KR20180132599A - Photosensitive compositions and novel compounds - Google Patents

Abstract

A photosensitive composition comprising a compound having a substituent represented by the following general formula (1).

(Wherein R ¹ and R ² are each independently 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, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic ring-containing group having 2 to 20 carbon atoms, or a trialkylsilyl group, j represents a number of 1 to 3, Means to combine with adjacent groups in.

Description

Photosensitive compositions and novel compounds

The present invention relates to a photosensitive composition which has a specific structure and is inert at room temperature and which is activated by heating to a predetermined temperature to express a function, and a novel compound. The present invention also relates to a colored photosensitive composition to which a coloring agent is added to the photosensitive composition and a color filter using the colored photosensitive composition.

In order to improve the weather resistance and heat resistance of the photosensitive composition, there is known a method of stabilizing by adding an ultraviolet absorber or an antioxidant (Patent Documents 1 to 4).

Phenol-based antioxidants and ultraviolet absorbers have an action of trapping radicals that greatly affect deterioration of the polymer. Therefore, when they are added to the polymerization system, they generally act as so-called polymerization inhibitors and cause curing (inhibition) The potential additive has been developed (Patent Document 5).

However, the conventional compositions using the latent additive have a problem that the outgass is large, and thus the heating device is contaminated or the physical properties of the composition are deteriorated. There is a problem of contamination of the apparatus and reduction of physical properties. In addition, the conventional composition using the latent additive has a low solvent resistance of the cured product, resulting in the elution of the cured product, for example, reducing the brightness of the color filter.

Patent Document 6 discloses a triallyl phenol compound useful as a curing agent, but a photosensitive composition containing the triallyl phenol compound is not suggested.

Japanese Laid-Open Patent Publication No. 2011-048382 U.S. Patent Application Publication No. 2016/016919 Japanese Laid-Open Patent Publication No. 2015-108649 Japanese Laid-Open Patent Publication No. 2015-132791 International Publication No. 2014/021023 Japanese Patent Application Laid-Open No. 3-232832

Accordingly, an object of the present invention is to provide a photosensitive composition which is inert at room temperature and which is activated by heating at a predetermined temperature and which exhibits a function as an antioxidant or an ultraviolet absorber, and which has low outgassing and high solvent resistance of the cured product. Another object of the present invention is to provide a colored photosensitive composition to which a coloring agent is added to the photosensitive composition, particularly a colored photosensitive composition suitable for a color filter.

As a result of intensive investigations, the inventors of the present invention have found that a photosensitive composition using a compound having a specific protecting group has little out-gas and has a high solvent resistance of the cured product. Further, the colored photosensitive composition, The inventors of the present invention have arrived at the present invention by knowing that they are suitable for a color filter for an image display apparatus such as a liquid crystal display panel without lowering the luminance of the filter (particularly, the color filter).

The present invention is based on the above finding, and provides a photosensitive composition containing a compound having a substituent represented by the following general formula (1).

(Wherein R ¹ and R ² each independently represent 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, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, which may have a substituent, a heterocyclic ring-containing group having 2 to 20 carbon atoms, which may have a substituent, or A trialkylsilyl group,

The methylene group in the alkyl group or arylalkyl group represented by R ¹ and R ² is preferably -O-, -S-, -CO-, -O-CO-, -CO-O-, -O- -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, -SS- or -SO ₂ - may be substituted with a group in which oxygen atoms are not adjacent to each other, and R 'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

j represents a number of 1 to 3,

* Means combining with adjacent groups in the * part.)

Hereinafter, the present invention will be described in detail based on preferred embodiments.

The photosensitive composition of the present invention contains a compound having a substituent represented by the general formula (I).

Among the compounds having a substituent represented by the general formula (I), those represented by the following general formula (I-A) are particularly preferable because they have high heat resistance and little outgassing.

(Wherein n represents an integer of 1 to 10,

X ¹ represents an n-valent coupler,

R ¹ , R ² and j are the same as in the general formula (I).)

Examples of the halogen atom represented by R ¹ and R ² include fluorine, chlorine, bromine and iodine,

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, Heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-butyl, tert-butyl, - octyl, adamantyl and the like,

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, Phenyl, 4-cyclohexylphenyl, 4-cyclohexylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-iso-butylphenyl, , 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, Butylphenyl, 2,4-di-tert-butylphenyl, 2,6-di-tert- Butylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'- -, 2,4,5-trimethylphenyl, ferrocenyl and the like,

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ² include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenylmethyl, Propyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, cinnamyl,

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ¹ and R ² include a pyridine ring, a pyrimidine ring, a pyridazine ring, a piperidine ring, a pyran ring, a pyrazoline ring, a triazine ring, A benzofuran ring, a thiazoline ring, a benzothiazoline ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, a thiophene ring, A group obtained by combining a methylene chain with a heterocycle such as an oxazoline ring, a benzoxazoline ring, an isothiazoline ring, an isoxazoline ring, an indole ring, a pyrrolidine ring, a piperidone ring and a dioxane ring,

Examples of the trialkylsilyl group represented by R ¹ and R ² include a silyl group substituted with an alkyl group having 1 to 6 carbon atoms (three alkyl groups being the same or different) such as trimethylsilane, triethylsilane, and ethyldimethylsilane.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R 'include those satisfying the predetermined number of carbon atoms in the alkyl group represented by R ¹ .

An alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ² , an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms Include ethylenic unsaturated groups such as vinyl, allyl, acryl, and methacryl; Halogen atoms such as fluorine, chlorine, bromine and iodine; Examples of the substituents are acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, An acyl group such as saloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl or carbamoyl; Acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, Wherein the alkyl moiety is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n- N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, N, N-dimethylaminosulfonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, A substituted amino group such as amino; A sulfonic acid group, a phosphoric acid group or a carboxyl group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a carboxyl group, An acid group, a salt of a phosphoric acid group, and the like.

As R ¹ and R ² , 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 the out gas is small. It is more preferable that R ¹ and R ² are any one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms having a branch, particularly a t-butyl group because the out gas is small.

In the general formula (IA), X ¹ represents an n-valent linking group, and specific examples thereof include a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, -CO-, -NH-CO-, -CO-NH-, -NR ³ -, -OR ³ , -SR ³ , -NR ³ R ⁴ or the same number of valency as n An aliphatic hydrocarbon group of 1 to 120 carbon atoms which may have a substituent, an aromatic ring-containing hydrocarbon group of 6 to 35 carbon atoms which may have a substituent, or a carbon atom which may have a substituent R ³ and R ^{4 each} represent a hydrogen atom, an aliphatic hydrocarbon group of 1 to 35 carbon atoms which may have a substituent, an aliphatic hydrocarbon group of 6 to 30 carbon atoms which may have a substituent, An aromatic ring-containing hydrocarbon group having 35 to 35 carbon atoms or a complex having 2 to 35 carbon atoms which may have a substituent An alicyclic hydrocarbon group, an aromatic ring-containing hydrocarbon group and a heterocyclic ring-containing group may be a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO- -CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH- CO-O-, -O-CO-NH-, -NR'-, -SS-, -SO ₂ - or a nitrogen atom.

Provided that when X ¹ is a nitrogen atom, a phosphorus atom or a bonding group represented by the following formula (Ia) or (Ib), n is 3 and X ¹ is an oxygen atom or a sulfur atom, -CO-, -NH- CO-NH- or -NR ³ - If, wherein n is 2, when X ¹ is a hydrogen atom, -OR ^3, -SR ³ or -NR ³ R ^4, n is 1, X ¹ is a benzene ring Or the like, to form a ring.

(* Means combining with adjacent groups in the * part.)

The compound represented by the general formula (IA) has a structure in which n specific groups are bonded to an n-valent bond group represented by X ¹ . These n groups are the same or different from each other. The value of n is 1 to 10, and preferably 2 to 6 from the viewpoint of low outgassing.

Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms, which may have a substituent and have a number of the same number as n, represented by X ¹ in the general formula (IA) include monovalent groups such as methyl , Ethyl, propyl, isopropyl, cyclopropyl, butyl, sec. Butyl, tert.butyl, isobutyl, amyl, isoamyl, tertiary amyl, cyclopentyl, hexyl, Cyclohexyl, 1-methylcyclohexyl, heptyl, 2heptyl, 3heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isonyl, An alkyl group; But are not limited to, methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert -butyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, Alkoxy groups such as heptyloxy, isoheptyloxy, heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy and decyloxy; Examples of the alkylthio include methylthio, ethylthio, propylthio, isopropylthio, butylthio, tert-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tertiary amylthio, hexylthio, cyclohexylthio, heptyl An alkylthio group such as thio, isoheptylthio, tert-pentylthio, n-octylthio, isooctylthio, tert-octylthio, or 2-ethylhexylthio; Propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, Alkenyl groups such as 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and tricosenyl; And groups in which these groups are substituted by substituents which will be described later.

n is divalent, and examples thereof include alkylenes such as methylene, ethylene, propylene, butylene and butyldiyl; The methylene chain of the alkylene being substituted with -O-, -S-, -CO-O-, -O-CO-; Diol residues such as ethanediol, propanediol, butanediol, pentanediol, and hexanediol; Residues of dithiol such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, and hexanedithiol; And groups in which these groups are substituted by substituents which will be described later.

n is trivalent, for example, alkylidines such as propylidene and 1,1,3-butylidine; And groups in which these groups are substituted by substituent groups described later.

Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, which may have a substituent and have the same number of valences as n, include monovalent groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, Arylalkyl groups such as reel and cinnamyl; Aryl groups such as phenyl and naphthyl; An aryloxy group such as phenoxy, naphthyloxy and the like; Arylthio groups such as phenylthio and naphthylthio; And groups in which these groups are substituted by substituents which will be described later.

n is an arylene group such as phenylene or naphthylene; Residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro [5,5] undecane and the like; And groups in which these groups are substituted by substituent groups described later,

n is 3, phenyl-1,3,5-trimethylene, and groups in which these groups are substituted by the substituents described below.

Examples of the heterocyclic ring-containing group having 2 to 35 carbon atoms, which may have a substituent and have the same number of valences as n, include those wherein n is monovalent, such as pyridyl, pyrimidyl, pyridazyl, piperidyl, Thiadiazolyl, thiazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazole, benzothiophene, thiadiazole, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dichloropyridazinone, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, Dioxyimidazolidin-3-yl, 2,4-dioxoxazolidin-3-yl, benzotriazolyl, etc .; And groups in which these groups are substituted by substituents which will be described later.

n is a divalent 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 groups in which these groups are substituted by substituent groups described later,

Examples of the trivalent n include a group having an isocyanuric ring and a group having a triazine ring; And groups in which these groups are substituted by substituent groups described later.

Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent and represented by R ³ and R ⁴ include an aliphatic hydrocarbon group represented by X ¹ and a combination of the aliphatic hydrocarbon group and the substituent group, , ≪ / RTI >

An aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, which may have a substituent, and a heterocyclic ring-containing group having 2 to 35 carbon atoms, which may have a substituent, represented by R ³ and R ⁴ , An aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a heterocyclic ring-containing group having 2 to 35 carbon atoms represented by ^1, and a group containing a combination of these groups and a substituent described below, have.

Examples of the substituent include an ethylenic unsaturated group such as vinyl, allyl, acryl, and methacryl; Halogen atoms such as fluorine, chlorine, bromine and iodine; Examples of the substituents are acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, An acyl group such as saloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl or carbamoyl; Acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, Wherein the alkyl moiety is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n- N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, N, N-dimethylaminosulfonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, A substituted amino group such as amino; A sulfonic acid group, a phosphoric acid group or a carboxyl group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a sulfonic acid group, a carboxyl group, An acid group, a salt of a phosphoric acid group and the like, and these groups may be further substituted. Further, the carboxyl group and the sulfo group may form a salt.

When n is 2 to 6 in the general formula (IA), X ¹ may be represented by the following general formulas (1) to (5), respectively.

(Wherein Y ¹ represents a single bond, -CR ⁵ R ⁶ -, -NR ⁷ -, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon having 6 to 35 carbon atoms Or a heterocyclic ring-containing group having 2 to 35 carbon atoms or any substituent represented by any one of the following (1-1) to (1-3)

The aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO ₂ -, -CONH- or -NHCO-, And may be substituted with a combinator group,

Z ¹ and Z ² each independently represents a direct bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO ₂ -, -SS-, Lt; ⁷ > - or -PR < ⁷ > -,

R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon having 6 to 35 carbon atoms which may have a substituent Or a heterocyclic ring-containing group having 2 to 35 carbon atoms which may have a substituent,

* Means combining with adjacent groups in the * part.)

(Wherein R ⁸ represents a hydrogen atom or a phenyl group which may have a substituent or a cycloalkyl group of 3 to 10 carbon atoms,

R ⁹ represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may have a substituent In some cases,

f is an integer of 0 to 5,

* Means combining with adjacent groups in the * part.)

(* Means combining with adjacent groups in the * part.)

(Wherein R ¹⁰ and R ¹¹ each independently represents an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 6 to 20 carbon atoms which may have a substituent, An aryloxy group having 6 to 20 carbon atoms, an arylthio group having 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 arylalkyl group having 7 to 20 carbon atoms which may have a substituent, a heterocyclic ring-containing group having 2 to 20 carbon atoms which may have a substituent, or a halogen atom,

The methylene group in the alkyl group and the arylalkyl group may be substituted with an unsaturated bond, -O- or -S-,

R < ¹⁰ > may form a ring with adjacent R < ¹⁰ >

p represents a number of 0 to 4,

q represents a number of 0 to 8,

g represents a number of 0 to 4,

h represents a number of 0 to 4,

the sum of the numbers of g and h is 2 to 4,

* Means combining with adjacent groups in the * part.)

(In the general formula (2), Y ¹¹ represents an aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, Containing heterocyclic group having a number of 2 to 35,

Z ¹ , Z ² and Z ³ each independently represents a direct bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO ₂ -, -SS-, SO-, -NR _12- or -PR ₁₂ - represents the,

R ¹² represents a hydrogen atom, an aliphatic hydrocarbon group of 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group of 6 to 35 carbon atoms which may have a substituent, or a carbon which may have a substituent A heterocyclic ring-containing group having 2 to 35 atoms,

The aliphatic hydrocarbon group may be a carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO ₂ -, -CONH- or -NHCO-, In some cases, it is substituted by a coupler which is not adjacent but is a combination of these.

* Means combining with adjacent groups in the * part.)

(In the general formula (3), Y ¹² represents a carbon atom or an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring containing 2 to 35 carbon atoms Lt; / RTI >

The aliphatic hydrocarbon group may be a carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO ₂ -, -CONH- or -NHCO-, In some cases, they are not adjacent to each other but are substituted by a combiner combining them.

Z ¹ to Z ⁴ each independently represent a group in the same range as the group represented by Z ¹ to Z ³ in the general formula (2)

* Means combining with adjacent groups in the * part.)

(In the general formula (4), Y ¹³ represents an aliphatic hydrocarbon group of 5 to 35 carbon atoms, an aromatic hydrocarbon group of 6 to 20 carbon atoms, or a heterocyclic ring-containing group of 2 to 20 carbon atoms,

The aliphatic hydrocarbon group may be a carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO ₂ -, -CONH- or -NHCO-, In some cases, they are not adjacent to each other but are substituted by a combiner combining them.

Z ¹ to Z ⁵ each independently represent a group in the same range as the group represented by Z ¹ to Z ³ in the general formula (2)

* Means combining with adjacent groups in the * part.)

(In the general formula (5), Y ¹⁴ represents an aliphatic hydrocarbon group of 6 to 35 carbon atoms, an aromatic hydrocarbon group of 6 to 35 carbon atoms, or a heterocyclic ring-containing group of 2 to 35 carbon atoms,

The aliphatic hydrocarbon group may be a carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO ₂ -, -CONH- or -NHCO-, In some cases, they are not adjacent to each other but are substituted by a combiner combining them.

Z ¹ to Z ⁶ each independently represent a group in the same range as the group represented by Z ¹ to Z ³ in the general formula (2)

* Means combining with adjacent groups in the * part.)

Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent and represented by R ⁵ , R ⁶ and R ⁷ in the above general formula ( ¹⁾ include those represented by X ¹ in the general formula (IA) the monovalent aliphatic hydrocarbon group exemplified as the n-valent linking group and the monovalent aliphatic hydrocarbon group represented by the formula (IA) in which the group represented by X &^lt; ¹ > , And the like,

Examples of the aromatic ring-containing hydrocarbon group of 6 to 35 carbon atoms which may have a substituent, represented by R ⁵ , R ⁶ and R ⁷ include the same groups as exemplified for the n-valent bond group represented by X ¹ in the formula (IA) Containing monovalent aromatic ring-containing hydrocarbon group, and those groups in which these groups are substituted by the groups exemplified as the substituent of the group representing the bonding group of X &^lt; ^{1 &gt}; represented by the general formula (IA) And the like,

Examples of the heterocyclic group having 2 to 35 carbon atoms, which may have a substituent, represented by R ⁵ , R ⁶ and R ⁷ include 1 to 3 groups exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) Containing heterocyclic group, and groups satisfying the predetermined number of carbon atoms among the groups substituted with those exemplified as the substituent of the group representing the bond of X &^lt; ¹ > in the formula (IA) .

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y ¹ in the general formula (1) include divalent aliphatic hydrocarbons exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) , And those in which the number of carbon atoms of the groups substituted with those exemplified as the substituent of the group denoting the bonding group of n represented by X ¹ in the general formula (IA) is satisfied,

Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 divalent carbon atoms represented by Y ¹ include a divalent aromatic ring-containing hydrocarbon group exemplified as an n-valent bond group represented by X ¹ in the formula (IA) And those satisfying the predetermined number of carbon atoms among the groups substituted as exemplified as the substituent of the group representing the n-valent bonding group represented by X &^lt; ¹ > in the general formula (IA)

Examples of the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by Y ¹ include a divalent aromatic ring-containing hydrocarbon group exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) And those satisfying the predetermined number of carbon atoms among the groups substituted as exemplified as the substituent of the group representing the n-valent bonding group represented by X &^lt; ¹ > in the formula (IA).

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁸ in the substituent represented by the above (1-1) include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl,

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁹ include groups satisfying a predetermined number of carbon atoms among the groups exemplified as alkyl groups having 1 to 40 carbon atoms represented by R ¹ and R ² , ,

Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁹ include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert -butyloxy, isobutyloxy, amyloxy, isoamyl Isobutyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyl, tertiary amyloxy, heptyloxy, heptyloxy, heptyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, Oxy, decyloxy and the like,

The substituent of the phenyl group, the cycloalkyl group, the alkyl group, the alkoxy group and the alkenyl group is the same as those exemplified as the substituent of the n-valent bond group represented by X ¹ in the general formula (IA).

In the group represented by (1-3), the alkyl group having 1 to 10 carbon atoms, which may have a substituent, represented by R ¹⁰ and R ¹¹ is preferably an alkyl group having 1 to 40 carbon atoms represented by R ¹ and R ² A group satisfying a predetermined number of carbon atoms among the groups exemplified as the alkyl group of

Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent and represented by R ¹⁰ and R ¹¹ include groups exemplified as aryl groups having 6 to 20 carbon atoms represented by R ¹ and R ² In addition,

Examples of the aryloxy group having 6 to 20 carbon atoms which may have a substituent and represented by R ¹⁰ and R ¹¹ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4 4-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-cyclohexylphenyloxy, 4-isopropylphenyloxy, 4- Dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,6-dimethylphenyloxy, 2,6-dimethylphenyloxy, 3,4-dimethylphenyloxy, Di-tert-butylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert- Phenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy and the like.

Examples of the arylthio group having 6 to 20 carbon atoms, which may have a substituent, represented by R ¹⁰ and R ¹¹ include an oxygen atom of an aryloxy group having 6 to 20 carbon atoms, which may have the above substituent, Substituted groups, and the like,

As the arylalkenyl group having 8 to 20 carbon atoms, which may have a substituent, represented by R ¹⁰ and R ¹¹ , an oxygen atom of an aryloxy group having 6 to 20 carbon atoms, which may have the above substituent And groups substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-

Examples of the arylalkyl group having 7 to 20 carbon atoms, which may have a substituent, represented by R ¹⁰ and R ¹¹ include the groups exemplified as arylalkyl groups having 7 to 20 carbon atoms represented by R ¹ and R ² However,

Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms, which may have a substituent, represented by R ¹⁰ and R ¹¹ include a group exemplified as a heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹ and R ² .

Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y ¹¹ in the general formula (2) include trivalent aliphatic hydrocarbon groups exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) those groups wherein the general formula (IA) of the group substituted by one exemplified as the substituent of the n-valent couplers represented by X ¹ in, such as to meet the predetermined number of carbon atoms, substituted with Z ^1, Z ² and Z ³ Trivalent group, and the like,

Examples of the trivalent alicyclic hydrocarbon group of 3 to 35 carbon atoms represented by Y ¹¹ in the above general formula (2) include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2 Cyclohexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, Bicyclo [2.1.0] pentyl, bicyclo [3.1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] Bicyclo [4.2.1] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4.2.0] octyl, ] Octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro [4,4] nonanyl, spiro [4,5] decanyl, decalin, Tricyclodecanyl, tetracyclododecanyl, hethrol, cyclododecanyl, and the like. It may be made of a trivalent group, and the like,

Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y ¹¹ include a trivalent aromatic ring-containing hydrocarbon group exemplified as an n-valent bond group represented by X ¹ in the formula (IA) And those satisfying the predetermined number of carbon atoms among the groups substituted by the substituent of the n-valent bonding group represented by X &^lt; ¹ > in the formula (IA)

Examples of the heterocyclic ring-containing group having 3 to 3 carbon atoms represented by Y ¹¹ include a trivalent heterocyclic ring-containing group exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) IA) in which the number of carbon atoms specified in the group substituted by the substituent of the n-valent bond group represented by X &^lt; ¹ > is satisfied.

Further, an aliphatic hydrocarbon group of 1 to 35 carbon atoms which may have a substituent, represented by R ¹² , an aromatic hydrocarbon group of 6 to 35 carbon atoms, which may have a substituent, and an aromatic hydrocarbon group which may have a substituent Examples of the heterocyclic ring-containing group having 2 to 35 carbon atoms include aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups exemplified in the description of R ⁵ , R ⁶ and R ⁷ in the general formula (1) .

Examples of the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y ¹² in the general formula (3) include monovalent to trivalent aliphatic groups exemplified as the linking group of the n-valent group represented by X ¹ in the general formula (IA) A hydrocarbon group and a group satisfying the predetermined number of carbon atoms among the quaternary groups derived from groups substituted by those groups exemplified as the substituent of the n-valent bond group represented by X &^lt; ¹ > in the general formula (IA) Can,

Examples of the aromatic ring-containing hydrocarbon group having 4 to 4 carbon atoms represented by Y ¹² include a monovalent to trivalent aromatic ring-containing hydrocarbon group exemplified as an n-valent bond group represented by X ¹ in the formula (IA) And the group satisfying the predetermined number of carbon atoms among the quadrivalent groups derived from the substituted group as exemplified as the substituent of the n-valent bonding group represented by X &^lt; ¹ > in the general formula (IA)

Examples of the heterocyclic ring-containing group having 4 to 4 carbon atoms represented by Y ¹² include a monovalent to trivalent heterocyclic ring-containing group exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) And examples of the quadrivalent group derived from the substituted group as exemplified as the substituent of the n-valent bonding group represented by X &^lt; ¹ > in the general formula (IA) satisfy the predetermined number of carbon atoms.

Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y ¹³ in the general formula (4) include the monovalent to trivalent aliphatic groups exemplified as the linking group of the n-valent group represented by X ¹ in the general formula (IA) A hydrocarbon group, and a group which satisfies the predetermined number of carbon atoms among the pentavalent groups derived from the substituted groups as exemplified as substituent groups of the n-valent group represented by X ¹ in the general formula (IA) Can,

Examples of the aromatic ring-containing hydrocarbon group having 5 to 5 carbon atoms represented by Y ¹⁴ include a monovalent to trivalent aromatic ring-containing hydrocarbon group exemplified as an n-valent bond group represented by X ¹ in the formula (IA) And the groups satisfying the predetermined number of carbon atoms among the pentavalent groups derived from the substituted groups as exemplified as the substituent of the n-valent bonding group represented by X &^lt; ¹ > in the general formula (IA)

Examples of the heterocyclic ring-containing group having 5 to 5 carbon atoms represented by Y ¹⁴ include a monovalent to trivalent heterocyclic ring-containing group exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) Examples of the substituent of the n-valent bonding group represented by X &^lt; ¹ > in the general formula (IA) include those satisfying the predetermined number of carbon atoms among the pentacyclic groups derived from the substituted group.

The general formula (5) Y ¹⁴ 6-valent aliphatic hydrocarbon group of a carbon atom number of 2-35 represented by in the above general formula (IA) one monovalent ~ aliphatic trivalent illustrated as an n-valent couplers represented by X ¹ in A hydrocarbon group and a group which satisfies the predetermined number of carbon atoms among the six groups represented by the substituent of the group represented by X &^lt; ¹ > in the general formula (IA) Can,

Examples of the aromatic ring-containing hydrocarbon group having 6 to 6 carbon atoms represented by Y ¹⁴ include a monovalent to trivalent aromatic ring-containing hydrocarbon group exemplified as an n-valent bond group represented by X ¹ in the formula (IA) And the groups satisfying the predetermined number of carbon atoms among the six-valent groups derived from the substituted groups exemplified as the substituent of the n-valent bonding group represented by X &^lt; ¹ > in the general formula (IA)

Examples of the heterocyclic ring-containing group having 6 to 6 carbon atoms represented by Y ¹⁴ include a monovalent to trivalent heterocyclic ring-containing group exemplified as an n-valent bond group represented by X ¹ in the general formula (IA) And those having a specified number of carbon atoms among the six-valent groups derived from the substituted group as exemplified as the substituent of the n-valent bonding group represented by X ¹ in the general formula (IA).

Among the compounds represented by the general formula (I-A), the compounds represented by the following general formulas (II-1) to (II-3) are preferable because they have high heat resistance.

(Wherein R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an 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, or a heterocyclic ring-containing group having 2 to 20 carbon atoms, and R ¹ and R ² are the same as in the general formula (I). )

(2) when r = 3 and r = 4 (2) when r = 3, wherein r = 2 to 6 and X ² is a group represented by the general formula (5), and R ⁹² and R ⁹³ are each independently a hydrogen atom or a group represented by the following formula (3) when r = 5, An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 7 to 20 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, An arylalkyl group or a heterocyclic ring-containing group having 2 to 20 carbon atoms, and R ¹ and R ² are the same as in the general formula (I).

(Wherein R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, the number is also carbon atom to which the case has 1 to 40 alkyl group, a heterocyclic ring of carbon atoms from 6 to 20 aryl group, a carbon atom number of 7-20 arylalkyl group or 2 to 20 carbon atoms of the monovalent contained, Y ¹ , Z ¹ and Z ² are the same as in the general formula (1).)

A halogen atom represented by R ⁸² , R ⁸³ and R ⁸⁴ in the general formula (II-1), an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, a carbon Examples of the arylalkyl group having 7 to 20 atoms and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R ¹ and R ² in the general formula (I).

A halogen atom represented by R ⁹² and R ⁹³ in the general formula (II-2), an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon atom number of 7 Examples of the arylalkyl group having 1 to 20 carbon atoms and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R ¹ and R ² in the general formula (I).

A halogen atom represented by R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ in the general formula (II-3) Examples of the alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring containing 2 to 20 carbon atoms include R ¹ and R ² in the general formula (I) As shown in Fig.

Among the compounds represented by the general formula (II-1)

R ¹ is an alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, and R ² is a hydrogen atom; R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom, 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, It is preferable that any one of R ⁸² , R ⁸³ and R ⁸⁴ is an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring-containing group having 1 to 10 carbon atoms.

Among the compounds represented by the above general formula (II-2)

R ¹ is an alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, and R ² is a hydrogen atom; R ⁹² and R ⁹³ each independently represents a hydrogen atom, 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, It is preferable that R ⁹² or R ⁹³ is an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring-containing group having 1 to 10 carbon atoms.

When X ² is that the above-mentioned general formula (1), Y ¹⁰ is the sulfur atom, the number of carbon atoms of 1 to 20 of the alkylene group, containing a divalent aromatic ring of carbon atoms 6-25 hydrocarbon group, the carbon atom to two to A divalent heterocyclic containing group having 1 to 21 carbon atoms, a divalent group derived from 2,4,8,10-tetraoxaspiro [5,5] undecane, particularly an alkylene group having 1 to 15 carbon atoms, A divalent aromatic ring-containing hydrocarbon group of 1 to 15 carbon atoms, and a divalent group derived from 2,4,8,10-tetraoxaspiro [5,5] undecane,

Z ¹ and Z ² are each a direct bond, -CO-O-, -O-CO-, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have a substituent Or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

, 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, or an arylalkyl group having 1 to 10 carbon atoms when X ² is the general formula (2) A trivalent group derived from a heterocyclic-containing group having from 1 to 10 carbon atoms, particularly an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 9 carbon atoms or a heterocyclic-containing group having from 1 to 6 carbon atoms Preferably,

Z ¹ , Z ² and Z ³ are preferably the same as Z ¹ and Z ² ,

When X ² is the above-described general formula (3), Y ¹² is preferably a quadrivalent group corresponding to the above-mentioned group as Y ¹¹ ,

Z ¹ to Z ⁴ are preferably the same as Z ¹ and Z ² ,

When X ² is the above general formula (4), Y ¹³ is preferably a five-valent group corresponding to the above-mentioned group as Y ¹¹ ,

Z ¹ to Z ⁵ are preferably the same as Z ¹ and Z ² ,

When X ² is the above-mentioned general formula (5), Y ¹⁴ is preferably a group having a hexadecane corresponding to the above-mentioned group as Y ¹¹ ,

Z ¹ to Z ⁶ are preferably the same as Z ¹ and Z ² .

Among the compounds represented by the above general formula (I), preferred compounds are those represented by the following formulas, but the present invention is not limited to these compounds.

The method for producing the compound having a substituent represented by the general formula (I) is not particularly limited, and examples thereof include compounds described in JP-A-57-111375, JP-A-3-173843, JP- Obtained by reacting a phenol compound prepared by the method described in each publication of Japanese Patent Application Laid-Open No. 7-206771, No. 7-252191 and Japanese Patent Publication No. 2004-501128 with a halogenated allyl compound or the like have.

The compound having a substituent represented by the general formula (I) can be used as a latent additive in the photosensitive composition of the present invention.

The latent additive is inert in a pre-baking process at room temperature or below 150 ° C, for example below 150 ° C, heated to 100-250 ° C or heated to 80-200 ° C in the presence of an acid / base catalyst Whereby the protecting group is released and becomes active.

The content of the compound having a substituent represented by the general formula (I) as a latent additive in the photosensitive composition of the present invention is preferably from 0.001 to 20 mass%, more preferably from 0.005 to 5 mass%, of the solid content of the composition of the present invention desirable.

The photosensitive composition of the present invention is a composition whose properties are changed by light irradiation and is a positive resist which is soluble to a chemical reaction and a negative resist which is insoluble to a chemical reaction Type resist. The photosensitive composition of the present invention contains, as a latent antioxidant, a compound having a substituent represented by the general formula (I) above, a polymerizable compound having an acidic unsaturated bond and a photoradical polymerization initiator, .

Examples of the polymerizable compound having an ethylenic unsaturated bond having an acid value include (meth) acrylic acid,? -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hemiamic acid, crotonic acid, isocrotonic acid, (Meth) acrylate, mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (metha) acrylate, cinnamic acid, sorbic acid, (Meth) acrylate, hydroxyethyl (meth) acrylate, maleate, hydroxypropyl (meth) acrylate, maleate, and dicyclopentyl (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, Unsaturated polybasic acids such as chloropentadiene maleate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; Novolak type epoxy compounds such as phenol and / or cresol novolak epoxy resin, biphenyl skeleton, novolak epoxy resin having naphthalene skeleton, bisphenol A novolak type epoxy compound and dicyclopentadiene novolak type epoxy compound, polyfunctional A polyphenylmethane type epoxy resin having an epoxy group, an epoxy compound represented by the following general formula (III), a resin obtained by allowing an unsaturated monobasic acid to act on the epoxy group of the epoxy resin, an unsaturated monobasic acid to the epoxy group of the epoxy resin, A resin obtained by reacting a polybasic acid anhydride with a hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like, and acidic acid which is a reaction product of a dibasic acid anhydride such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride , And the like.

(Wherein X ⁴¹ represents a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, or a substituent represented by the above-mentioned (1-1)

R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms An alkenyl group having 2 to 5 carbon atoms which may have a substituent, or a halogen atom,

and m is an integer of 0 to 10.)

The polymerizable compounds having an ethylenic unsaturated bond having these acid values can be used alone or in combination of two or more kinds and can be used in combination with a polymerizable compound having an ethylenically unsaturated bond having no acid value. When two or more of them are mixed and used, they may be copolymerized in advance and used as a copolymer.

In the photosensitive composition of the present invention, the content of the polymerizable compound having an acid value and having an ethylenically unsaturated bond is preferably from 20 to 80 mass% in the solid content of the composition of the present invention, more preferably from 30 to 70 mass% .

Examples of the polymerizable compound having an ethylenically unsaturated bond having no acid value include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) , The following compounds No. A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t- butyl (meth) acrylate, cyclohexyl stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl , Ethylhexyl (meth) acrylate, (meth) acrylic acid (Meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, trimethylol ethane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as acrylate oligomers; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) Acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl ansuccinic acid, and anhydrous methyl hemiamic acid; (Meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriamintris (meth) acrylamide, xylylenebis (meth) acrylamide, alpha -chloroacrylamide, N-2-hydroxyethyl Amides of unsaturated monobasic acids and polyamines such as methacrylamide; Unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile,? -Chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Vinylbenzene sulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, and vinylbenzenesulfonic acid. Unsaturated aromatic compounds such as vinylbenzyl methyl ether and vinyl benzyl glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Indene such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers 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 and polysiloxane; (Meth) acrylonitrile, other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomers and polystyrene macromonomers, monocarboxylic acids such as monocyclohexane Methacrylate, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc., and copolymers of (meth) acrylic acid, and unsaturated compounds such as car lenses MOI and AOI of Showa Denko Co., A copolymer of (meth) acrylic acid in which an isocyanate compound having a bond is reacted and a copolymer of vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphite, triallyl isocyanurate, vinyl thioether, vinyl Imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and polyisocyanate compounds Containing vinyl monomers and vinyl epoxy compounds of polyepoxy compounds, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and other hydroxyl group-containing polyfunctional acrylates, tolylene diisocyanate, hexamethylene diisocyanate, and the like And a reaction product of a polyfunctional isocyanate.

In order to improve the developability of the photosensitive composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound may be used together with the polymerizable compound having an acid value and having an ethylenically unsaturated bond. The polymerizable compound having an acid value and having an ethylenic unsaturated bond preferably has an acid value of 5 to 120 mg KOH / g as the solid content, and the amount of the monofunctional or polyfunctional epoxy compound used is selected so as to satisfy the above acid value .

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, Butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether Ethylhexyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-ethylhexyl glycidyl ether, Propyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butyl phenol glycidyl ether, cresyl glycidyl ether Diester, 2-methylcresylglycidyl ether, 4 - nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, Vinyl cyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide and the like .

As the polyfunctional epoxy compound, use of at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers is preferable because a photosensitive composition having better characteristics can be obtained. As the bisphenol-type epoxy compound, for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can be used besides the epoxy compound represented by the general formula (III). Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, tri Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (Glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) ethane, 1,1,1- Dioxymethyl) methane.

In addition, novolak type epoxy compounds such as phenol novolak type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds and dicyclopentadiene novolak type epoxy compounds; Epoxy cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl Alicyclic epoxy compounds such as 3,4-epoxycyclohexane; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and dimeric acid glycidyl ester; Glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; A dioxide compound such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, and the like.

The photo radical polymerization initiator may be any compound which can initiate radical polymerization by being irradiated with light. For example, it may be a ketone compound such as an acetophenone compound, a benzyl compound, a benzophenone compound or a thioxanthone compound , Oxime-based compounds, and the like can be exemplified as preferable ones.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy- , 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p- tertiary butyldichloroacetone Phenocone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo Phenyl-2-hydroxy-2-methyl-1-propan-1-one, and the like can be given. have.

Examples of the benzyl compound include benzyl and anisyl.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, '-Methyldiphenyl sulfide and the like.

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

As the oxime-based compound, a compound represented by the following general formula (IV) or (V) is particularly preferable in view of sensitivity and heat resistance.

(Wherein R ⁵¹ and R ⁵² each independently represents a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 6 to 30 carbon atoms An aryl group, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic ring-containing group having 2 to 20 carbon atoms, which may have a substituent,

R ⁵³ and R ⁵⁴ each independently represents a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ⁵⁵ , OR ⁵⁶ , SR ⁵⁷ , NR ⁵⁸ R ⁵⁹ , COR ⁶⁰ , SOR ⁶¹ , SO ₂ R ⁶² or CONR ⁶³ R ⁶⁴ , R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring,

R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms, which may have a substituent, or a heterocyclic ring having 2 to 20 carbon atoms, which may have a substituent Containing group,

X ³ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁷⁵ R ⁷⁶ , CO, NR ⁷⁷ or PR ⁷⁸ ,

X ⁴ represents a single bond or CO,

R ⁷⁵ to R ⁷⁸ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and the methylene group in the alkyl or arylalkyl group may be substituted with a halogen atom, A nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic ring-containing group, or may be substituted with -O-,

R ⁵³ and R ⁵⁴ are each independently a monovalent aromatic hydrocarbon group which may be bonded to any adjacent benzene ring to form a ring,

a represents an integer of 0 to 4,

and b represents an integer of 0 to 5.)

(Wherein R ¹⁰¹ and R ¹⁰² each independently represent R ¹¹¹ , OR ¹¹¹ , COR ¹¹¹ , SR ¹¹¹ , CONR ¹¹² R ¹¹³ or CN,

R ¹¹¹ , R ¹¹² and R ¹¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, A heterocyclic ring-containing group having 1 to 20 carbon atoms,

R ^111, a hydrogen atom of the group represented by R ¹¹² and R ¹¹³ are, and ^{R 121, OR 121, COR 121} , SR 121, NR 122 R 123, CONR 122 R 123, -NR 122 -OR 123, -NCOR 122 - OCOR ¹²³ , NR ¹²² COR ¹²¹ , OCOR ¹²¹ , COOR ¹²¹ , SCOR ¹²¹ , OCSR ¹²¹ , COSR ¹²¹ , CSOR ¹²¹ , hydroxyl, nitro, CN,

R ¹²¹ , R ¹²² and R ¹²³ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, A heterocyclic ring-containing group having 1 to 20 carbon atoms,

The hydrogen atom of the group represented by R ¹²¹ , R ¹²² and R ¹²³ may also be substituted with a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,

The alkylene moiety of the group represented by R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹²¹ , R ¹²² and R ¹²³ is preferably -O-, -S-, -COO-, -OCO-, -NR ¹²⁴ -, -NR ^{124 COO-, -OCONR 124 -, -SCO-,} -COS-, -OCS-, or -CSO- case by which is substituted 1-5 times under the conditions that do not neighbor each other, an oxygen atom, and also,

R ¹²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms,

The alkyl moiety of the group represented by R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ may have a branched side chain or may be a cyclic alkyl,

R ¹⁰³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms, R the alkyl portion of the group represented by ¹⁰³ is also the case of FIG., and cyclic alkyl If a branch chain, and, R ¹⁰³ and R ^107, R ¹⁰³ and R ^108, R ¹⁰⁴ and R ^105, R ¹⁰⁵ and R ^106, and R ¹⁰⁶ and R ¹⁰⁷ may be a single ring to form a ring,

The hydrogen atoms of the group represented by R ^103, also ^{R 121, OR 121, COR 121} , SR 121, NR 122 R 123, CONR 122 R 123, -NR 122 -OR 123, -NCOR 122 -OCOR 123, NR 122 COR COOR ¹²¹ , OCOR ¹²¹ , COOR ¹²¹ , SCOR ¹²¹ , OCSR ¹²¹ , COSR ¹²¹ , CSOR ¹²¹ , hydroxyl, nitro, CN, halogen atoms, or COOR ¹²¹ ,

R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ are each independently selected from the group consisting of R ¹¹¹ , OR ¹¹¹ , SR ¹¹¹ , COR ¹¹⁴ , CONR ¹⁵¹ R ¹¹⁶ , NR ¹¹² COR ¹¹¹ , OCOR ¹¹¹ , COOR ¹¹⁴ , SCOR ¹¹¹ , OCSR ¹¹¹ , COSR ¹¹⁴ , CSOR ¹¹¹ , hydroxyl group, CN or a halogen atom; R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁵ and R ^106, and R ¹⁰⁶ and R ¹⁰⁷ are taken together to form a ring,

R ¹¹⁴ , R ¹¹⁵ and R ^{116 each} represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

R ¹⁰⁸ is selected from the group consisting of R ¹¹¹ , OR ¹¹¹ , SR ¹¹¹ , COR ¹¹¹ , CONR ¹¹² R ¹¹³ , NR ¹¹² COR ¹¹¹ , OCOR ¹¹¹ , COOR ¹¹¹ , SCOR ¹¹¹ , OCSR ¹¹¹ , COSR ¹¹¹ , CSOR ¹¹¹ , Lt; / RTI >

w represents 0 or 1.)

Examples of other photo radical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1- ] Titanium and the like.

These photoradical polymerization initiators may be used alone or in combination of two or more thereof according to the desired performance.

The content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the photosensitive composition of the present invention. If the content of the photo radical polymerization initiator is less than 0.1% by mass, the curing by exposure may become insufficient, and if it is more than 30% by mass, the initiator may precipitate in the photosensitive composition.

The photosensitive composition of the present invention may also be made into a colored photosensitive composition by adding a colorant. The cured product of the colored photosensitive composition is suitably used as a color filter.

In the colored photosensitive composition of the present invention, the amount of the colorant to be added is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass in the solid content of the colored photosensitive composition of the present invention. If the content of the coloring agent is less than 0.01% by mass, a desired chromaticity may not be obtained. If the content is more than 50% by mass, the coloring agent may be precipitated in the colored photosensitive composition.

Examples of the colorant include a dye and a pigment.

The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm, and examples thereof include azo compounds, anthraquinone compounds, indigoid compounds, triarylmethane compounds, xanthene compounds, alizarin compounds, , Stilbene compounds, thiazole compounds, naphthol compounds, quinoline compounds, nitro compounds, indanamine compounds, oxazine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanoethenyl compounds, dicyanostyrene compounds, rhodamine compounds , A perylene compound, a polyene naphtholactam compound, a coumarin compound, a squarylium compound, a croconium compound, a spiropyran compound, a spirooxazine compound, a merocyanine compound, an oxolin compound, a styryl compound, A compound, an oxazolone compound, a phthalimide compound, a cinnoline compound, a naphthoquinone compound, A quinacridone compound, a quinacridone compound, a diketopyrrolopyrrole compound, an indigo compound, an acridine compound, an azine compound, an azomethine compound, an aniline compound, a quinacridone compound, a quinacridone compound, A dyes such as a thallone compound, a quinone imine compound, an iridium complex compound, and a europium complex compound, and these may be used in combination.

As the pigment, an inorganic pigment or an organic pigment can be used. Examples of the pigment include a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, A quinacridone compound, an anthanthrone compound, a perinone compound, a perylene compound, a diketopyrrolopyrrole compound, a thioindigo compound, a dioxazine compound, a triphenylmethane compound, a quinophthalone compound, Naphthalene tetracarboxylic acid; Azo dyes, metal complex compounds of cyanine dyes; Lake pigment; Carbon black obtained by a furnace method, a channel method, and a thermal method, or carbon black such as acetylene black, Kechen black or lamp black; The carbon black is adjusted and coated with an epoxy resin. The carbon black is dispersed in a solvent in advance in a solvent to adsorb a resin of 20 to 200 mg / g. The carbon black is subjected to an acidic or alkaline surface treatment , An average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen amount calculated from CO and CO ₂ in a volatile fraction 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 airgel, fullerene; Aniline black, pigment black 7, titanium black; Cobalt blue, manganese, ferrocyanide, phosphates, tungsten, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, yellow Inorganic pigments or organic pigments such as lead, zinc sulfur, spinach (red iron oxide (III)), cadmium red, synthetic iron black and amber may be used. These pigments may be used singly or in combination.

As the inorganic pigment or organic pigment, commercially available pigments may be used. 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, , 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 and the like.

A solvent may also be added to the photosensitive composition and the colored photosensitive composition of the present invention. The solvent is usually a solvent capable of dissolving or dispersing the above components such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone , Cyclohexanone, and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, amyl alcohol and diacetone alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, Ether-based solvents such as 1-t-butoxy-2-propanol, 3-methoxybutyl acetate and cyclohexanol acetate; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene type hydrocarbon oils such as turpentine oil, D-limonene, and pinene; Paraffin type solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu Co., Ltd.) and Solvesso # 100 (Exxon Kagaku Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; A solvent such as acetone, acetonitrile, carbon dioxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water These solvents can be used singly or as a mixed solvent of two or more kinds. Of these, ketones, ether ester solvents and the like, especially propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone, are preferred because they have good compatibility between the resist and the photo-radical polymerization initiator in the photosensitive composition Do. When a solvent is used, it is preferable to use the solvent in an amount such that the solid content of the photosensitive composition or colored photosensitive composition of the present invention is 25 to 35% by mass from the viewpoint of handling and the like.

The photosensitive composition and the colored photosensitive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; The present invention relates to a method for producing a cement admixture, which comprises the steps of mixing a cement admixture with a cement admixture to form a layered clay mineral, a milky blue, a calcium carbonate, a magnesium carbonate, a cobalt, Silicate, aluminum hydroxide, platinum, gold, silver, copper and the like.

When a colorant such as a pigment and / or an inorganic compound is used in the photosensitive composition and the colored photosensitive composition of the present invention, a dispersant may be added. The dispersion agent is not particularly limited as long as it can disperse and stabilize the colorant and the inorganic compound. Commercial dispersants such as BYK series and BYK series can be used. Polyesters having basic functional groups, polyether , A polymeric dispersant composed of polyurethane, a functional group having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom, an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g are suitably used.

The photosensitive composition and the colored photosensitive composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine and the like; Plasticizers; Adhesion promoters; Fillers; Defoamer; Leveling agents; Surface modifiers; Antioxidants such as phenol-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants; Ultraviolet absorber; Dispersing aids; An anti-aggregation agent; catalyst; Effect promoters; A crosslinking agent; A common additive such as a thickener may be added.

The properties of the cured product of the photosensitive composition and the colored photosensitive composition of the present invention may be improved by using another organic polymer together with the polymerizable compound having an acid value and having an ethylenic 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, Acrylonitrile, 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, Among them, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. Among them, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, desirable.

A chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like may be used in combination in the photosensitive composition and the colored photosensitive composition of the present invention.

As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. 3-mercaptopropionic acid, N- (2-mercaptopropionyl) glycine, 2-mercapto nicotinic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid and the like are exemplified by thioglycolic acid, thiomalic acid, thiosalicylic acid, 2- mercaptopropionic acid, - [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid , 3-mercaptopropane sulfonic acid, 4-mercaptobutane sulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto- 2-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol, 2 -Mercapto benzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptopropionate). Mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, alkyl iodides such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid, trimethylolpropane tris (3- Mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisstiouropionate, butanediol bisthioglycolate, ethylene Trimethylolpropane trisphosphate, glycol bistioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiouropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, Ritol tetrakis thioglycolate, tris hydroxyethyl tris Aliphatic polyfunctional thiol compounds such as trimethylolpropane tri (meth) acrylate, trimethylolpropane tris (2-hydroxyethyl) isocyanurate and the like, car lenses MT BD1, PE1, NR1 and the like manufactured by Showa Denko Co., .

Examples of the surfactant include fluorine surfactants such as perfluoroalkylphosphoric acid esters and perfluoroalkylcarboxylic acid salts, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, higher amine halides, A surfactant such as a nonionic surfactant such as a polyethylene glycol alkyl ether, a polyethylene glycol fatty acid ester, a sorbitan fatty acid ester, a fatty acid monoglyceride, an amphoteric surfactant, or a silicone surfactant may be used as a cationic surfactant, And they may be used in combination.

Examples of the silane coupling agent include silane coupling agents such as KBE-9007, KBM-502 and KBE-403, which are available from Shin-Etsu Chemical Co., Ltd. Among these, silane coupling agents having an isocyanate group, a methacryloyl group, Silane coupling agents are suitably used.

With the melamine compound, the (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzo guar active methylol group of the nitrogen compounds, such as namin, (poly) methylol urea (CH ₂ OH groups) (At least two) of all or some of them are alkyl-etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same or different. In addition, the methylol group which is not alkyl-etherified may be self-condensed in one molecule, and may be condensed between two molecules, resulting in formation of an oligomer component. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Of these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

The photosensitive composition and the colored photosensitive composition of the present invention can be suitably used in various applications such as a soda glass, a quartz glass, a semiconductor substrate, a metal, a paper, a plastic And the like. Alternatively, the film may be once transferred onto a support such as a film, and then transferred onto another support. There is no limitation on the application method.

As the light source of active light used for curing the photosensitive composition and the colored photosensitive composition of the present invention, those emitting light having a wavelength of 300 to 450 nm can be used. For example, ultra violet mercury vapor, mercury vapor arc, carbon arc , Xenon arc, etc. can be used.

Further, by using the laser light for the exposure light source, the laser direct drawing method for forming an image directly from digital information such as a computer without using a mask can improve not only productivity but also resolution and positional accuracy Light having a wavelength of 340 to 430 nm is suitably used as the laser beam, and a laser beam having a wavelength of 340 to 430 nm is suitably used. The laser beam is emitted in a visible to infrared region such as an argon ion laser, a helium neon laser, a YAG laser, Is also used. In the case of using these lasers, a sensitizing dye which absorbs the above-mentioned infrared region in visible is added.

The photosensitive composition and the colored photosensitive composition of the present invention may be subjected to patterning through a double patterning process in which two photosensitive compositions or colored photosensitive compositions are used to perform patterning in two portions.

The method of curing the photosensitive composition or the colored photosensitive composition of the present invention can be carried out by a known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, On a support such as metal, paper or plastic to form a coating film, and a step of exposing the coating film to the active light to cure the coating film.

The photosensitive composition and the colored photosensitive composition (or a cured product thereof) of the present invention can be used as a light-curable coating material or an adhesive such as a varnish or a photocurable adhesive, a printed substrate, or a color display such as a color TV, a PC monitor, a portable information terminal, A color filter in a liquid crystal display panel of a CCD image sensor, a color filter of a CCD image sensor, a photo spacer, a black column spacer, an electrode material for a plasma display panel, a touch panel, a touch sensor, a powder coating, a printing ink, a printing plate, The present invention relates to a method of manufacturing a color filter for a resin, a gel coat, a photoresist for electronic engineering, an electroplating resist, an etching resist, a liquid and a dried film, a solder resist and various display applications, or a plasma display panel, A resist for forming a structure in a manufacturing process, a composition for enclosing electric and electronic parts, , A magnetic recording medium, a microscopic mechanical part, a waveguide, an optical switch, a plating mask, an etching mask, a color test system, a glass fiber cable coating, a stencil for screen printing, a stereolithography Decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible light materials, materials for holographic recording, image recording materials, A photoresist material for forming a dielectric layer in a laminated layer of a printed circuit board, a photoresist material for a 3D mounting, a protective film, and the like, and the use thereof is not particularly limited none.

The photosensitive composition of the present invention can be used as a transparent structure by curing. As the transparent structure, for example, a photo-spacer (PS), a mold (columnar body) called a column spacer (CS); (Nano) fine pattern of imprint; A large advertising signboard and the like, and an ink-jet receiving layer used for manufacturing electronic devices such as color filters for liquid crystal displays and printing of alignment films. The transparent structure of the present invention is suitably used for a display device.

The photosensitive composition of the present invention can be used for a transparent conductive film, a reflective film, a polarizing plate, a protective film and the like, and it is preferable that each desired layer is sequentially coated on a transparent substrate, active light is irradiated through a mask having a predetermined pattern shape, Developing with a developing solution, and heating the film after development to form a laminated transparent laminate. As the transparent laminate, for example, a transparent thin film layer composed of a composite oxide of indium oxide and cerium oxide and a metal thin film layer alternating with each other can be cited. The photosensitive composition of the present invention containing as a latent additive a compound having a substituent represented by the general formula (I) in each of the above-mentioned respective layers may be used, or the photosensitive composition may be used in any one layer. Further, the transparent laminate is suitably used for a display device.

The colored photosensitive composition of the present invention is used for forming a pixel of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel.

(1) a step of forming a coating film of the colored photosensitive composition of the present invention on a substrate, (2) a step of irradiating the coating film with active light via a mask having a predetermined pattern shape, (3) ) A step of developing the film after exposure with a developer, and (4) a step of heating the film after development. Further, the colored photosensitive composition of the present invention is also useful as an inkjet type colored photosensitive composition free from a development process.

As the mask, a multi-gradation mask such as a halftone mask or a gray-scale mask may be used.

Next, the novel compounds of the present invention will be described. The novel compounds of the present invention are represented by any one of the following structures.

The method for producing the novel compound of the present invention is not particularly limited, and examples thereof include compounds described in JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, -206771, JP-A-7-252191, and JP-A-2004-501128, with a halogenated allyl compound or the like.

The novel compounds of the present invention can be used as latent antioxidants, latent ultraviolet absorbers, dissolution regulators, and the like.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and the like, but the present invention is not limited to these Examples and the like.

[Example 1-1] Synthesis of Compound No. 1

Potassium carbonate (2 equivalents based on one phenol group) was added to a 1-equivalent dimethylacetamide solution (three times the theoretical yield) of the phenol compound of the following compound No. 1 ', and the mixture was stirred at room temperature for 30 minutes. Allyl bromide (1.5 equivalents based on one phenol group) was added, and the mixture was stirred at 60 占 폚 for 5 hours. Ethyl acetate was added thereto, followed by washing with a 1% hydrochloric acid solution, followed by water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and crystallization was carried out. The obtained solid was dried under reduced pressure at 60 DEG C for 3 hours to obtain a target product. It was confirmed by ¹ H-NMR and IR that the obtained solid was the target. The results are shown in [Table 1] to [Table 2].

[Examples 1-2 to 1-6] Synthesis of Compound No. 2 to 6

The procedure of Example 1-1 was repeated except that the phenol compound of the following compound Nos. 2 'to 6' was used instead of the phenol compound of the following compound No. 1 ' ~ 6 were synthesized. It was confirmed by ¹ H-NMR and IR that the obtained solid was the target. The results are shown in [Table 1] to [Table 2].

[Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-3] Preparation of Photosensitive Composition Nos. 1 to 2 and Comparative Photosensitive Compositions No. 1 to 3

50.0 g of SPC-1000 (a PGMEA solution having a solid content of 29%, manufactured by Showa Denko K.K.), 11.6 g of Aronix M-450 (manufactured by Doagosei Co., Ltd.), 0.3 g of NCI-930 (manufactured by ADEKA), 34.7 g of PGMEA, (PGMEA solution, solid content 1%) and 0.81 g of the compound described in [Table 3] were mixed and stirred until the insolubles disappeared. Thus, Photosensitive Composition No. 1 to No. 2 and Comparative Photosensitive Composition Nos. 1 to 3 were obtained.

[Evaluation Example 1-1 and Comparative Evaluation Example 1-1] Outgassing evaluation

5 mg of each of Compound No. 1, Compound No. 2 and Comparative Compound No. 2 was weighed, and the mixture was heated to room temperature (230 ° C) (20 ° C / min.) With a thermogravimeter and maintained at 230 ° C for 30 minutes The weight loss rate at one point in time was measured to give an outgass evaluation of Photosensitive Composition Nos. 1 to 2 and Comparative Photosensitive Composition No. 2. The smaller the weight loss is, the less the outgass is. The results are shown in Table 4.

From the above results, it is apparent that the compound according to the present invention has little outgas, and the photosensitive composition of the present invention containing the compound according to the present invention has a small outgass.

[Evaluation Example 2-1 and Comparative Evaluation Examples 2-1 to 2-2] Evaluation of solvent resistance

The photosensitive composition No. 1 obtained in Example 2-1 and the comparative photosensitive compositions No. 1 and No. 3 obtained in Comparative Examples 2-1 and 2-3 were coated on a glass substrate under the conditions of 410 rpm x 7 seconds, The plate was dried (90 DEG C x 90 seconds). The obtained coating film was exposed (40 mJ / cm 2) with an ultra-high pressure mercury lamp. The coated film after the exposure was fired at 230 캜 for 30 minutes. The film thickness of the obtained coating film was measured and then immersed in PGMEA, cyclohexanone, N-methylpyrrolidone and N-ethylpyrrolidone at room temperature for 30 minutes, and the film thickness after immersion was measured. The solvent resistance was evaluated to be higher as the film thickness ratio before and after immersion (film thickness after immersion × 100 / film thickness before immersion) was closer to 100%.

[Table 5] shows that the cured product of the comparative photosensitive composition No. 1 containing the conventional phenolic antioxidant has a lower solvent resistance than the cured product of the comparative photosensitive composition No. 3 containing no antioxidant, It is clear that the photosensitive composition No. 1 using the compound according to the present invention as a latent additive maintains the same solvent resistance as that in the case of not containing the antioxidant.

From the above results, it is apparent that the photosensitive composition using the compound of the present invention as a latent additive has little outgas, and the cured product has excellent solvent resistance.

According to the present invention, it is possible to provide a photosensitive composition which is inert at room temperature and which is activated by heating at a predetermined temperature to produce a compound that exhibits a function as an antioxidant or an ultraviolet absorber and has low outgassing and high solvent resistance of the cured product.

Claims (9)

A photosensitive composition comprising a compound having a substituent represented by the following general formula (I).

(Wherein R ¹ and R ² each independently represent 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, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, which may have a substituent, a heterocyclic ring-containing group having 2 to 20 carbon atoms, which may have a substituent, or A trialkylsilyl group,
The methylene group in the alkyl group or arylalkyl group represented by R ¹ and R ² is preferably -O-, -S-, -CO-, -O-CO-, -CO-O-, -O- -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, -SS- or -SO ₂ - may be substituted with a group in which oxygen atoms are not adjacent to each other, and R 'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
j represents a number of 1 to 3,
* Means combining with adjacent groups in the * part.) The method according to claim 1,
Wherein the compound having a substituent represented by the general formula (I) is a compound represented by the following general formula (IA).

(Wherein n represents an integer of 1 to 10,
X ¹ represents an n-valent coupler,
R ¹ , R ² and j are the same as in the general formula (I).) A cured product of the photosensitive composition according to any one of claims 1 to 3. A display device comprising at least a part of a transparent laminate or a transparent structure formed by using the cured product according to claim 3. A colored photosensitive composition comprising the photosensitive composition according to any one of claims 1 to 3, further comprising a colorant. A cured product of the colored photosensitive composition according to claim 5. A color filter formed using the cured product according to claim 6. A process for producing a photosensitive composition, comprising the steps of applying the photosensitive composition described in claim 1 or 2 or the colored photosensitive composition of claim 5 on a support to form a coating film, and a step of exposing the coating film to active light to cure Or the photosensitive composition according to claim 2 or the colored photosensitive composition according to claim 5 is cured. A novel compound represented by any one of the following structures (A) to (O).