (meth) acryloyl group and a carboxyl group. The hydrophilic epoxy resin (J) is, e epoxy resin (J0) and (meth) ring-opening reaction product of an acryloyl group-containing monocarboxylic acid (j) and a polycarboxylic acid and / or polycarboxylic acid anhydrides ( The photosensitive composition according to claim 13 or 14, which is a reaction product with z). Wherein the crosslinking agent is (K), and silane compound represented by the following general formula (27) and (p1) as an essential constituent monomer, a condensation product of ^{[OR 51} of the general formula (27) in] the alkoxy group The photosensitive composition according to claim 13, which is polysiloxane (K ¹ ).
[Wherein, R ⁴⁹ is one or more selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidylalkyl group, a mercaptoalkyl group, and an aminoalkyl group having 1 to 6 carbon atoms in the alkylene group moiety. Represents an organic group. R ⁵⁰ represents an alkyl group having 1 to 12 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ⁵¹ represents an alkyl group having 1 to 4 carbon atoms. m is an integer of 0 or 1. ]   The photosensitive composition according to any one of claims 13 to 16, wherein the crosslinking agent (K) is a melamine resin (K2).   The photosensitive composition according to claim 13, which is used for forming a negative resist pattern. The color filter containing the pattern formed using the photosensitive composition in any one of Claims 13-18.