JP2017008219A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a coated film containing a latent antioxidant and excellent in sensitivity and transparency.SOLUTION: There is provided a composition containing (A) a latent antioxidant which is inactive in a process of single temperature or pre-baking and become active with detachment of a protective group by heating at 100 to 250°C or heating to 80 to 200°C in presence of an acid/base catalyst and (B) a polymerization initiator containing one or more kind of oxime ester compound represented by the formula (I). The content of the oxime ester compound represented by the formula (I) in the polymerization initiator (B) is preferably 20 to 100 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a composition containing a latent antioxidant which is inactive at room temperature and is activated by heating to a predetermined temperature to exhibit a function, and a polymerization initiator having a specific structure.

  Photosensitive compositions are widely used in paints, coating agents, various resists and the like.

  Patent Document 1 discloses a photosensitive coloring composition for a color filter containing an antioxidant, and Patent Document 2 discloses a photosensitive resin composition containing a phenol antioxidant, It is described that the heat resistance of the composition can be improved by containing an antioxidant. However, Patent Documents 1 and 2 do not describe that a highly sensitive and highly transparent composition can be obtained by using a latent antioxidant.

JP 2012-247591 A JP 2014-052424 A

  Accordingly, an object of the present invention is to provide a composition having excellent sensitivity and transparency.

  As a result of intensive studies, the present inventors contain a latent antioxidant (A) and a polymerization initiator (B) containing at least one oxime ester compound represented by the following general formula (I). The inventors have found that the composition can achieve the above object, and have reached the present invention.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ³及びＲ⁴は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ⁵、ＯＲ⁶、ＳＲ⁷、ＮＲ⁸Ｒ⁹、ＣＯＲ¹⁰、ＳＯＲ¹¹、ＳＯ₂Ｒ¹²又はＣＯＮＲ¹³Ｒ¹⁴を表し、Ｒ³及びＲ⁴は、互いに結合して環を形成していてもよく、Ｒ³同士、Ｒ⁴同士が互いに結合して環を形成していてもよく、
Ｘ¹は、酸素原子、硫黄原子、セレン原子、ＣＲ¹⁵Ｒ¹⁶、ＣＯ、ＮＲ¹⁷又はＰＲ¹⁸を表し、
Ｘ²は、単結合又はＣＯを表し、
Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ¹、Ｒ²、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸中の炭素原子数１〜２０のアルキル基は、直鎖状でも分岐上でも環状でも直鎖と環の組み合わせでも分岐と環の組み合わせでもよく、
Ｒ¹、Ｒ²、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸中の炭素原子数１〜２０のアルキル基又は炭素原子数７〜２０のアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、複素環含有基又は下記一般式（ＩＩ）で表される置換基で置換されていてもよく、−Ｏ−で中断されていてもよく、
ａは、０〜４の整数を表し、
ｂは、０〜５の整数を表す。）

Wherein R ¹ and R ² are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms. Represents a group or a heterocyclic group containing 2 to 20 carbon atoms,
R ³ and R ⁴ are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ⁵ , OR ⁶ , SR ⁷ , NR ⁸ R ⁹ , COR ¹⁰ , SOR ¹¹ , SO ₂ R ¹² or CONR ¹³ R ¹⁴ , R ³ and R ⁴ may be bonded to each other to form a ring, R ³ and R ⁴ may be bonded to each other to form a ring,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁵ R ¹⁶ , CO, NR ¹⁷ or PR ¹⁸ ,
X ² represents a single bond or CO,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently the number of carbon atoms. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms,
^{R 1, R 2, R 5} , R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, carbon in R ^16, R ¹⁷ and R ¹⁸ The alkyl group having 1 to 20 atoms may be linear, branched, cyclic, linear and ring combinations, or branched and ring combinations,
^{R 1, R 2, R 5} , R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, carbon in R ^16, R ¹⁷ and R ¹⁸ The methylene group in the alkyl group having 1 to 20 atoms or the arylalkyl group having 7 to 20 carbon atoms is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a heterocyclic group, or the following general formula (II) May be substituted with a substituent represented by the formula:
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

（式中、Ｒ¹⁹及びＲ²⁰は、それぞれ独立に、水素原子、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表す。）

Wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms. Represents a group or a C2-C20 heterocycle-containing group.)

  The composition of the present invention containing a latent antioxidant having a specific structure and a polymerization initiator having a specific structure is excellent in sensitivity and transparency.

  Hereinafter, the composition of this invention is demonstrated based on preferable embodiment.

  The composition of the present invention contains a latent antioxidant (A) and a polymerization initiator (B) containing one or more oxime ester compounds represented by the above general formula (I). Hereinafter, each component will be described in order.

<Latent antioxidant (A)>
The latent antioxidant (A) used in the composition of the present invention is inactive at room temperature or in the pre-baking step, and is heated at 100 to 250 ° C. or 80 to 200 ° C. in the presence of an acid / base catalyst. The protecting group is eliminated and becomes active by heating with. In the composition of the present invention, the latent antioxidant (A) having a skeleton represented by the following general formula (III) is preferable because it is easy to synthesize and has high heat resistance.

（式中、環Ａ¹は、五員環又は六員環の炭化水素環又は複素環を表し、
Ｒ⁶¹は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ⁶²は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数２〜２０のアルケニル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又はトリアルキルシリル基を表し、
Ｒ⁶¹及びＲ⁶²で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｓ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−ＮＲ^'−、−Ｓ−Ｓ−又は−ＳＯ₂−から選ばれた基を酸素原子が隣り合わない条件で組み合わせた基で置き換えていてもよく、Ｒ’は、水素原子又は炭素原子数１〜８のアルキル基を表し、
複数のＲ⁶¹同士は結合してベンゼン環又はナフタレン環を形成していてもよく、
ｄは、１〜５の整数を表し、
ｋは、１〜５の整数を表すが、ｄとｋの合計は、環Ａ¹が取り得る置換基の数より少ない。）

(In the formula, ring A ¹ represents a 5-membered or 6-membered hydrocarbon ring or heterocyclic ring,
R ⁶¹ is independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R ⁶² each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon Represents a heterocyclic group containing 2 to 20 atoms or a trialkylsilyl group,
The methylene group in the alkyl group or arylalkyl group represented by R ⁶¹ and R ⁶² is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O. -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, - NH-CO -, - NH-CO-O -, - NR '-, - replaced by an oxygen atom a group selected from the combination conditions are not adjacent group - S-S- or -SO ₂ R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R ⁶¹ may be bonded to each other to form a benzene ring or a naphthalene ring,
d represents an integer of 1 to 5;
k represents an integer of 1 to 5, but the sum of d and k is less than the number of substituents that ring A ¹ can take. )

  Among the latent antioxidants (A) having a skeleton represented by the above general formula (III), those represented by the following general formula (III-A) are particularly preferable because of their high heat resistance.

（式中、環Ａ¹、Ｒ⁶¹、Ｒ⁶²、ｄ及びｋは、上記一般式（ＩＩＩ）と同じであり、ｍは、１〜１０の整数を表し、
Ｘ⁵は、ｍ価の有機基を表す。）

(In the formula, rings A ¹ , R ⁶¹ , R ⁶² , d and k are the same as in the above general formula (III), m represents an integer of 1 to 10,
X ⁵ represents an m-valent organic group. )

Examples of the five-membered hydrocarbon ring represented by A ¹ in the general formula (III) include cyclopentadiene, and examples of the five-membered heterocyclic ring include furan, thiophene, pyrrole, pyrrolidine, pyrazolidine, and pyrazole. , Imidazole, imidazolidine, oxazole, isoxazole, isoxazolidine, thiazole, isothiazole, isothiazolidine, etc., as the six-membered hydrocarbon ring, benzene and the like, and as the six-membered heterocyclic ring, Piperidine, piperazine, morpholine, thiomorpholine, pyridine, pyrazine, pyrimidine, pyridazine, triazine and the like, and these rings may be condensed or substituted with other rings, for example, Quinoline, isoquinoline, indole, urolidine, benzoxazo , Benzotriazole, azulene, naphthalene, anthracene, fluorene, perylene, pyrene, and the like.
Examples of the halogen atom represented by R ⁶¹ include fluorine, chlorine, bromine, and iodine (in the following description, all the halogen atoms are the same as described above).
Examples of the alkyl group having 1 to 40 carbon atoms represented by R ⁶¹ include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert- Amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl , Adamantyl and the like.
Examples of the substituent for substituting the alkyl group having 1 to 40 carbon atoms represented by R ⁶¹ include ethylenically unsaturated groups such as vinyl, allyl, acrylic and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; Acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n -Acyl groups such as octadecyloxycarbonyl and carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2- Tilhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, Lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N- Methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethyla Substituted amino groups such as nosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group , Sulfonamide groups, phosphonic acid groups, phosphoric acid groups or carboxyl groups, sulfo groups, phosphonic acid groups, salts of phosphoric acid groups, and the like.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ⁶¹ and R ⁶² include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4- Vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert Butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5 -Di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ⁶¹ and R ⁶² include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenylmethyl, 9-fluorenyl, 3 -Phenylpropyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, cinnamyl and the like.
Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R ⁶¹ and R ⁶² include a pyridine ring, pyrimidine ring, pyridazine ring, piperidine ring, pyran ring, pyrazoline ring, triazine ring, pyrroline ring, quinoline ring, Isoquinoline ring, imidazoline ring, benzimidazoline ring, triazoline ring, furan ring, benzofuran ring, thiadiazoline ring, thiazoline ring, benzothiazoline ring, thiophene ring, oxazoline ring, benzoxazoline ring, isothiazoline ring, isoxazoline ring, indole ring, pyrrolidine Examples include groups in which a hetero ring such as a ring, piperidone ring, dioxane ring and the like and a methylene chain are combined.
Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁶² include those exemplified as the aforementioned alkyl group having 1 to 40 carbon atoms.
Examples of the alkenyl group having 2 to 20 carbon atoms represented by R ⁶² include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group.
The trialkylsilyl group represented by R ^62, trimethylsilane, triethylsilane, silyl alkyl group having 1 to 6 carbon atoms such as ethyl dimethylsilane (three alkyl groups may be the same or different) substituted with Groups.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ include those satisfying a predetermined number of carbon atoms among the above alkyl groups represented by R ⁶¹ .
Among R ⁶¹ , a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable because of easy synthesis.
Among R ⁶² , those in which —CO—O— is bonded to the terminal on the oxygen atom side of the alkyl group having 1 to 8 carbon atoms are preferable because the functions are efficiently exhibited as a latent additive.

In the general formula (III-A), X ⁵ represents an m-valent organic group, specifically, a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, the following (III-a Or a group represented by (III-b),>C═O,> NR ⁶³ , —OR ⁶³ , —SR ⁶³ , —NR ⁶³ R ⁶⁴ or a substituent having the same valence as m An optionally substituted aliphatic hydrocarbon group having 1 to 120 carbon atoms, an optionally substituted aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and an optionally substituted carbon A heterocyclic group having 2 to 35 atoms is represented.
R ⁶³ and R ⁶⁴ are each a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an optionally substituted aromatic ring having 6 to 35 carbon atoms. Represents a hydrocarbon-containing group having 2 to 35 carbon atoms which may have a contained hydrocarbon group or a substituent, and the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group are Carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO- , -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR ''-,- A group selected from S—S—, —SO ₂ —, or a nitrogen atom may be replaced with a group in which oxygen atoms are not adjacent to each other. R ″ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or an aromatic ring having 6 to 35 carbon atoms which may have a substituent. It represents a C2-C35 heterocycle-containing group that may have a hydrocarbon group or a substituent.
However, when X ⁵ is a nitrogen atom, a phosphorus atom or a group represented by the following (III-a) or (III-b), m is 3, X ⁵ is an oxygen atom or a sulfur atom,> C═O , —NH—CO—, —CO—NH— or> NR ⁶³ , m is 2, and when X ⁵ is —OR ⁶³ , —SR ⁶³ or —NR ⁶³ R ⁶⁴ , m is 1. X ⁵ may form a ring together with A ¹ .

The latent antioxidant represented by the general formula (III-A) has a structure in which m specific groups are bonded to specific m-valent atoms or groups represented by X ⁵ . The m groups may be the same as or different from each other. The value of m is 1 to 10, and preferably 2 to 6 from the viewpoint of ease of synthesis.

As the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m, represented by X ⁵ in the general formula (III-A), m is monovalent, for example, methyl , Ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methyl Alkyl groups such as cyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl; methyloxy, ethyloxy, propyloxy, Isopropyloxy, butyloxy, sec-butyloxy, tert-butyl Xyl, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy , Alkoxy groups such as nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, sec Alkylthio groups such as triheptylthio, n-octylthio, isooctylthio, tertiary octylthio, 2-ethylhexylthio; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, Examples include alkenyl groups such as pentadecenyl, eicosenyl, and tricosenyl, and groups in which these groups are substituted with a substituent described later.
As the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m, represented by X ⁵ in the general formula (III-A), m is divalent, methylene, ethylene Alkylene, such as propylene, butylene, butyldiyl, etc .; in which the methylene chain of the alkylene is replaced by —O—, —S—, —CO—O—, —O—CO—; ethanediol, propanediol, butanediol, Residues of diols such as pentanediol and hexanediol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, and hexanedithiol, and groups in which these groups are substituted by substituents described later, etc. .
As the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m represented by X ⁵ in the general formula (III-A), m is trivalent, for example, Examples thereof include alkylidine such as pyridine and 1,1,3-butyridine, and groups in which these groups are substituted with a substituent described later.
As the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, which is represented by X ⁵ in the general formula (III-A) and has the same valence as m, Are monovalent, arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; phenylthio and naphthylthio; Examples include arylthio groups and groups in which these groups are substituted with a substituent described later.
As the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, which is represented by X ⁵ in the general formula (III-A) and has the same valence as m, Are divalent, arylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro [5,5] undecane and the like A group substituted by a substituent described later, and
As the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, which is represented by X ⁵ in the general formula (III-A) and has the same valence as m, Is a group in which phenyl-1,3,5-trimethylene and these groups are substituted with a substituent described later.
The heterocycle-containing group having 2 to 35 carbon atoms which may have a substituent, which is represented by X ⁵ in the general formula (III-A) and has the same valence as m, is 1 in m. As valences, pyridyl, pyrimidyl, pyridadyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl , Oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine -3-yl, benzotri Benzoyl and the like, and groups substituted by a substituent which these groups will be described later and the like,
The heterocycle-containing group having 2 to 35 carbon atoms which may have a substituent, which is represented by X ⁵ in the general formula (III-A) and has the same valence as m, is 2 in number. Examples of the valent group include a group having a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring, or the like, and a group in which these groups are substituted with a substituent described later.
The heterocycle-containing group having 2 to 35 carbon atoms which may have a substituent having the same valence as m represented by X ⁵ in the general formula (III-A) is 3 Examples of the valence include a group having an isocyanuric ring, a group having a triazine ring, and a group in which these groups are substituted with a substituent described later.
The aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, represented by R ⁶³ and R ⁶⁴ , is a monovalent aliphatic hydrocarbon group represented by X ⁵ above. Alternatively, among the combinations of aliphatic hydrocarbon groups and the following substituents, those satisfying a predetermined number of carbon atoms can be mentioned.
An aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R ⁶³ and R ⁶⁴ or a heterocyclic ring having 2 to 35 carbon atoms which may have a substituent As the containing group, the monovalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the monovalent heterocyclic group containing 2 to 35 carbon atoms represented by X ⁵ or the following substitution with these groups: And a group in combination with a group.
Examples of the substituent for substituting the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group represented by X ⁵ , R ^63, and R ⁶⁴ include vinyl, allyl, acrylic, methacryl, and the like Ethylenically unsaturated groups; halogen atoms such as fluorine, chlorine, bromine, iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl , Salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl and other acyl groups; acetyloxy, benzoyloxy and other acyloxy groups; amino, ethylamino, dimethylamino, di Tilamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino Amino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino , N-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycal Substituted amino groups such as nylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group Nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid group, salt of phosphoric acid group, etc. May be substituted. Moreover, the carboxyl group and the sulfo group may form a salt.

In the above general formula (III-A), when m is 2, X ⁵ can also be represented by the following general formula (1).

（上記一般式（１）中、Ｙ¹⁰は、単結合、−ＣＲ⁶⁵Ｒ⁶⁶−、−ＮＲ⁶⁷−、二価の炭素原子数１〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環含有基、又は、下記（１−１）〜（１−３）で表されるいずれかの置換基を表し、
該脂肪族炭化水素基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＮＨ−、あるいは酸素原子が隣り合うことなしにこれらを組み合わせた結合基で中断されていてもよく、
Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、＞ＣＯ、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、＞ＮＲ⁶⁷又は＞ＰＲ⁶⁷を表し、
Ｒ⁶⁵、Ｒ⁶⁶及びＲ⁶⁷は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１〜３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６〜３５の芳香族炭化水素基又は置換基を有していてもよい炭素原子数２〜３５の複素環含有基を表す。）

(In the general formula (1), Y ¹⁰ represents a single bond, —CR ⁶⁵ R ⁶⁶ —, —NR ⁶⁷ —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or 6 to 35 carbon atoms. An aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, or any one of the substituents represented by the following (1-1) to (1-3):
The aliphatic hydrocarbon group is interrupted by -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a linking group that combines these without adjacent oxygen atoms. You may,
Z ¹ and Z ² are each independently a direct bond, —O—, —S—,> CO, —CO—O—, —O—CO—, —SO ₂ —, —SS—, —SO—, Represents> NR ⁶⁷ or> PR ⁶⁷ ,
R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an optionally substituted carbon atom. It represents a heterocyclic ring-containing group having 2 to 35 carbon atoms, which may have an aromatic hydrocarbon group having 6 to 35 or a substituent. )

（上記式中、Ｒ⁷¹は水素原子、置換基を有していてもよいフェニル基、又は炭素原子数３〜１０のシクロアルキル基を表し、
Ｒ⁷²は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有していてもよく、
ｆは０〜５の整数である。）

(In the above formula, R ⁷¹ represents a hydrogen atom, an optionally substituted phenyl group, or a cycloalkyl group having 3 to 10 carbon atoms,
R ⁷² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group are substituents. You may have
f is an integer of 0-5. )

（上記式中、Ｒ⁷³及びＲ⁷⁴は、それぞれ独立に、置換基を有していてもよい炭素原子数１〜１０のアルキル基、置換基を有していてもよい炭素原子数６〜２０のアリール基、置換基を有していてもよい炭素原子数６〜２０のアリールオキシ基、置換基を有していてもよい炭素原子数６〜２０のアリールチオ基、置換基を有していてもよい炭素原子数８〜２０のアリールアルケニル基、置換基を有していてもよい炭素原子数７〜２０のアリールアルキル基、置換基を有していてもよい炭素原子数２〜２０の複素環含有基又はハロゲン原子を表し、
該アルキル基及びアリールアルキル基中のメチレン基は不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、
Ｒ⁷³は、隣接するＲ⁷³同士で環を形成していてもよく、
ｐは０〜４の数を表し、
ｑは０〜８の数を表し、ｇは０〜４の数を表し、
ｈは０〜４の数を表し、
ｇとｈの数の合計は２〜４である。）

(In the above formula, R ⁷³ and R ⁷⁴ are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 to 20 carbon atoms which may have a substituent. An aryloxy group having 6 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, and a substituent. Or an arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a complex having 2 to 20 carbon atoms which may have a substituent. Represents a ring-containing group or a halogen atom,
The methylene group in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-,
R ⁷³ may form a ring with adjacent R ⁷³ ,
p represents a number from 0 to 4;
q represents a number from 0 to 8, g represents a number from 0 to 4,
h represents a number from 0 to 4;
The total number of g and h is 2-4. )

In the general formula (III-A), when m is 3, X ⁵ can also be expressed as in the following general formula (2).

（上記一般式（２）中、Ｙ¹¹は、単結合、三価の炭素原子数３〜３５の脂肪族炭化水素基、炭素原子数３〜３５の脂環族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環含有基を表し、
Ｚ¹、Ｚ²及びＺ³は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、＞ＣＯ、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、＞ＮＲ⁶⁸又は＞ＰＲ⁶⁸を表し、
Ｒ⁶⁸は、水素原子、置換基を有していてもよい炭素原子数１〜３５の脂肪族炭化水素基、置換基を有していてもよい炭素原子数６〜３５の芳香族炭化水素基又は置換基を有していてもよい炭素原子数２〜３５の複素環含有基を表し、該脂肪族炭化水素基は、炭素一炭素二重結合、−Ｏ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−又は−ＳＯ₂−で中断されていてもよい。）

(In the above general formula (2), Y ¹¹ represents a single bond, a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 carbon atoms. Represents a -35 aromatic hydrocarbon group or a C2-C35 heterocycle-containing group,
Z ¹ , Z ² and Z ³ are each independently a direct bond, —O—, —S—,> CO, —CO—O—, —O—CO—, —SO ₂ —, —SS—, — Represents SO-,> NR ⁶⁸ or> PR ⁶⁸ ,
R ⁶⁸ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 35 carbon atoms. Or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, wherein the aliphatic hydrocarbon group is a carbon-carbon double bond, -O-, -CO-, -O-. CO -, - CO-O- or -SO ₂ - may be interrupted by. )

In the general formula (III-A), when m is 4, X ⁵ can also be expressed as in the following general formula (3).

（上記一般式（３）中、Ｙ¹²は、単結合、炭素原子、又は、四価の炭素原子数１〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基若しくは炭素原子数２〜３５の複素環含有基を表し、
該脂肪族炭化水素基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で中断されていてもよく、Ｚ¹〜Ｚ⁴は、それぞれ独立に、上記一般式（２）におけるＺ¹〜Ｚ³で表される基と同じ範囲の基である。）

(In General Formula (3), Y ¹² represents a single bond, a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or Represents a heterocyclic group containing 2 to 35 carbon atoms,
The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—, and Z ^{1 to} Z ⁴ are each independently It is a group in the same range as the group represented by Z ^{1 to} Z ³ in the general formula (2). )

In the general formula (III-A), when m is 5, X ⁵ can also be expressed as in the following general formula (4).

（上記一般式（４）中、Ｙ¹³は、単結合、五価の炭素原子数２〜３５の脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基又は炭素原子数２〜２０の複素環含有基を表し、
該脂肪族炭化水素基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で中断されていてもよく、
Ｚ¹〜Ｚ⁵は、それぞれ独立に、上記一般式（２）におけるＺ¹〜Ｚ³で表される基と同じ範囲の基である。）

(In the general formula (4), Y ¹³ represents a single bond, a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or 2 to 2 carbon atoms. Represents 20 heterocycle-containing groups,
The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
Z ^{1 to} Z ⁵ are each independently a group in the same range as the group represented by Z ^{1 to} Z ³ in the general formula (2). )

In the above general formula (III-A), when m is 6, X ⁵ can also be represented by the following general formula (5).

（上記一般式（５）中、Ｙ¹⁴は、単結合、六価の炭素原子数２〜３５の脂肪族炭化水素基、炭素原子数６〜３５の芳香族炭化水素基又は炭素原子数２〜３５の複素環含有基を表し、
該脂肪族炭化水素基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で中断されていてもよく、
Ｚ¹〜Ｚ⁶は、それぞれ独立に、上記一般式（２）におけるＺ¹〜Ｚ³で表される基と同じ範囲の基である。）

(In the general formula (5), Y ¹⁴ represents a single bond, an aliphatic hydrocarbon group having 2 to 35 carbon atoms having 6 valent carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or 2 to 2 carbon atoms. Represents 35 heterocycle-containing groups,
The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
Z ^{1 to} Z ⁶ are each independently a group in the same range as the group represented by Z ^{1 to} Z ³ in the general formula (2). )

Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent and represented by R ⁶⁵ , R ⁶⁶ and R ⁶⁷ in the general formula (1) include the above general formula (III-A ) monovalent aliphatic hydrocarbon groups and those groups exemplified as the m-valent organic group represented by X ⁵ in the an m-valent organic group represented by X ⁵ in the above general formula (III-a) And those satisfying a predetermined number of carbon atoms among the groups substituted by those exemplified as the substituent of the group to be represented, and the m valence represented by X ⁵ in these groups or the above general formula (III-A) A divalent group obtained by substituting the divalent aliphatic hydrocarbon group exemplified as the organic group with Z ¹ and Z ² is a divalent aliphatic hydrocarbon having 1 to 35 carbon atoms represented by Y ¹⁰ As a group.
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is represented by X ⁵ in the general formula (III-A). And monovalent aromatic ring-containing hydrocarbon groups exemplified as the m-valent organic group, and the substituent of the group in which these groups represent the m-valent organic group represented by X ⁵ in the general formula (III-A) A divalent aromatic ring-containing hydrocarbon group exemplified as an m-valent organic group represented by X ⁵ in the above general formula (III-A). Is a divalent group substituted with Z ¹ and Z ² as a divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹⁰ .
The heterocyclic group having 2 to 35 carbon atoms which may have a substituent represented by R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is represented by X ⁵ in the general formula (III-A). Examples of monovalent heterocycle-containing groups exemplified as m-valent organic groups, and those groups exemplified as substituents of groups representing m-valent organic groups represented by X ⁵ in formula (III-A). The divalent aromatic ring-containing hydrocarbon group exemplified as the m-valent organic group represented by X ⁵ in these groups or the above general formula (III-A) is Z ¹ and A divalent group substituted with Z ² is exemplified as a divalent heterocyclic group having 2 to 35 carbon atoms represented by Y ¹⁰ .

In the substituent represented by (1-1) above, examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷¹ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohebutyl, cyclooctyl and the like. ,
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷² include groups satisfying a predetermined number of carbon atoms among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ^61. Can be mentioned.
Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁷² include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy Hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like.
Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁷² include groups satisfying a predetermined number of carbon atoms among the groups exemplified as the alkenyl group having 2 to 20 carbon atoms represented by R ^62. Can be mentioned.
The substituents of the phenyl group, alkyl group, alkoxy group and alkenyl group are the same as those exemplified as the substituent of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A). is there.

In the group represented by (1-3) above, the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ is a carbon represented by R ^61. Among the groups exemplified as the alkyl group having 1 to 40 atoms, groups satisfying a predetermined number of carbon atoms are exemplified.
The aryl group having 6 to 20 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ is exemplified as an aryl group having 6 to 20 carbon atoms represented by R ⁶¹ and R ⁶² And the like.
Examples of the aryloxy group having 6 to 20 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6- Dimethylphenyloxy, 3.4-dimethylphenyloxy, 3.5- Methylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert-pentylphenyloxy, 2, Groups such as 5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy and the like are donated.
As the arylthio group having 6 to 20 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ , an aryloxy group having 6 to 20 carbon atoms which may have the above substituent A group in which the oxygen atom is substituted with a sulfur atom, etc.
Examples of the arylalkenyl group having 8 to 20 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include aryloxy having 6 to 20 carbon atoms which may have the above-described substituent. Examples include groups in which the oxygen atom of the group is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ⁷³ and R ⁷⁴ include groups exemplified as the arylalkyl group having 7 to 20 carbon atoms represented by R ⁶¹ and R ⁶² .
Examples of the heterocyclic group having 2 to 20 carbon atoms which may have a substituent represented by R ⁷³ and R ⁷⁴ include a heterocyclic ring having 2 to 20 carbon atoms represented by R ⁶¹ and R ⁶² The group etc. which were illustrated as a containing group are mentioned.

Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y ¹¹ in the general formula (2) include an m-valent organic compound represented by X ⁵ in the general formula (III-A). Examples of the monovalent to trivalent aliphatic hydrocarbon group exemplified as the group and those substituents of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A) Examples of the group substituted by a group satisfying a predetermined number of carbon atoms include trivalent groups substituted with Z ¹ , Z ² and Z ³ .
Examples of the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by Y ¹¹ in the general formula (2) include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2- Adamantyl, noradamantyl, 2-methyladamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1. 0] pentyl, bicyclo [3.1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2. 0] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] Octyl, bicyclo [4.2.0] octyl, bicyclo [4.1.1] octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] Groups such as octyl, spiro [4,4] nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, cedrol, cyclododecanyl are substituted with Z ¹ , Z ² and Z ³ And a trivalent group formed.
Examples of the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹¹ include the monovalent compounds exemplified as the m-valent organic group represented by X ⁵ in the general formula (III-A). A group substituted by a trivalent aromatic ring-containing hydrocarbon group and those groups exemplified by the substituents for the group representing the m-valent organic group represented by X ⁵ in formula (III-A). And the like include trivalent groups substituted with Z ¹ , Z ² and Z ³ .
Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y ¹¹ include monovalent to 3 exemplified as the m-valent organic group represented by X ⁵ in the general formula (III-A). A valent heterocyclic group and a group substituted by those exemplified as the substituent of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A), ^And trivalent groups substituted with ¹ , Z ² and Z ³ .
Further, the aliphatic hydrocarbon group of 1 to 35 carbon atoms which may have a substituent represented by R ^68, an aromatic hydrocarbon optionally carbon atoms 6 to 35 which may have a substituent Examples of the heterocyclic group having 2 to 35 carbon atoms which may have a group and a substituent are aliphatic hydrocarbon groups exemplified in the description of R ⁶⁵ and R ⁶⁶ in the general formula (1), An aromatic ring containing hydrocarbon group and a heterocyclic ring containing group are mentioned.

The tetravalent aliphatic hydrocarbon group having a carbon number of 1 to 35 represented by Y ¹² in general formula (3), m-valent organic represented by X ⁵ in the above general formula (III-A) Examples of the monovalent to trivalent aliphatic hydrocarbon group exemplified as the group and those substituents of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A) Examples of the group substituted by ¹ include those having a predetermined number of carbon atoms, such as tetravalent groups substituted with Z ¹ , Z ² , Z ³ and Z ⁴ .
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹² is monovalent to trivalent exemplified as an m-valent organic group represented by X ⁵ in the general formula (III-A). Z ¹ is a group substituted by the aromatic ring-containing hydrocarbon group, and those groups exemplified by those exemplified as the substituent of the group representing the m-valent organic group represented by X in the general formula (III-A). , Z ² , Z ^3, and Z ⁴ substituted with a tetravalent group.
The tetravalent heterocyclic containing group having a carbon number of 2 to 35 represented by Y ^12, the general formula (III-A) 1 monovalent exemplified as m-valent organic group represented by X ⁵ in to 3 Z ¹ is a group substituted with a valent heterocyclic ring-containing group or a group such as those exemplified as the substituent of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A). , Z ² , Z ^3, and Z ⁴ substituted with a tetravalent group.

The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y ¹³ in the general formula (4) is an m-valent organic compound represented by X ⁵ in the general formula (III-A). Examples of the monovalent to trivalent aliphatic hydrocarbon group exemplified as the group and those substituents of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A) Among the groups substituted by the above, there may be mentioned pentavalent groups in which those satisfying the predetermined number of carbon atoms are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ .
The pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹⁴ is a monovalent exemplified as an m-valent organic group represented by X ⁵ in the general formula (III-A). A group substituted by a trivalent aromatic ring-containing hydrocarbon group and a group in which these groups are exemplified as a substituent of a group representing an n-valent organic group represented by X ⁵ in the general formula (IA) And pentavalent groups substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ .
The pentavalent C2-C35 heterocycle-containing group represented by Y ¹⁴ is an n-valent organic compound represented by X in the m-valence represented by X ⁵ in the general formula (III-A). The monovalent to trivalent heterocyclic-containing groups exemplified as the groups and those exemplified as the substituents of the groups representing the m-valent organic groups represented by X ⁵ in the general formula (III-A) Examples include pentavalent groups in which a substituted group or the like is substituted with Z ¹ , Z ² , Z ³ , Z ^{4, or} Z ⁵ .

The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y ¹⁴ in the general formula (5) is an m-valent organic compound represented by X ⁵ in the general formula (III-A). Examples of the monovalent to trivalent aliphatic hydrocarbon group exemplified as the group and those substituents of the group representing the m-valent organic group represented by X ⁵ in the general formula (III-A) Among the groups substituted by the above, those having a predetermined number of carbon atoms and the like are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ .
Examples of the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹⁴ include the monovalent compounds exemplified as the m-valent organic group represented by X ⁵ in the general formula (III-A). A group substituted by a trivalent aromatic ring-containing hydrocarbon group and those groups exemplified by the substituents for the group representing the m-valent organic group represented by X ⁵ in formula (III-A). And the like include hexavalent groups substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ .
Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y ¹⁴ include monovalent to 3 exemplified as the m-valent organic group represented by X ⁵ in the general formula (III-A). Z ¹ is a group substituted with a valent heterocyclic ring-containing group or a group such as those exemplified as the substituent of the group representing the n-valent organic group represented by X ⁵ in the general formula (IA). , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , and the like.

In the general formula (III-A), the sum of d and k is less than the number of substituents that can be taken by the ring A ¹ . For example, when the ring A ¹ is a six-membered aromatic ring, the possible substituents of the ring A ¹ are 6, and d + k ≦ 5. When the ring A ¹ is a five-membered heterocyclic ring, the possible substituents of the ring A ¹ are 4, and d + k ≦ 3.

  Among the compounds represented by the general formula (III-A), those represented by the following general formulas (IV) to (VI) are preferable because they are easy to synthesize and have high heat resistance.

（式中、環Ａ²は、六員環の脂環、芳香環又は複素環であり、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴及びＲ⁸⁵は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又は−Ｏ−Ｒ⁶²を表し、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴及びＲ⁸⁵のうち少なくとも１つは水素原子でなく、Ｒ⁶²は、上記一般式（ＩＩＩ）と同じである。）

(In the formula, ring A ² is a six-membered alicyclic ring, aromatic ring or heterocyclic ring, and R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ are a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group. , A nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, the number of carbon atoms 2 to 20 heterocycle-containing groups or —O—R ⁶² , wherein at least one of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is not a hydrogen atom, and R ⁶² represents the above general formula ( Same as III).)

（式中、Ｘ¹¹は、上記一般式（１）で表される基であり、Ｒ⁸⁶、Ｒ⁸⁷、Ｒ⁸⁸及びＲ⁸⁹は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、Ｒ⁸⁶、Ｒ⁸⁷、Ｒ⁸⁸及びＲ⁸⁹のうち少なくとも１つは水素原子でなく、Ｒ⁶²は、上記一般式（ＩＩＩ）と同じであり、環Ａ²は、上記一般式（ＩＶ）と同じである。）

(Wherein X ¹¹ is a group represented by the above general formula (1), and R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, Group, optionally substituted alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, or complex having 2 to 20 carbon atoms Represents a ring-containing group, at least one of R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ is not a hydrogen atom, R ⁶² is the same as in the above general formula (III), and ring A ² is Same as formula (IV).)

（式中、ｒ＝２〜６であり、Ｘ³は、ｒ＝２のとき上記一般式（１）で表される基であり、ｒ＝３のとき上記一般式（２）で表される基であり、ｒ＝４のとき上記一般式（３）で表される基であり、ｒ＝５のとき上記一般式（４）であり、ｒ＝６のとき上記一般式（５）であり、Ｒ⁹¹、Ｒ⁹²、Ｒ⁹³及びＲ⁹⁴は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有していてもよい炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、Ｒ⁹¹、Ｒ⁹²、Ｒ⁹³及びＲ⁹⁴のうち少なくとも１つは水素原子でなく、Ｒ⁶²は、上記一般式（ＩＩＩ）と同じであり、環Ａ²は、上記一般式（ＩＶ）と同じである。）

(In the formula, r = 2 to 6, and X ³ is a group represented by the general formula (1) when r = 2, and represented by the general formula (2) when r = 3. A group represented by the general formula (3) when r = 4, a general formula (4) when r = 5, and a general formula (5) when r = 6. , R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms, and at least one of R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ One is not a hydrogen atom, R ⁶² is the same as in the general formula (III), and the ring A ² is the same as in the general formula (IV).

Examples of the six-membered alicyclic, aromatic or heterocyclic ring represented by the ring A ² in the general formula (IV) include those exemplified in the description of A ¹ in the general formula (III).
A halogen atom represented by R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ , an optionally substituted alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, Examples of the arylalkyl group having 7 to 20 carbon atoms and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R ⁶¹ or R ⁶² in the general formula (III).
The halogen atom represented by R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ in the general formula (V), an alkyl group having 1 to 40 carbon atoms which may have a substituent, and 6 to 20 carbon atoms. Examples of the aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R ⁶¹ or R ⁶² in the general formula (III). ,
The halogen atom represented by R ⁹¹ , R ²⁹² , R ⁹³ and R ⁹⁴ in the general formula (VI), an alkyl group having 1 to 40 carbon atoms which may have a substituent, and 6 to 20 carbon atoms. As the aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring-containing group having 2 to 20 carbon atoms, those exemplified in the description of R ⁶¹ or R ⁶² in the general formula (III) can be given. .

Among the compounds represented by the general formula (IV),
Ring A ² is preferably benzene or naphthalene,
Among R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ , examples of the group other than a hydrogen atom include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. 12 arylalkyl group, heterocyclic-containing group, particularly any one of an alkyl group or a heterocycle-containing group having 1 to 10 carbon atoms having 1 to 4 carbon atoms R ⁸¹ to R ⁸⁵ having 1 to 10 carbon atoms Are preferred,
R ⁶² preferably has the following substituents via —CO—O—.
An alkyl group having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl)
・ Arylalkyl group having 1 to 10 carbon atoms (particularly benzyl group)
-C2-C6 alkenyl group (especially propen-1-yl group)

Among the compounds represented by the general formula (V),
Ring A ² is preferably benzene or naphthalene,
Among R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ , the groups other than hydrogen atoms include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aryls having 7 to 12 carbon atoms. Preferred are alkyl groups, 1-10 heterocycle-containing groups, particularly alkyl groups having 1-8 carbon atoms, and heterocycle-containing groups having 1-10 carbon atoms,
R ⁶² preferably has the following substituents via —CO—O—.
An alkyl group having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl)
・ Arylalkyl group having 1 to 10 carbon atoms (particularly benzyl group)
-C2-C6 alkenyl group (especially propen-1-yl group)
In the general formula (1) representing X ¹¹ , Y ¹⁰ is preferably a sulfur atom, an aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, or a heterocyclic ring-containing group having 2 to 21 carbon atoms,
Z ¹ and Z ² are a direct bond, —CO—O—, —O—CO—, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. A hydrocarbon group, particularly an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, is preferred.

Among the compounds represented by the general formula (VI),
Among groups R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ , examples of the group other than a hydrogen atom include an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and a group having 1 to 10 carbon atoms. A heterocyclic ring-containing group, particularly, any one of R ^{91 to} R ⁹⁴ is preferably an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring-containing group having 1 to 10 carbon atoms.
R ⁶² preferably has the following substituents via —CO—O—.
An alkyl group having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl)
・ Arylalkyl group having 1 to 10 carbon atoms (particularly benzyl group)
-C2-C6 alkenyl group (especially propen-1-yl group)
When X ³ is the general formula (1), Y ¹⁰ is a sulfur atom, an alkyl group having 1 to 20 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, a heterocyclic ring-containing group having 2 to 21 carbon atoms, 2,4,8,10-tetraoxaspiro [5,5] undecane, especially alkyl groups having 1 to 15 carbon atoms, hydrocarbon groups containing 6 to 15 aromatic rings, 2,4,8,10-tetraoxa Preferred is spiro [5,5] undecane,
Z ¹ and Z ² are a direct bond, —CO—O—, —O—CO—, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. A hydrocarbon group, particularly an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, is preferred.
When X ³ is the above general formula (2), Y ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and a heterocyclic ring-containing group having 1 to 10 carbon atoms. In particular, preferred are alkyl groups having 1 to 8 carbon atoms, 6 to 9 aryl groups, and 1 to 6 heterocycle-containing groups.
Z ¹ , Z ² and Z ³ are preferably the same as Z ¹ and Z ² .
When X ³ is the above general formula (3), Y ¹² is preferably the same as Y ¹¹ ,
Z ^{1 to} Z ⁴ are preferably the same as Z ¹ and Z ² .
When X ³ is the general formula (4), Y ¹³ is preferably the same as Y ¹¹ ,
Z ^{1 to} Z ⁵ are preferably the same as Z ¹ and Z ² .
When X ³ is the general formula (5), Y ¹⁴ is preferably the same as Y ¹¹ ,
Z ^{1 to} Z ⁶ are preferably the same as Z ¹ and Z ² .

  In the composition of the present invention, the content of the latent additive (A) is preferably 0.001 to 20% by mass, and more preferably 0.005 to 5% by mass.

<Polymerization initiator (B)>
The polymerization initiator (B) used in the composition of the present invention contains one or more oxime ester compounds represented by the above general formula (I).

In the group represented by the above general formula (I), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ^As the alkyl group having 1 to 20 carbon atoms represented by ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ⁶¹ , Examples include groups satisfying the number of carbon atoms.
R ^1, is represented by ^{R 2, R 5, R 6} , R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17 and R ¹⁸ that the aryl group having 6 to 20 carbon atoms, such as the groups exemplified for the aryl group having 6 to 20 carbon atoms represented by R ⁶² can be mentioned.
R ^1, is represented by ^{R 2, R 5, R 6} , R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17 and R ¹⁸ that the aryl alkyl group having 7 to 20 carbon atoms, such as the groups exemplified for the aryl alkyl group having 7 to 20 carbon atoms represented by R ⁶² can be mentioned.
R ^1, is represented by ^{R 2, R 5, R 6} , R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17 and R ¹⁸ that as the heterocyclic ring-containing group having 2 to 20 carbon atoms, such as the groups exemplified for the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ⁶² can be mentioned.

In the general formula (II), the alkyl group having 1 to 20 carbon atoms represented by R ¹⁹ and R ²⁰ is the group exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ^61. A group satisfying a predetermined number of carbon atoms, etc.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹⁹ and R ²⁰ include groups exemplified as the aryl group having 6 to 20 carbon atoms represented by R ⁶² .
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹⁹ and R ²⁰ include groups exemplified as the arylalkyl group having 7 to 20 carbon atoms represented by R ⁶² , and the like.
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ¹⁹ and R ²⁰ include groups exemplified as the heterocyclic group having 2 to 20 carbon atoms represented by R ⁶² .

  Of the oxime ester compounds represented by the general formula (I), structures represented by the following general formulas (IA) to (ID) are preferable from the viewpoint of sensitivity and transparency.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ¹⁵、Ｒ¹⁶、Ｘ²、ａ及びｂは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ¹⁵ , R ¹⁶ , X ² , a and b are the same as those in the general formula (I).)

（式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ¹⁷、Ｘ²、ａ及びｂは、上記一般式（Ｉ）と同じである。）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ¹⁷、Ｘ²、ａ及びｂは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ⁴ , R ¹⁷ , X ² , a and b are the same as those in the general formula (I).)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ¹⁷ , X ² , a and b are the same as those in the general formula (I).)

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｘ²、ａ及びｂは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , X ² , a and b are the same as those in the general formula (I).)

Preferable specific examples of the oxime ester compound represented by the general formula (I) include the following compound Nos. 1-No. 68. However, the present invention is not limited by the following compounds.

  The polymerization initiator (B) can be used by mixing a plurality of oxime ester compounds represented by the above general formula (I), and other than the oxime ester compounds represented by the above general formula (I). It can also be used in combination with a known polymerization initiator.

  Preferred examples of the known polymerization initiator include acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, bisimidazole compounds, acridine compounds, acylphosphine compounds, and the like.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1, benzo In, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one etc. are mentioned.

  Examples of the benzyl compound include benzyl.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. It is done.

  Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

  As the bisimidazole compound, hexaarylbisimidazole (HABI, dimer of triaryl-imidazole) can be used. Specifically, for example, 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) Nyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,4,5,2 ′, 4 ′, 5′-hexaphenyl Bisimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbisimidazole, 2,2′-bis (2-bromophenyl) -4,5,4 ′, 5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5, ', 5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4', 5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2 -Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -bisimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 '-Bis (3,4-dimethoxyphenyl) bisimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4', 5'-tetraphenylbisimidazole, 2,2'-bis ( 2-Nitrophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbisimidazole, 2,2 '-Bis (2-ethoxyphenyl)- , 5,4 ', 5'-tetraphenylbisimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbisimidazole, 5'-tetra (p -Iodophenyl) biimidazole, 2,2'-bis (o-chlorophenyl-4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole), 2,2'-bis (p-methylthiophenyl) ) -4,5,4 ', 5'-diphenyl-1,1'-biimidazole, bis (2,4,5-triphenyl) -1,1'-biimidazole, 5,5'-tetra (p -Chloronaphthyl) biimidazole and the like, and tautomers covalently bonded to 1,2'-, 1,4'-, 2,4'- disclosed in JP-B-45-37377, WO00 / Compounds described in Japanese Patent No. 52529 Can be mentioned.

Examples of the acridine compound include acridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-iso-propylphenyl) acridine, 9- (p -N-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methyl) Phenyl) acridine, 9- (mn-propylphenyl) acridine, 9- (mi so-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) Acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (cyanophenyl) acridine, 9- (m-chlorophenyl) acridine , 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-cyanoethylacridine, 9-hydroxyethylacridine, 9-chloroethyl Acridine, 9-bromoacridine, 9 Hydroxyacridine, 9-nitroacridine, 9-aminoacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-n-propoxyacridine, 9-iso-propoxyacridine, 9-chloroethoxyacridine, 4,6-bis (dimethyl) Amino) acridine, 10-acetic acid acridine, 10-methyl acetate acridine, 3,6-dimethylacridine, 7,13-dimethylacridine, 7,13-bis (dimethylamino) acridine, 3,6-dimethyl-10-acetic acid acridine 3,5-dimethyl-10-methyl acetate acridine, 7,13-dimethyl-10-acetic acid acridine, 7,13-dimethyl-10-methyl acetate acridine, 1,7-bis (9-acridinyl) heptane, 1, 5-bis (9-acridini L) pentane, 1,3-bis (9-acridinyl) propane, 2,7-dibenzoyl-9-phenylacridine, 2,7-bis (α-hydroxybenzyl) -9-phenylacridine, 2,7-bis ( α-acetoxybenzyl) -9-phenylacridine, 2,7-dimethyl-9- (4-methylphenyl) acridine, 2,7-dimethyl-9-phenylacridine, 2,7-bis (3,4-dimethyl-) Benzoyl) -9- (3,4-dimethylphenyl) acridine, 2,7-bis (α-acetoxy-4-tert-butylbenzyl) -9- (4-tert-butylphenyl) acridine, 2,7-dimethyl -9- (3,4-dichlorophenyl) acridine, 2,7-dimethyl-9- (4-benzoylphenyl) acridine, 2,7-bis (2- Lolobenzoyl) -9- (2-chlorophenyl) acridine, 2- (α-hydroxy-3-bromobenzyl) -6-methyl-9- (3-bromophenyl) acridine, 2,5-bis (4-tert- Butylbenzoyl) -9- (4-tert-butylphenyl) acridine, 1,4-bis (2,7-dimethyl-9-acridinyl) benzene, 2,7-bis (α-phenylaminocarbonyloxy-3,4) -Dimethylbenzyl) -9- (3,4-dimethylphenyl) acridine and 2,7-bis (3,5-dimethyl-4-hydroxy-4'-fluorodiphenylmethyl) -9- (4-fluorophenyl) acridine 9,10-dihydroacridine, 1-methylacridine, 4-methylacridine, 2,3-dimethylacridine, 1-phenyl Kurijin, 4-phenyl acridine, 1-benzyl-acridine, 4-benzyl acridine, 1-chloro-acridine, 2,3-dichloro-acridine,
10-butyl-2-chloroacridine-9 (10H) -one, 10-propyl-2-chloroacridine-9 (10H) -one, 10-butyl-2-chloroacridine-9 (10H) -one 1,2 -Bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) butane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9 -Acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, 1,14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) ) Hexadecane, 1,18-bis (9-acridinyl) octadecane, 1,20-bis (9-acridinyl) eicosane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5-bis (9 -Acridinyl) -3-thiapentane 7-methyl-benzo [c] acridine, 7-ethyl-benzo [c] acridine, 7-propyl-benzo [c] acridine, 7-butyl-benzo [c] acridine, 7-pentyl -Benzo [c] acridine, 7-hexyl-benzo [c] acridine, 7-heptyl-benzo [c] acridine, 7-octyl-benzo [c] acridine, 7-nonyl-benzo [c] acridine, 7-decyl -Benzo [c] acridine, 7-undecyl-benzo [c] acridine, 7-dodecyl-benzo [c] acridine, 7- Tridecyl-benzo [c] acridine, 7-tetradecyl-benzo [c] acridine, 7-pentadecyl-benzo [c] acridine, 7-hexadecyl-benzo [c] acridine, 7-heptadecyl-benzo [c] acridine, 7 -Octadecyl-benzo [c] acridine, 7-nonadecyl-benzo [c] acridine, 1,1-bis (7-benzo [c] acridinyl) methane, 1,2-bis (7-benzo [c] acridinyl) ethane 1,3-bis (7-benzo [c] acridinyl) propane, 1,4-bis (7-benzo [c] acridinyl) butane, 1,5-bis (7-benzo [c] acridinyl) pentane, , 6-bis (7-benzo [c] acridinyl) hexane, 1,7-bis (7-benzo [c] acridinyl) heptane, 1,8- Bis (7-benzo [c] acridinyl) octane, 1,9-bis (7-benzo [c] acridinyl) nonane, 1,10-bis (7-benzo [c] acridinyl) decane, 1,11-bis ( 7-benzo [c] acridinyl) undecane, 1,12-bis (7-benzo [c] acridinyl) dodecane, 1,13-bis (7-benzo [c] acridinyl) tridecane, 1,14-bis (7- Benzo [c] acridinyl) tetradecane, 1,15-bis (7-benzo [c] acridinyl) pentadecane, 1,16-bis (7-benzo [c] acridinyl) hexadecane, 1,17-bis (7-benzo [7 c] acridinyl) heptadecane, 1,18-bis (7-benzo [c] acridinyl) octadecane, 1,19-bis (7-benzo [c] acridiny ) Nonadecane, 1,20-bis (7-benzo [c] acridinyl) eicosane, 7-phenyl-benzo [c] acridine, 7- (2-chlorophenyl) -benzo [c] acridine, 7- (4-methyl) Phenyl) -benzo [c] acridine, 7- (4-nitrophenyl) -benzo [c] acridine, 1,3-bis (7-benzo [c] acridinyl) benzene, 1,4-bis (7-benzo [ c] acridinyl) benzene, 7- [1-propen-3-yl (benzo [c] acridine)], 7- [1-ethylpentyl- (benzo [c] acridine)], 7- [8-heptadecenyl- ( Benzo [c] acridine)], 7,8-diphenyl-1,14-bis (7-benzo [c] acridinyl) tetradecane, 1,2-bis (7-benzo [c] acridiny ) Ethylene, 1-methyl-1,2-bis (7-benzo [c] acridinyl) ethylene, 7-styryl-benzo [c] acridine, 7- (1-propenyl) -benzo [c] acridine, 7- ( 1-pentenyl) -benzo [c] acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine, 9- (4-pyrimidinyl) acridine, 9- ( 2-pyrazinyl) acridine, 9 (5-methyl-2-pyrazinyl) acridine, 9- (2-quinolinyl) acridine, 9- (2-pyridyl) -2-methyl-acridine, 9- (2-pyridyl) -2 -Ethylacridine, 9- (3-pyridyl) -2-methyl-acridine, 9- (3-pyridyl) -2,4-diethyl-acridine, 3,6-diamino-acridine Examples include lysine sulfonate, 3,6-bis- (dimethylamino) -acridine sulfonate, 3,6-diamino-10-methyl-acridinium chloride, and 9-acridine carboxylic acid.

  Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO; manufactured by BASF), isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, and pivaloyl-phenylphosphinic acid methyl. Ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenyl Phosphinic acid methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, acryloyl-phenylphosphine Methyl ester, isobutyryl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-toluyl-diphenylphosphine oxide, p-tert-butylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide, acryloyl-diphenyl Phosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid vinyl ester, adipoyl-bis-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, 4- (tertiarybutyl) -benzoyl-diphenyl Phosphine oxide, 2-methylbenzoyl-diphenylphosphine oxa 2-methyl-2-ethylhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester, 4-octylphenylphosphine oxide , Terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, versatoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-diisobutoxyphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819; manufactured by BASF), bis (2, 4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6 -Dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) ) -4-Ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-) 1-naphthoyl) -2,5-dimethylphenylphosphine Oxide, bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dioctyloxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4- Diisopropoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dihexyloxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-propoxy-4-methylphenylphosphine Oxide, bis (2, 4, 6-trimethylbenzoyl) -2,4-diisopentyloxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, Bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylph Examples include phosphine oxide (CGI403) and 6-trimethylbenzoyl-ethyl-phenyl-phosphinate (SPEEDCURE TPO-L; manufactured by Lambson).

  The content of the oxime ester compound represented by the general formula (I) in the polymerization initiator (B) used in the present invention is preferably 20 to 100% by mass, more preferably 50 to 100% by mass.

  In the composition of the present invention, the total content of the polymerization initiator is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass, based on the solid content of the composition of the present invention. If the content of the polymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and if it is more than 30% by mass, the initiator may be precipitated in the resin composition.

  The composition of the present invention is a mixture of a latent antioxidant (A) and a polymerization initiator (B), a resin, a photopolymerizable unsaturated monomer and, if necessary, a solvent, an inorganic compound, a coloring material, and the like. It can also be used as a photosensitive composition.

The resin is not particularly limited as long as it is compatible with the polymerization initiator and the photopolymerizable unsaturated monomer. For example, a repeating unit derived from the photopolymerizable unsaturated monomer may be used. Examples thereof include a homopolymer or a copolymer.
Among them, methacrylic acid ester copolymers, polyvinyl alcohol / polyvinyl ether / polyvinyl ester copolymers, unsaturated polyesters and the like are preferable because they have good compatibility with the photopolymerizable unsaturated monomers, and resins having an acid value. Is preferable from the viewpoint of photolithography.

  As the resin having the acid value (or its monomer), (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, highmic acid, crotonic acid, isocrotonic acid, vinyl Acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono Mono (meth) acrylate, hydroxyethyl (meth) acrylate / malate, hydroxypropyl (meth) acrylate / malate, dicyclopentadiene / malate or one polymer having a carboxy group and a hydroxyl group at both ends, such as (meth) acrylate Having two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; unsaturated monobasic acids such as dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate and esters of polyhydric alcohols or polyphenols; 4 -Unsaturated aromatic compounds such as hydroxystyrene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl glycidyl ether; vinyl alcohols such as allyl alcohol and crotyl alcohol; pentaerythritol triacrylate, Reaction product of hydroxyl group-containing polyfunctional acrylate such as dipentaerythritol pentaacrylate and dibasic anhydride such as succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride; bisphenol type epoxy compound or novolak Reaction product of an epoxy compound and an unsaturated monobasic acid; can be used as the acid anhydride is reacted in the reaction product of a bisphenol type epoxy compound or a novolak type epoxy compound with an unsaturated monobasic acid. These monomers can be used individually by 1 type or in mixture of 2 or more types. Moreover, it is preferable that resin which has said acid value contains 0.2-1.0 equivalent of unsaturated groups.

Examples of the unsaturated monobasic acid that acts on the epoxy group of the bisphenol type epoxy compound or novolak type epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / Examples thereof include malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate.
In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride , Pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride Acid, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride Maleic anhydride adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 It is preferable that the acid anhydride structure of the polybasic acid anhydride has a ratio of 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

  In order to improve the developability of the composition of the present invention by adjusting the acid value of the resin (A) having the acid value, a monofunctional or polyfunctional epoxy compound can be further used. The resin having the acid value preferably has a solid acid value in the range of 5 to 120 mgKOH / g, and the usage amount of the monofunctional or polyfunctional epoxy compound is selected so as to satisfy the acid value. preferable.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compound No. A2, No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers because an alkali-developable photosensitive composition with better characteristics can be obtained. As the bisphenol-type epoxy compound, the epoxy compound represented by the general formula (1) can be used, and for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like can also be used.

  Among the resins having an acid value, unsaturated polybasic acids and polyfunctional acrylates having an acid value are preferable, and polyfunctional acrylates having an acid value are particularly preferable from the viewpoints of compatibility, alkali developability, and heat resistance.

  Commercially available resins can be used as the resin having the acid value, for example, SPC-1000, SPC-3000 (manufactured by Showa Denko KK), AX3-BX, AX3-RD1, AX3-RD2 (manufactured by Nippon Shokubai Co., Ltd.). , JET2000 (manufactured by Osaka Organic Chemical Co., Ltd.) and the like.

  The polymerizable unsaturated monomer is not particularly limited, and those conventionally used in photosensitive compositions can be used. Examples thereof include ethylene, propylene, butylene, isobutylene, vinyl chloride, and vinylidene chloride. , Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, Vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone Mono (meth) of polymer having carboxy group and hydroxyl group at both ends such as mono (meth) acrylate Chryrate: Hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups Unsaturated monobasic acids such as: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.

  Among the above-mentioned various compounds mentioned as the polymerizable unsaturated monomer, in particular, it is possible to use unsaturated monobasic acid and polyhydric alcohol or polyhydric phenol ester from the viewpoint of curability and chromaticity characteristics. preferable.

  When the composition of the present invention is a photosensitive composition, the content of the polymerizable unsaturated monomer is the resin: the photopolymerizable unsaturated monomer = 35 to 95: 5 to 65 parts by mass, Preferably it is 40-90: 10-60 mass parts.

  When the composition of the present invention is a photosensitive composition, the total amount of the resin and the polymerizable unsaturated monomer is preferably 20 to 80% by mass in the solid content of the composition of the present invention. More preferably, it is 30-70 mass%. If the total content of both is less than 20% by mass, the cured film may not be sufficiently hardened. If it is more than 80% by mass, the colorant may be small and the color characteristics may be insufficient.

  The solvent is usually a solvent capable of dissolving or dispersing each of the above components (polymerization initiator, resin, photopolymerizable unsaturated monomer, etc.) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone. Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethers such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether Solvents; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene glycol mono Cellosolve solvents such as tilether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1 -Ether ester solvents such as monomethyl ether-2-acetate (PGMEA), 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; benzene BTX solvents such as toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene, Terpene-based hydrocarbon oils such as minerals; paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like can be mentioned, and these solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate (PGMEA), cyclohexanone and the like are preferable because the compatibility of the resist and the polymerization initiator is good in the colored composition.

  When the composition of the present invention is a photosensitive composition, the amount of the solvent used is preferably such that the concentration of the composition other than the solvent is 5 to 30% by mass. When the concentration of the components of the composition other than the solvent is less than 5% by mass, it is difficult to increase the film thickness and the desired wavelength light cannot be sufficiently absorbed. This is not preferable because the storage stability of the composition is reduced due to the precipitation and the viscosity is improved and the handling is reduced.

Examples of the inorganic compound include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina, and other metal oxides; layered clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt-based, manganese-based, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper, etc. are mentioned.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by mass, more preferably 10 to 800 parts by mass with respect to 100 parts by mass of the resin. These inorganic compounds can be used alone or in combination of two or more.

  These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  A dispersing agent for dispersing a colorant and / or an inorganic compound can be added to the photosensitive composition of the present invention. The dispersing agent is not limited as long as it can disperse and stabilize a coloring material or an inorganic compound, and a commercially available dispersing agent such as BYK series manufactured by BYK Chemie Corporation can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof. And those having an amine value of 1 to 100 mgKOH / g are preferably used.

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

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with an epoxy resin, carbon black previously dispersed with a resin in a solvent, 20 to 200 mg / g of resin adsorbed, carbon black treated with an acidic or alkaline surface, average Graphite having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ² of the surface area of carbon black; Graphite , Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series , Ferrocyanide Organic or inorganic such as phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber Pigments can be used. These pigments can be used alone or in combination.

  Commercially available pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

  As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

  When using the composition of this invention as a photosensitive composition, content of the said coloring material becomes like this. Preferably it is 50-350 mass parts with respect to 100 mass parts of said resins, More preferably, it is 100-250 mass parts.

  In the composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, etc .; plasticizer; adhesion promoter; filler; Leveling agent; Surface modifier; Antioxidant; UV absorber; Dispersion aid; Aggregation inhibitor; Catalyst; Effect accelerator; Crosslinking agent; Thickener; Chain transfer agent; Coupling agents; conventional additives such as melamine can be added.

  In the composition of the present invention, optional components other than the latent additive (A) and the polymerization initiator (B) (however, the other photopolymerization initiator, resin, photopolymerizable unsaturated monomer, inorganic The amount of the compound (excluding the filler, colorant and solvent) is appropriately selected depending on the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less based on 100 parts by mass of the resin. To do.

Moreover, in the photosensitive composition of this invention, the characteristic of hardened | cured material can also be improved by using another organic polymer with the polymeric compound which has the said ethylenically unsaturated bond. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Examples thereof include polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin and the like. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. Arbitrariness.
When using another organic polymer, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the resin.

  As a light source for activating the polymerization initiator (B) used in the composition of the present invention to cure the composition, one that emits light having a wavelength of 300 to 450 nm can be used. Mercury vapor arc, carbon arc, xenon arc, etc. can be used.

  The exposure time of the composition of the present invention to the energy rays depends on the strength of the energy rays, the coating thickness and the polymerizable organic compound, but usually about 0.1 to 10 seconds is sufficient. However, it is preferable to take a longer irradiation time for a relatively thick coating. From 0.1 seconds to several minutes after the irradiation with energy rays, most of the compositions are dry to the touch by polymerization. However, in order to accelerate the polymerization, it is sometimes preferable to use heat or thermal energy by a thermal head or the like.

When the composition of the present invention is used as a photosensitive composition, a pattern can be formed by the following steps.
That is, (1) a step of forming a coating film of the composition of the present invention on a substrate, (2) a step of irradiating the coating film with a mask having a predetermined pattern shape, (3) after exposure A pattern is preferably formed by a baking step, (4) a step of developing the film after exposure, and (5) a step of heating the film after development.
As the mask, a multi-tone mask such as a halftone mask or a gray scale mask can be used.

  Specific applications of the composition of the present invention include optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices, LED packages, Sealants for liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic parts, separation membranes, molding materials, putty, glass fiber impregnating agents, sealants, for semiconductors and solar cells Passivation films such as thin film transistors (TFTs), liquid crystal display devices, organic EL display devices, interlayer insulating films used for printed circuit boards, surface protective films, printed circuit boards, color televisions, PC monitors, portable information terminals, CCD image sensors Color filter, electrode material for plasma display panel, printing ink, dental composition, resin for stereolithography, both liquid and dry film, micro mechanical parts Glass fiber cable coating, holographic recording material, magnetic recording material, optical switch, plating mask, etching mask, screen printing stencil, touch panel such as transparent conductive film, MEMS element, nanoimprint material, 2D and 3D of semiconductor package Used for photofabrication such as high-density mounting, decorative sheets, artificial nails, glass replacement optical films, electronic paper, optical disks, microlens arrays used in projectors and lasers for optical communications, and backlights for liquid crystal display devices Lenses of lens sheets such as prism lens sheets, Fresnel lens sheets used for screens of projection televisions, lenticular lens sheets, or backlights using such sheets, micro lenses Optical lenses such as imaging lenses, optical elements, optical connectors, optical waveguides, insulating packings, heat-shrinkable rubber tubes, O-rings, sealants for display devices, protective materials, optical fiber protective materials, adhesives, die bonding agents, High heat dissipation material, high heat-resistant sealing material, solar cell / fuel cell / secondary battery material, solid electrolyte for battery, insulation coating material, photosensitive drum for copying machine, gas separation membrane, concrete protective material / lining / soil injection agent・ Sealing agents ・ Cool storage materials ・ Glass coatings ・ Construction materials such as foam, tubes, sealing materials, coating materials, sealing materials for sterilization equipment, contact lenses, oxygen-enriched membranes, biochips, and other medical materials It can be used for various applications such as automobile parts and various machine parts, and there are no particular restrictions on the applications.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Examples 1 to 26 and Comparative Examples 1 to 5] Production and evaluation of compositions
Compositions were prepared according to the formulations in [Table 1] to [Table 5]. This was spin-coated on a glass substrate (900 rpm, 10 seconds), pre-baked at 90 ° C. for 90 seconds using a hot plate, and exposed using a high-pressure mercury lamp as a light source. A 2.5% by mass aqueous sodium carbonate solution was used as a developing solution, developed for 40 seconds with a spin developing machine, washed well with water, and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. In addition, the numerical value in a table | surface is a mass part.

  The symbols A-1 to A-4, B′-1 to B′-4, and C-1 to C-3 in the table represent the following. In addition, Compound No. 1, 2, 7, 11-17, 19, 21-28, 36 and 42 correspond to the numbers of the oxime ester compounds exemplified as preferred specific examples of the oxime ester compound represented by the general formula (I). A compound.

B′-1 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (HABI)
B′-2 N-1717 (acridine compound: manufactured by ADEKA)
B'-3 Lucirin TPO (manufactured by BASF)
B'-4 Benzophenone

C-1 SPC-1000 (manufactured by Showa Denko KK, PGMEA solution with a solid content of 29%)
C-2 Kayalad DPHA (polyfunctional acrylate; manufactured by Nippon Kayaku Co., Ltd.)
C-3 Propylene glycol-1-monomethyl ether-2-acetate

[Evaluation Examples 1-1 to 1-26 and Comparative Evaluation Examples 1-1 to 1-5] Sensitivity Evaluation The heights of the patterns obtained in Examples 1 to 26 and Comparative Examples 1 to 5 The measurement was performed using a measuring instrument (manufactured by Keyence), and the residual film ratio (%) was obtained from the following formula to obtain the radiation sensitivity. Incidentally, when the exposure dose giving a residual film ratio of 70% or more of ~20mJ / cm ² is A, when 20~100~mJ / cm ² of B, when 100~200mJ / cm ² is C, 200 mJ / When cm ² ~, it was set to D. The test results are shown in [Table 1] to [Table 5].
Residual film ratio (%) = (pattern height after post-baking / initial film thickness) × 100

[Evaluation Examples 2-1 to 2-26 and Comparative Evaluation Examples 2-1 to 2-5] Transparency Evaluation After Firing Using the composition obtained above, a coating that was separately cured entirely without using a mask The film was baked under conditions of 230 ° C. × 120 minutes, and the transmittance of the baked coating film at 400 nm was measured. When the transmissivity was 95% or more, a, 90 to 94% was b, and when 89% or less, c. The results are shown in [Table 1] to [Table 5].

  From the above results, since the composition of the present invention contains a latent antioxidant, the transmittance of the coating film is high even after firing, that is, yellowing due to thermal deterioration of the coating film is prevented, and the heat resistance is high. Clearly it is expensive.

Claims (4)

A composition containing a latent antioxidant (A) and a polymerization initiator (B) containing at least one oxime ester compound represented by the following general formula (I).

Wherein R ¹ and R ² are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms. Represents a group or a heterocyclic group containing 2 to 20 carbon atoms,
R ³ and R ⁴ are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ⁵ , OR ⁶ , SR ⁷ , NR ⁸ R ⁹ , COR ¹⁰ , SOR ¹¹ , SO ₂ R ¹² or CONR ¹³ R ¹⁴ , R ³ and R ⁴ may be bonded to each other to form a ring, R ³ and R ⁴ may be bonded to each other to form a ring,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ¹⁵ R ¹⁶ , CO, NR ¹⁷ or PR ¹⁸ ,
X ² represents a single bond or CO,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently the number of carbon atoms. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms,
^{R 1, R 2, R 5} , R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, carbon in R ^16, R ¹⁷ and R ¹⁸ The alkyl group having 1 to 20 atoms may be linear, branched, cyclic, linear and ring combinations, or branched and ring combinations,
^{R 1, R 2, R 5} , R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, carbon in R ^16, R ¹⁷ and R ¹⁸ The methylene group in the alkyl group having 1 to 20 atoms or the arylalkyl group having 7 to 20 carbon atoms is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a heterocyclic group, or the following general formula (II) May be substituted with a substituent represented by the formula:
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

Wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms. Represents a group or a C2-C20 heterocycle-containing group.) The composition according to claim 1, wherein the latent antioxidant (A) has a skeleton represented by the following general formula (III).

(In the formula, ring A ¹ represents a 5-membered or 6-membered hydrocarbon ring or heterocyclic ring,
R ⁶¹ is independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R ⁶² each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon Represents a heterocyclic group containing 2 to 20 atoms or a trialkylsilyl group,
The methylene group in the alkyl group or arylalkyl group represented by R ⁶¹ and R ⁶² is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O. -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, - NH-CO -, - NH-CO-O -, - NR '-, - replaced by an oxygen atom a group selected from the combination conditions are not adjacent group - S-S- or -SO ₂ R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R ⁶¹ may be bonded to each other to form a benzene ring or a naphthalene ring,
d represents an integer of 1 to 5;
k represents an integer of 1 to 5, but the sum of d and k is less than the number of substituents that ring A ¹ can take. ) The composition according to claim 1 or 2, wherein the latent antioxidant (A) comprises a compound represented by the following general formula (III-A).

(In the formula, ring A ¹ represents a 5-membered or 6-membered hydrocarbon ring or heterocyclic ring,
R ⁶¹ is independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R ⁶² each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon Represents a heterocyclic group containing 2 to 20 atoms or a trialkylsilyl group,
The methylene group in the alkyl group or arylalkyl group represented by R ⁶¹ and R ⁶² is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O. -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, - NH-CO -, - NH-CO-O -, - NR '-, - replaced by an oxygen atom a group selected from the combination conditions are not adjacent group - S-S- or -SO ₂ R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R ⁶¹ may be bonded to each other to form a benzene ring or a naphthalene ring,
m represents an integer of 1 to 10,
d represents an integer of 1 to 5;
k represents an integer of 1 to 5, but the sum of d and k is less than the number of substituents that ring A ¹ can take,
X ⁵ represents an m-valent organic group. ) The oxime ester compound represented by the general formula (I) is represented by the following general formula (IA), (IB), (IC) or (ID). The composition as described in any one of Claims 1-3.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ¹⁵ , R ¹⁶ , X ² , a and b are the same as those in the general formula (I).)

(In the formula, R ¹ , R ² , R ⁴ , R ¹⁷ , X ² , a and b are the same as those in the general formula (I).)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ¹⁷ , X ² , a and b are the same as those in the general formula (I).)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , X ² , a and b are the same as those in the general formula (I).)