KR101725262B1 - Colored photosensitive resin composition - Google Patents

Abstract

(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F)
Wherein the colorant (A) comprises both of the dye (A-1) and the pigment (A-2) comprising a compound represented by the formula (1)
The surfactant (F) is a surfactant having a fluorine atom and / or a silicon atom,
Wherein the content of the surfactant (F) is 0.0005 parts by mass or more and 0.3 parts by mass or less based on 100 parts by mass of the colored photosensitive resin composition.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition.

The conventional photosensitive resin composition contains a pyrazole-based squarylium compound as a dye and a blue pigment Pigment Blue (P.B) 15: 6 as a pigment (for example, Patent Document 1, etc.).

However, in the coating film obtained using this photosensitive resin composition, the brightness and the flatness were not sufficient in some cases.

[Patent Document 1]

Japanese Patent Application Laid-Open No. 2006-79012

It is another object of the present invention to provide a colored photosensitive resin composition which can improve the brightness and flatness of a coating film (coating film).

[One]. (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F)

Wherein the colorant (A) comprises both of a dye (A-1) and a pigment (A-2) containing a compound represented by the formula (1)

Wherein the surfactant (F) is a surfactant having a fluorine atom and / or a silicon atom and the content of the surfactant (F) is 0.0005 parts by mass or more and 0.3 parts by mass or less based on 100 parts by mass of the colored photosensitive resin composition .

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms A halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or -SO ₂ N (R ⁸ ) R ⁹ .

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ Or it represents a ^{_{-SO 2 N (R 8) R}} 9.

m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.

X represents a halogen atom. a represents an integer of 0 or 1;

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms. -CH ₂ - contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with -O-, -CO- or -NR ⁷ -.

R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.

R ⁸ and R ⁹ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Or R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms. The alkyl group and the hydrogen atom contained in the cycloalkyl group may be substituted with a halogen atom, -OH, -Q, -CH = CH ₂ or -CH = CHR ⁶ .

The alkyl group and -CH ₂ - contained in the cycloalkyl group may be substituted with -O-, -CO-, -NH- or -NR ⁶ -. The hydrogen atom contained in the heterocycle having 1 to 10 carbon atoms may be substituted with -R ⁶ , -OH or -Q.

Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 5 to 10 member rings and the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is halogen An atom, -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH═CH ₂ or -CH═CHR ⁶ .

M represents a sodium atom or a potassium atom.

However, the number of + electric charges and the number of electric charges of the compound represented by formula (1) are the same.]

[2]. The composition according to [1], wherein the ratio of the content of the dye (A-1) to the content of the pigment (A-2) is from 1:99 to 99: 1.

[3]. When the pigment (A-2) is C.I. The composition according to [1] or [2], which is a pigment containing Pigment Blue 15: 6.

[4]. The composition according to any one of [1] to [3], wherein the solvent (E) is a solvent containing one kind of a hydroxyl group-containing solvent.

[5]. A coloring pattern formed using the composition according to any one of [1] to [4].

[6]. A color filter containing a coloring pattern according to [5].

[7]. The color filter according to [6], which is formed by photolithography.

[8]. A liquid crystal display device comprising the color filter according to [6] or [7].

[9]. Use of the composition according to any one of [1] to [4] for producing a color filter.

The colored photosensitive resin composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F).

In the present specification, examples of the substituents described later are the same as in any of the chemical structural formulas, although they vary depending on the number of carbon atoms, unless otherwise specified. Incidentally, any of those capable of taking both of a straight chain and a branch may be included.

The colorant (A) includes both a dye (A-1) containing a compound represented by the formula (1) and a pigment (A2).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms A halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or -SO ₂ N (R ⁸ ) R ⁹ .

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ Or it represents a ^{_{-SO 2 N (R 8) R}} 9.

m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.

X represents a halogen atom. a represents an integer of 0 or 1;

R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms. -CH ₂ - included in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with -O-, -CO- or -NR ⁷ -.

R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.

R ⁸ and R ⁹ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Or R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms. The alkyl group and the hydrogen atom contained in the cycloalkyl group may be substituted with a halogen atom, -OH, -Q, -CH = CH ₂ or -CH = CHR ⁶ .

The alkyl group and -CH ₂ - contained in the cycloalkyl group may be substituted with -O-, -CO-, -NH- or -NR ⁶ -. The hydrogen atom contained in the heterocycle having 1 to 10 carbon atoms may be substituted with -R ⁶ , -OH or -Q.

Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 5 to 10 member rings and the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is preferably a halogen atom and is optionally substituted by ^{-OH, -R 6, -OR 6,} -NO 2, -CH = CH 2 or -CH = CHR ^6.

M represents a sodium atom or a potassium atom.

However, the number of + electric charges and the number of electric charges of the compound represented by formula (1) are the same.]

Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an aryl group substituted with an alkyl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the aryl group substituted with an alkyl group include those in which the above-mentioned aryl group is optionally combined with the alkyl group shown below.

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

The saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group obtained by arbitrarily combining these substituents, or an alkyl group substituted with a cycloalkyl group.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, Propyl group, a 1,2-dimethylpropyl group, a 1-methylpropyl group, a 1-methylpropyl group, a 1-methylpropyl group, a 1-methylbutyl group, Dimethylpropyl group, and 2,2-dimethylpropyl group.

Examples of the cycloalkyl group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecanyl group.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, Propyloxy group, 2-methylpropoxy group, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, A 1,2-dimethylpropoxy group, a 2,2-dimethylpropoxy group, and the like.

The heterocyclic group may be aromatic or non-aromatic.

As the aromatic heterocyclic group,

As the heterocyclic ring having no aromaticity,

And the like. In addition, the combined hand of the complex ventilation can be set at any position other than the above-mentioned position.

Examples of -OR ⁶ include an alkoxy group such as a methoxy group, ethoxypropoxy group, butoxy group, hexyloxy group, and 2-ethylhexyloxy group.

Examples of -CO ₂ R ⁶ include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxy A cyclohexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cycloheptyloxycarbonyl group, a cycloheptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a cyclooctyloxycarbonyl group, a nonyloxycarbonyl group, a decanyloxycarbonyl group, a tricyclodecanyl An oxycarbonyl group, a methoxypropyloxycarbonyl group, an ethoxypropyloxycarbonyl group, a hexyloxypropyloxycarbonyl group, a 2-ethylhexyloxypropyloxycarbonyl group, and a methoxyhexyloxycarbonyl group.

Examples of -SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

Examples of R ⁹ is ^{_{-SO 2 N (R 8) R}} 9 ( that is -SO ₂ NHR ⁸⁾ a hydrogen atom, a sulfamoyl group, N- (methyl) sulfamoyl, N- (ethyl) sulfamoyl group, N- (Propyl) sulfamoyl group, N- (isopropyl) sulfamoyl group, N- (butyl) sulfamoyl group, N- (isobutyl) sulfamoyl group, N- ), Sulfamoyl group, N- (neopentyl) sulfamoyl group, N- (cyclopentyl) sulfamoyl group, N- (hexyl) sulfamoyl group, N- (cyclohexyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (Decyl) sulfamoyl group, N- (tricyclodecyl) sulfamoyl group, N- (methoxypropyl) sulfamoyl group, N- (Ethoxypropyl) sulfamoyl group, N- (propoxypropyl) sulfamoyl group, N- (isopropoxypropyl) sulfamoyl group, N- (hydroxyoxypropyl) sulfamoyl group, N- Siloxypropyl) Sulfamoyl, N- (methoxy-hexyl) sulfamoyl, N- (3- phenyl-1-methylpropyl), and the sulfamoyl group and the like.

Examples of -SO ₂ N (R ⁸ ) R ^{9 in} which R ⁹ is a hydrogen atom include groups represented by the following formulas. In the following formulas, X ¹ represents a halogen atom. X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include perfluoromethyl and the like in addition to the above-mentioned alkyl group.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include the above-mentioned alkyl groups, particularly methoxy group, ethoxy group and propoxy group.

Examples of -SO ₂ N (R ⁸ ) R ^{9 in} which R ⁸ and R ⁹ are other than hydrogen atoms include the following groups.

Examples of the heterocycle formed by bonding R ⁸ and R ⁹ to each other include groups represented by the following formulas.

Among them, as R ⁸ and R ⁹ , a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, a hydroxyl group having 2 to 8 carbon atoms Containing alkyl and aryl groups, alkoxy group-containing alkyl and aryl groups having 2 to 8 carbon atoms, and branched alkyl groups having 6 to 8 carbon atoms are more preferred.

As the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms, an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, -SO ₃ R ⁶ or -SO ₂ N (R ⁸ ) R ^{9 in} which R ⁹ is a hydrogen atom are preferable. Here, -SO ₂ N R ⁹ is a hydrogen atom (R ⁸⁾ R ⁹ Examples of R ⁸ in, particularly, a cycloalkyl group of 3 to 30 carbon atoms and the alkyl group is straight chain or branched having 1 to 10 carbon atoms are preferred, and a carbon number of 1 More preferably a linear or branched alkyl group having from 1 to 10 carbon atoms, further preferably a branched alkyl group having from 6 to 8 carbon atoms, particularly preferably 2-ethylhexyl.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexylphenyl group, a decanylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, A phenyl group, a dimethoxyphenyl group, an ethoxyphenyl group, a hexyloxyphenyl group, a decanyloxyphenyl group, and a trifluoromethylphenyl group, and groups in which -SO ₂ N (R ⁸ ) R ⁹ is substituted for these phenyl groups.

At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

R ¹ and R ² And at least one of R ³ and R ⁴ is more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

R ⁵ represents a carboxyl group, an ethoxycarbonyl group, a sulfo group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- -Methylpropyl) sulfamoyl group, and N- (isopropoxypropyl) sulfamoyl group.

The compound represented by the formula (1) is preferably at least one compound selected from the group consisting of the compounds represented by the formulas (1-1) to (1-4).

[In the formulas (1-1) to (1-4)

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, -R ⁶ Or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, -CO ₂ H, CO ₂ R ⁶ , -SO ₃ R ⁶ Or -SO ₂ NR ⁸ R ⁹ .

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ N (R ⁸ ) R ⁹ .

R ¹⁶ represents -SO ₃ ^- , -SO ₃ H or -SO ₂ N (R ⁸ ) R ⁹ .

R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ Or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ Or -SO ₂ NHR ²⁸ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or SO ₂ NHR ²⁸ .

R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 10 carbon atoms or a halogen atom.

R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ Or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with -R ²⁶ or -OR ²⁶ .

R ³¹ and R ³² each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group. The hydrogen atom contained in the aromatic hydrocarbon group is preferably a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ Or -SO ₂ NHR ²⁸ .

R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ⁴¹ and R ⁴² each independently represent an aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group. The hydrogen atom contained in the aromatic hydrocarbon group is -R ²⁶ Or -SO ₂ NHR ²⁸ .

R ⁴³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meanings as defined above.

Among them, the formula (1-4) is preferable.

Examples of the compound represented by the formula (1) include compounds represented by the formulas (1a) to (1f). However, the numbers of + charge and - charge in the compound represented by the formula (1) are the same.

(Wherein R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H or -SO ₂ NHR ^a .

R ^d , R ^e and R ^f independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a .

R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a .

R ^a represents an alkyl group of 1 to 10, preferably a 2-ethylhexyl group.

X and a have the same meanings as defined above.

The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).

Among them, the formulas (1e) and (1f) are preferable.

The compound represented by the formula (1) can be obtained by, for example, chlorinating a dye or a dye intermediate having -SO ₃ H by a method of preparation and converting the resulting dye or dye intermediate having -SO ₂ Cl into R ⁸ -NH ₂ Amine in the presence of a base. In addition, the dye prepared by the method described in the upper right column to the lower left column on page 3 of Japanese Patent Laid-Open Publication No. 3-78702 can be produced by chlorination followed by reaction with an amine in the same manner as described above.

Examples of the pigment (A-2) contained in the colorant (A) include organic pigments such as C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38, and the like. Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, and 15: 6, and preferably at least one pigment selected from the group consisting of C.I. Pigment Blue 15: 6 is particularly preferable. These pigments may be used alone or in combination of two or more.

If necessary, the organic pigment may be subjected to surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, graft treatment on the pigment surface with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water for removing the ionic impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

The organic pigment preferably has a uniform particle diameter. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants, and acrylic surfactants. These pigment dispersing agents may be used alone or in combination of two or more.

When a pigment dispersant is used, the amount thereof to be used is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less, per 1 part by mass of the pigment (A-2). When the amount of the pigment dispersant is within the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained, which is preferable.

The content of the colorant (A) is preferably from 5 to 60 mass%, more preferably from 8 to 55 mass%, and still more preferably from 10 to 50 mass%, based on the solid content in the colored photosensitive resin composition. Here, the solid content refers to the total of the components in the colored photosensitive resin composition excluding the solvent.

When the content of the colorant (A) is in the above-mentioned range, the color density when the color filter is formed is sufficient, and since a required amount of the binder polymer can be contained in the composition, a pattern having sufficient mechanical strength can be formed Do.

The content of the dye (A-1) in the colorant (A) is 3 to 80%, preferably 3 to 70% by mass, and more preferably 3 to 50% by mass.

The content of the pigment (A-2) in the colorant (A) is 20 to 97%, preferably 30 to 97% by mass, and more preferably 50 to 97% by mass.

The content ratio (mass ratio) of the dye (A-1) to the pigment (A-2) is preferably from 1:99 to 99: 1, more preferably from 1:99 to 60:40, : ≪ / RTI > By setting the ratio to the above range, the transmission spectrum can be easily optimized, and high contrast and high brightness can be obtained. Further, heat resistance and chemical resistance are improved.

Especially C.I. The mass ratio of Pigment Blue 15: 6 to the dye (A-1) is preferably 97: 3 to 50: 50, more preferably 97: 3 to 70:30.

The colored photosensitive resin composition of the present invention comprises an alkali-soluble resin (B). The alkali-soluble resin (B) is not particularly limited, and any resin may be used. For example, the alkali-soluble resin (B) contains a constituent unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from (meth) acrylic acid is preferably from 16% by mole to 40% by mole, more preferably from 18% by mole to 38% by mole, of the total structural units constituting the alkali-soluble resin (B) Mol% or less. When the content of the constituent unit derived from (meth) acrylic acid is within the above-mentioned range, solubility of the non-combustible part becomes good at the time of development. It is also preferable that the residue tends to remain in the non-combusted portion after development.

Examples of other monomers which derive constituent units other than the constituent units derived from (meth) acrylic acid constituting the alkali-soluble resin (B) include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters , Unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups or monoethers at the ends of polymer molecular chains (Meth) acryloyl group, a unit represented by the formula (II) and a unit represented by the formula (III).

[In the formulas (II) and (III), R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom or a methyl group. R ⁵⁴ and R ⁵⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the alkali-soluble resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate (II), R ⁵³ represents a methyl group or a methacrylate group, or a structural unit represented by the following formula (II): wherein R ⁵³ represents a methyl group And R ⁵⁴ represents a hydrogen atom.] / Benzyl methacrylate copolymer, a structural unit represented by the formula (II) wherein R ⁵³ represents a methyl group and R ⁵⁴ represents a hydrogen Wherein R ⁵⁵ represents a methyl group, and R ⁵⁶ represents a hydrogen atom (hereinafter referred to as a " hydrogen atom " .] / Styrene copolymer / tricyclodecanyl methacrylic Sites include copolymer.

Further, the alkali-soluble resin (B) represented by the formula (IV) is preferable from the viewpoints of curability and developability.

An alkali-soluble resin (B) having a constituent component represented by the formula (II), for example, a constituent component represented by methacrylic acid / formula (II) wherein R ⁵³ represents a methyl group , And R ⁵⁴ represents a hydrogen atom.] / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and then mixing the resultant two-component polymer with a compound represented by formula (V) Here, in formula (V), R ⁵⁷ represents a hydrogen atom.].

[In the formula (V), R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

Methacrylic acid / a constituent component represented by the formula (III) (wherein, in the formula (III), R ⁵⁵ represents a methyl group and R ⁵⁶ represents a hydrogen atom] / styrene copolymer / tricyclodecanyl methacrylate The late copolymer can be obtained by reacting glycidyl methacrylate with a monomethacrylate copolymer of benzyl methacrylate, methacrylic acid and tricyclodecane skeleton.

The copolymerization is generally carried out in a solvent using a polymerization initiator.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (methyl 2-methylpropionate), peroxides such as benzoyl peroxide and peroxide-tert- Etc. are used.

The solvent is not particularly limited as long as it dissolves the respective monomers and includes, for example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, A solvent exemplified as the solvent (E) to be explained is used.

The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator, the boiling point of the solvent and the monomer, and the like.

Further, the side chain of the copolymer thus obtained may be modified with a compound having a polymerizable group to obtain a photosensitive alkali-soluble resin (B). At this time, a catalyst for introducing a polymerizable group into the resin may be added.

Examples of the catalyst include trisdimethylaminomethylphenol and the like. In addition, an additive for preventing side reaction may be added. Examples of the additive include hydroquinone and the like.

As the alkali-soluble resin (B), for example, the following copolymers [K1] to [K4] and the like are exemplified.

(B1) (hereinafter sometimes simply referred to as "(B1)") and a monomer (B2) having a group having a cyclic ether of 2 to 4 carbon atoms, (Hereinafter sometimes simply referred to as " (B2) ").

[K2] A copolymer obtained by polymerizing (B1) and (B2) and a monomer (B3). Herein, the monomer (B3) (hereinafter sometimes simply referred to as "(B3)") may be a monomer copolymerizable with (B1) and / or (B2) It is a monomer.

[K3] A copolymer obtained by reacting a part of carboxyl groups derived from (B1) with a group having a cyclic ether having 2 to 4 carbon atoms derived from (B2), in a copolymer of (B1) and (B3).

[K4] Copolymer of (B1) and (B3).

Among them, the copolymer is preferably a copolymer obtained by polymerizing at least (B1) and (B2).

(B1) include, for example, an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride. Specifically,

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

(Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [(meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and? - (hydroxymethyl) acrylic acid, and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.

Of these, acrylic acid, methacrylic acid or maleic anhydride are preferable from the viewpoint of copolymerization reactivity and alkali solubility.

These may be used alone or in combination of two or more. In the present specification, any of the exemplified compounds, components, and the like may be used singly or in combination of two or more, unless otherwise specified.

(B2) has at least one group selected from the group consisting of, for example, a group having a cyclic ether having 2 to 4 carbon atoms (for example, an oxiranyl group, an oxetanyl group and a tetrahydrofuryl group) And is preferably a monomer having an unsaturated bond.

(B2) include, for example, a monomer having an oxiranyl group, a monomer having an oxetanyl group, a monomer having a tetrahydrofuryl group, and the like.

The monomer having an oxiranyl group as referred to above means, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxiranyl group and an alicyclic oxiranyl group.

The monomer having an oxiranyl group is preferably a compound having at least one group selected from the group consisting of an aliphatic oxiranyl group and an alicyclic oxiranyl group and also having an unsaturated bond and is preferably a compound having an oxiranyl group and a (meth) acryloyloxy group Is more preferable.

The aliphatic oxiranyl group refers to a structure obtained by epoxidizing an aliphatic olefin.

Specific examples of the compound having an aliphatic oxiranyl group include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) acrylate, glycidyl vinyl ether , Compounds represented by the following formula (VI) described in Japanese Patent Application Laid-Open No. 7-248625, and the like.

[In the formula (VI), R ⁶¹ to R ⁶³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m ¹ is an integer of ¹ to 5].

Examples of the compound represented by the formula (VI) include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl- Glycidyl ether,? -Methyl-m-vinylbenzyl glycidyl ether,? -Methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4- Diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyl Methylstyrene, dodecylmethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, and 2,4,6-triglycidyloxymethylstyrene.

The alicyclic oxiranyl group refers to a structure obtained by epoxidizing an alicyclic olefin.

Examples of the monomer having an alicyclic oxiranyl group include a monomer having an aliphatic monocyclic oxylan group, a monomer having an aliphatic polycyclic oxylan group, and the like. The monomer having an aliphatic monocyclic oxylanyl group means a polymerizable compound having a structure obtained by epoxidizing a monocyclic aliphatic olefin. The monomer having an aliphatic polycyclic oxylanyl group means a polymerizable compound having a structure in which a polycyclic aliphatic olefin is epoxidized.

The monomer having an oxiranyl group is preferably a compound having an aliphatic olefin epoxidized structure and having an unsaturated bond, and the structure obtained by epoxidizing an alicyclic olefin is also preferably a compound having a (meth) acryloyl group Do.

Examples of the monocyclic aliphatic olefin include cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like. Among them, a compound having 5 to 7 carbon atoms is preferable.

Specific examples of the monomer having an aliphatic monocyclic oxylanyl group include vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, CYRAMER A400; Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, cyclomer M100; (Manufactured by Daicel Chemical Industries, Ltd.).

Examples of the polycyclic aliphatic olefin include dicyclopentene, tricyclodecene, norbornane, isonorbornene, bicyclooctene, bicyclononene, bicycloundecene, tricyclodecene, bicyclo dodecene Tricyclododecene, and the like.

Among them, a compound having 8 to 12 carbon atoms is preferable.

Examples of the monomer having an aliphatic polycyclic oxylanyl group include 3,4-epoxy norbornyl acrylate, 3,4-epoxy norbornyl methacrylate, a compound represented by the formula (VII) ), And the like.

In the formulas (VII) and (VIII), R ⁷¹ and R ⁷² each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a hydroxy group.

X ⁷¹ and X ⁷² each independently represent a single bond, an alkanediyl group having 1 to 6 carbon atoms or * - (CH ₂ ) _s - X '- (CH ₂ ) _t -, wherein X' O- or -NH-, s represents an integer of 1 to 6, and t represents an integer of 0 to 6. Where s + t? 6. * Represents the hand with O.]

Specific examples of R ⁷¹ and R ⁷² include a hydrogen atom; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxyethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, Hydroxy-substituted alkyl groups such as a hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

Among them, preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group. More preferably a hydrogen atom or a methyl group.

Specific examples of the alkanediyl group having 1 to 6 carbon atoms include a single bond; A methylene group, an ethylene group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group and a 1,6-hexanediyl group.

Among them, a single bond, a methylene group, an ethylene group, -O-CH ₂ -, and -O- (CH ₂ ) ₂ - are preferable. More preferably a single bond, -O- (CH ₂ ) ₂ -.

At least one kind of compound selected from the group consisting of a compound represented by the formula (VII) and a compound represented by the formula (VIII) is a compound consisting of a compound represented by the following formula (VII ') and a compound represented by the formula (VIII' Is preferably at least one kind of compound selected from the group consisting of

In the formulas (VII ') and (VIII'), R ^{71 '} and R ^72' have the same meanings as R ⁷¹ and R ⁷² , respectively.

Examples of the compound represented by the formula (VII) include compounds represented by the formula (VII-1) to (VII-15). (VII-1), VII-3, VII-5, VII-7, VII-9, )to be. (VII-1), (VII-7), (VII-9) and (VII-15).

Examples of the compound represented by the formula (VIII) include compounds represented by the formula (VIII-1) to (VIII-15). (VIII-1), VIII-3, VIII-5, VIII-7, VIII-9, VIII- )to be. (VIII-1), (VIII-7), (VIII-9) and (VIII-15).

The compound represented by formula (VII) and the compound represented by formula (VIII) may be used alone. In addition, they can be mixed at an arbitrary ratio. When mixing, the mixing ratio thereof is preferably 5: 95 to 95: 5, more preferably 10: 90 to 90: 10, more preferably 20: 80 to 80:20.

The above-mentioned oxetanyl group-containing monomer means, for example, a polymerizable compound having an oxetanyl group. The monomer having an oxetanyl group is preferably a compound having an oxetanyl group and having an unsaturated bond, more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.

Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3- 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxy ethyl oxetane, 3-methyl- 3-ethyl-3-acryloxyethyloxetane and the like.

The monomer having a tetrahydrofuryl group as described above refers to, for example, a polymerizable compound having a tetrahydrofuryl group. The monomer having a tetrahydrofuryl group is preferably a compound having a tetrahydrofuryl group and having an unsaturated bond, and is preferably a compound having a tetrahydrofuryl group and a (meth) acryloyloxy group.

Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. have.

As the copolymerizable monomer (B3), for example,

Acrylic acid alkyl ester such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

(Meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decan- (Meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [ 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept- 2,1-hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cycarbonylbicyclo [ 2.2.1] hept-2-ene, 5,6-di (tertiary butoxycarbonyl) bicyclo [2.2.1] hept- Non-cyclic unsaturated compounds such as cyclo [2.2.1] hept-2-ene;

N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide and N-propylmaleimide;

N-cycloalkyl maleimides such as N-cyclopentyl maleimide, N-cyclohexyl maleimide and N-cyclooctyl maleimide;

N-bridged carbocyclic group substituted maleimides such as N-adamantyl maleimide and N-norbornyl maleimide;

N-aryl maleimides such as N-phenyl maleimide;

N-aralkyl maleimides such as N-benzyl maleimide;

N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N- Dicarbonylimide derivates such as phytonate, N- (9-acridinyl) maleimide, and the like;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoint of copolymerization reactivity and alkali solubility.

The copolymers [K1] to [K4] can be prepared, for example, by the method described in the "Experimental Method of Polymer Synthesis" (published by KODOKI Corporation, 1st Ed., 1st Ed., March 1, 1972, And can be produced by referring to the reference documents listed in the document.

Concretely, a predetermined amount of the monomers (B1) and (B2) and optionally (B3) constituting the copolymer, the polymerization initiator and the solvent are placed in a reaction vessel, oxygen is replaced by nitrogen, , And warmed to obtain a polymer. The polymerization conditions such as the feeding method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

As the polymerization initiator and the solvent to be used herein, any of those commonly used in the field can be used. For example, a polymerization initiator and a solvent described later can be used.

The solution obtained after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, or it may be drawn out as a solid (powder) by re-precipitation or the like.

In particular, by using a solvent described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

It is preferable that the copolymer [K1] has a molar ratio with respect to the total number of moles of the monomers constituting the copolymer [K1] within the following ranges.

(B1), more preferably 10 to 90 mol%, further preferably 10 to 50 mol%

(B2), more preferably 10 to 90 mol%, still more preferably 50 to 90 mol%.

It is preferable that the copolymer [K2] has a molar ratio with respect to the total number of moles of the monomers constituting the copolymer [K2] within the following ranges.

(B1) in an amount of 2 to 40 mol%, more preferably 5 to 35 mol%

(B2) in an amount of 2 to 95 mol%, more preferably 5 to 80 mol%

(B3) is 1 to 65 mol%, more preferably 1 to 60 mol%.

The copolymer [K3] can be produced through a two-step process.

First, (B1) and (B3) are copolymerized in the same manner as the above-mentioned method to obtain a copolymer.

In this case, it is preferable that the ratio of each monomer is in the following range with respect to the total number of moles of the monomers constituting the resin.

(B1) of 5 to 50 mol%, preferably 10 to 45 mol%

(B3) is 50 to 95 mol%, preferably 55 to 90 mol%.

Next, a part of the carboxylic acid and / or carboxylic acid anhydride of (B1) derived from the copolymer of (B1) and (B3) is reacted with an oxiranyl, oxetanyl or tetrahydrofuryl group derived from (B2) .

To this end, the atmosphere in the flask is replaced by air from nitrogen, (B2), the reaction catalyst and the polymerization inhibitor are placed in a flask, and the reaction is continued at 60 to 130 DEG C for 1 to 10 hours, for example do. The reaction conditions such as the feeding method, the reaction temperature and the time can be suitably adjusted in consideration of the amount of heat generated by the production equipment or polymerization.

In this case, the number of moles of (B2) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol% with respect to the number of moles of (B1).

The reaction catalyst is suitably used, for example, as a catalyst for reaction with a carboxyl group and an oxiranyl, oxetanyl or tetrahydrofuryl group. Specific examples thereof include tris (dimethylaminomethyl) phenol and the like.

The amount of the reaction catalyst to be used is, for example, about 0.001 to 5% by weight based on the total amount of (B1) to (B3).

As the polymerization inhibitor, for example, hydroquinone is exemplified.

The amount of the polymerization inhibitor to be used is, for example, about 0.001 to 5% by weight based on the total amount of (B1) to (B3).

It is preferable that the copolymer [K4] has a ratio of each monomer to the total number of moles of the monomers constituting the copolymer [K4] in the following range.

(B1) in an amount of 2 to 40 mol%, more preferably 5 to 35 mol%

(B2), more preferably 65 to 95 mol%.

The weight average molecular weight of the copolymers [K1] to [K4] in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000.

The dispersion degree (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymers [K1] to [K4] are preferably 1.1 to 6.0 and more preferably 1.2 to 4.0 .

The weight average molecular weight of the alkali-soluble resin (B) in terms of polystyrene is usually from 5,000 to 35,000, preferably from 6,000 to 30,000, and particularly preferably from 7,000 to 28,000. When the molecular weight is within the above-mentioned range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution tends to be improved.

The acid value of the alkali-soluble resin (B) is 50 to 150, preferably 60 to 135, particularly preferably 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the alkali-soluble resin (B), and can be determined by appropriately using an aqueous solution of potassium hydroxide.

The content of the alkali-soluble resin (B) is 7 to 65% by mass, preferably 13 to 60% by mass, and more preferably 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the alkali-soluble resin (B) is within the above-mentioned range, it is preferable that a pattern can be formed and the resolution and the residual film ratio tend to be improved.

The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is not particularly limited so long as it is a compound which can be polymerized by an active radical, an acid generated from the photopolymerization initiator (D) upon irradiation with light. For example, a compound having a polymerizable carbon-carbon unsaturated bond.

The photopolymerizable compound (C) is preferably a multifunctional photopolymerizable compound having three or more functional groups. Examples of the polyfunctional photopolymerizable compound having three or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, and the like. The photopolymerizable compound (C) may be used singly or in combination of two or more kinds.

The content of the photopolymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition . When the content of the photopolymerizable compound (C) is within the above-mentioned range, the curing is sufficiently carried out, the ratio of the film thickness before and after the development is improved, the undercut is difficult to be introduced into the pattern, Do.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D).

Examples of the photopolymerization initiator (D) include an active radical generator and an acid generator. The active radical generator generates active radicals by being irradiated with light. The acid generator generates an acid by being irradiated with light.

Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and the like.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2-hydroxy-2-methyl- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, ] Propane-1-one, and the like, and preferably 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propoxyoctanoate and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3 , 5-triazine, and the like.

Examples of the above oxime compounds include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) -butan-1-one-2- Amine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy- 1- [ 3-yl] ethan-1-imine, N-acetoxy-1- [ Oxy) benzoyl} -9H-carbazol-3-yl] ethanone-1-imine.

As the active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, Or the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene sulfonate, p-toluene sulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Onium salts such as diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate and the like, nitrobenzyl tosylates, benzoin tosylates and the like.

Among the compounds described above as the above-mentioned active radical generator, there are compounds which generate an acid at the same time as an active radical. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above-mentioned range, it is preferable because a high sensitivity is obtained and the exposure time is shortened and productivity is improved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiator (F). The photopolymerization initiator (F) is generally used in combination with the photopolymerization initiator (D) and is a compound used for promoting the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator.

Examples of the photopolymerization initiator (F) include an amine compound, an alkoxyanthracene compound, and a thioxanthone compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylbenzoic acid Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- ) Benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxy Anthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propoxyoctanoate and the like.

The photopolymerization initiator (F) may be used alone or in combination of two or more. A commercially available photopolymerization initiator (F) may be a commercially available photopolymerization initiator (F), for example, a trade name "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.) .

Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiator (G) in the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2- (4-methylphenyl) propane-1-on / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, benzyldimethylketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethyl Amino) benzophenone, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, and the like, It may be mentioned 2-methyl-2-morpholino-1- (4-methylsulfanyl-phenyl) propan-1-one / 4,4-bis (diethylamino) benzophenone.

When these photopolymerization initiator (G) is used, the amount thereof to be used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (D).

The solvent (E) contained in the colored photosensitive resin composition of the present invention is not particularly limited, and a solvent commonly used in the field can be used.

Examples of the solvent include esters (solvents containing -COO-), ethers other than esters (solvents containing -O-), ketones other than esters (solvents containing -CO-), alcohols, aromatics Hydrocarbons, amides, N-methylpyrrolidone, dimethylsulfoxide and the like.

Examples of the esters include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, Methoxyacetic acid, methyl methoxyacetate, methyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxyethyl methoxyacetate, ethyl methoxyacetate, Methyl propionate, ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl, ethyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, There may be mentioned 2-oxo-butanoic acid methyl, 2-oxo-butanoic acid ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, cyclohexanol acetate, butyl γ- lactone ol.

Examples of the above-mentioned ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol,

Tetrahydrofuran, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene Propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Anisole, phenetole, methyl anisole and the like.

Examples of the ketones include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, Pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

Examples of the above-mentioned aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

Among them, it is preferable to include one kind of a hydroxyl group-containing solvent. Examples of the hydroxyl group-containing solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, and 4-hydroxy-4-methyl-2-pentanone.

The content of the solvent (E) in the colored photosensitive resin composition is from 70 to 95% by mass, and more preferably from 75 to 92% by mass, based on the colored photosensitive resin composition. In other words, it is preferable to adjust the content of the solvent (E) so that the solid content is 5 to 30 mass%, preferably 8 to 25 mass%, based on the colored photosensitive resin composition. When the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes good and the color characteristic is not insufficient when the color filter is formed, so that the display characteristics tend to be good.

As the surfactant (F) contained in the colored photosensitive resin composition of the present invention, a surfactant having a fluorine atom or a silicon atom is suitable. Specific examples include at least one selected from the group consisting of a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactants include surfactants having a siloxane bond. Specifically, the following materials were used: Dore silicon DC3PA, Dole silicone SH7PA, Dore silicon DC11PA, Dole silicone SH21PA, Dole silicone SH28PA, Dore silicone SH29PA, Dore silicone SH30PA, Polyether modified silicone oil SH8400 (trade name: (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460, KP321, KP323, KP324, KP326, KP340 and KP341 [manufactured by Dow Corning Toray Co., Momentive Performance Materials, Japan Joint Association].

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of such a solvent include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, (Trade name) EF301, Epson EF303, Epson EF351, Epson EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.)], Megapack F489, Megapack F554, Megapack R30 (Manufactured by Daikin Fine Chemical Research Institute, Ltd.), BM-1000, BM-1100 [manufactured by Asahi Glass Co., Ltd.], E5844 Trade name: BM Chemie).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by DIC Corporation) and the like.

These surfactants may be used singly or in combination of two or more kinds.

The content of the surfactant (F) is preferably 0.0005 to 0.3 part by mass, more preferably 0.001 to 0.1 part by mass based on 100 parts by mass of the colored photosensitive resin composition. When the content of the surfactant (F) is within this range, flatness tends to be improved, which is preferable.

The colored photosensitive resin composition of the present invention is preferably a negative-type photosensitive resin composition.

The colored photosensitive resin composition of the present invention can be suitably used for forming a color filter or a colored pattern, and it is possible to obtain a colored pattern and a color filter having good color density, brightness, contrast, sensitivity, resolution, heat resistance and the like. It is also possible to use an optical film, an array substrate or the like having these color filters or colored patterns as a part of their constituent parts or a display device provided with these color filters or colored patterns, optical films or array substrates, A liquid crystal display device, an organic EL device, a solid-state image pickup device, and the like.

As a method of forming a color filter or a pattern using the colored photosensitive resin composition of the present invention, for example, a method of forming a colored photosensitive resin composition of the present invention on a substrate or another resin layer (for example, A photosensitive resin composition layer or the like), removing volatile components such as a solvent to form a colored layer, exposing and developing the colored layer through a photomask, and a method of developing an inkjet apparatus that does not require photolithography And the like.

The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material to be used and the application and is, for example, about 0.1 to 30 m, preferably about 1 to 20 m, For example, about 1 to 6 mu m.

Examples of the application method of the colored photosensitive resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method and a die coating method. It may also be coated using a coater such as a dip coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (die coater, curtain flow coater, or spinless coater). Among them, it is preferable to apply by using a spin coater.

The removal / drying of the solvent includes, for example, natural drying, air drying, and vacuum drying. The specific heating temperature is preferably about 10 to 120 占 폚, and preferably about 25 to 100 占 폚. The heating time is preferably about 10 seconds to about 60 minutes, preferably about 30 seconds to about 30 minutes. The reduced-pressure drying is performed under a pressure of about 50 to 150 Pa at a temperature of about 20 to 25 캜.

The colored photosensitive resin composition of the present invention can be suitably used for forming a colored image constituting a color filter used for a liquid crystal display element or a solid-state image pickup element.

Example

Hereinafter, the colored photosensitive resin composition and the color filter of the present invention will be described in more detail with reference to Examples. In the examples, "% " and " part "

Synthesis Example 1: Synthesis of Dye A1

In a flask equipped with a cooling tube and a stirrer, 15 parts of a coloring matter represented by the formula A-0-1 (a jugation agent), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were fed, And 10.9 parts of thionyl chloride was added dropwise thereto while being kept. After completion of the dropwise addition, the temperature was raised to 50 캜, and the reaction was maintained at the same temperature for 5 hours, followed by cooling to 20 캜. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine with stirring while maintaining the temperature at 20 ° C or lower. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added to the reaction mixture. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of dye A1 (mixed dye of dye A1-1 to dye A1-8).

[In formula (A1), R _c independently represents -SO ₂ NH-R _a , -SO ₃ H, -SO ₃ ^- or -H.

R _a represents 2-ethylhexyl.

Synthesis Example 2: Synthesis of Resin B1

210 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was changed from nitrogen to air, 22.0 g (0.10 mol) of mono methacrylate of tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) and 50.0 g of propylene glycol mono (methacrylic acid) And 215 g of methyl ether acetate, to which 3.6 g of 2,2'-azobisisobutylonitrile had been added was added dropwise, and further stirring was continued at 100 ° C.

Next, 35.5 g (0.25 mol) of glycidyl methacrylate (50 mol% based on the carboxyl group of methacrylic acid used in the present reaction) of 0.9 g of trisdimethylaminomethylphenol And 0.145 g of hydroxyquinone were charged into a flask, and the reaction was continued at 110 캜 to obtain a resin solution B1 having a solid acid value of 79 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 3.0 x 10 ⁴ .

The measurement of the polystyrene reduced weight average molecular weight of the above resin was carried out by the GPC method under the following conditions.

Device ; HLC-8120 GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01%

Dose; 50 μL

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

                      F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION)

Example 1

[Preparation of colored photosensitive resin composition 1]

(A-2) Pigment: C.I. Pigment Blue 15: 6 3.0 parts

Acrylic pigment dispersant 1.0 part

Propylene glycol monomethyl ether acetate 23 parts

And the pigment is sufficiently dispersed using a bead mill, and then,

(A-1) Dye: 0.5 part of dye A1

(B) Resin: Resin solution B1 16 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

    [KAYARAD DPHA; (Manufactured by Nippon Yakuza Co., Ltd.) 4.6 parts

(D) Photopolymerization initiator: OXE-01

    [Manufactured by Chiba and Japan] 1.4 parts

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts

(F) Surfactant: polyether-modified silicone oil

[SH8400 manufactured by Dow Corning Toray Co., Ltd.] 0.0005 part

To obtain a colored photosensitive resin composition 1.

[Formation of Evaluation Coating Film]

The colored photosensitive resin composition was coated on a glass substrate (Eagle 2000; Corning) having a 3-inch square by spin coating, and then pre-baked in a clean oven at 100 占 폚 for 3 minutes. After cooling, the substrate was irradiated with light at an exposure dose (365 nm) of 150 mJ / cm 2 under an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) and heated at 220 占 폚 for 20 minutes, Respectively. The film thickness of the coated film was measured using a film thickness measuring device [DEKTAK3; Manufactured by Nippon Vacuum Technology Co., Ltd.), and found to be 2.8 탆.

[Evaluation of flatness]

The obtained coating film surface was visually confirmed. The results are shown in Table 3.

[Brightness evaluation]

The obtained coating film on the glass substrate was measured with a colorimeter [OSP-SP-200; (Bx, By) and brightness in an XYZ colorimetric system of CIE were measured using a C light source. The results are shown in Table 3.

Examples 2 to 3

Colored photosensitive resin compositions 2 and 3 were obtained in the same manner as in Example 1, except that (F) was changed to the number shown in Table 1 in the colored photosensitive resin composition 1. In addition, the evaluation coating film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

                       (Unit: part) Example 2 Example 3 (F) 0.01 0.1

Example 4

[Preparation of colored photosensitive resin composition 4]

(A-2) Pigment: C.I. Pigment Blue 15: 6 3.0 parts

Acrylic pigment dispersant 1.0 part

Propylene glycol monomethyl ether acetate 23 parts

And the pigment is sufficiently dispersed using a bead mill, and then,

(A-1) Dye: 0.5 part of dye A1

(B) Resin: Resin solution B1 16 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4.6 parts

(D) Photopolymerization initiator: OXE-01

(Manufactured by Chiba Japan) 1.4 parts

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts

(F) Surfactant: Megafac F554

        [Manufactured by DIC Corporation] 0.003 part

To obtain a colored photosensitive resin composition 4.

[evaluation]

The evaluation coating film was prepared and evaluated in the same manner as in Example 1. [ The results are shown in Table 3.

Examples 5 to 6

A colored photosensitive resin composition was obtained in the same manner as in Example 4 except that the components (B) to (F) in the colored photosensitive resin composition 4 were changed to the number shown in Table 2. The evaluation coating film was prepared and evaluated in the same manner as in Example 4. The results are shown in Table 3.

                     (Unit: part) Example 5 Example 6 (B) 16 15 (C) 4.6 4.5 (D) 1.4 1.3 (E) 51 51 (F) 0.01 0.3

Surfactant (F) content Flatness Bx By brightness Example 1 0.0005 part ○ 0.141 0.071 7.4 Example 2 0.010 part ○ 0.141 0.071 7.3 Example 3 0.100 part ○ 0.142 0.068 6.8 Example 4 0.003 part ○ 0.141 0.069 7.0 Example 5 0.010 part ○ 0.141 0.071 7.4 Example 6 0.300 part ○ 0.141 0.070 7.1

In Table 3, the content of the surfactant is represented by the content with respect to 100 parts by mass of the colored photosensitive resin composition.

In Examples 1 to 6, a smooth coating film having no unevenness was obtained, and excellent brightness was confirmed.

According to the present invention, it is possible to provide a colored photosensitive resin composition which gives a coating film and a color filter excellent in brightness and flatness.

Claims (9)

(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and a surfactant (F)
Wherein the colorant (A) comprises both of the dye (A-1) and the pigment (A-2) comprising a compound represented by the formula (1)
The surfactant (F) is a surfactant having a fluorine atom, a silicon atom, or a fluorine atom and a silicon atom,
Wherein the content of the surfactant (F) is 0.0005 parts by mass or more and 0.3 parts by mass or less based on 100 parts by mass of the colored photosensitive resin composition.

[In the formula (1)
R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or -SO ₂ N (R ⁸ ) R ⁹ may be substituted.
R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ or -SO ₂ N (R ⁸ ) R ⁹ .
m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.
X represents a halogen atom. a represents an integer of 0 or 1;
R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms. -CH ₂ - contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with -O-, -CO- or -NR ⁷ -.
R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms.
R ⁸ and R ⁹ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Or R ⁸ and R ⁹ may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms. The alkyl group and the hydrogen atom contained in the cycloalkyl group may be substituted with a halogen atom, -OH, -Q, -CH = CH _2, or -CH = CHR ⁶ .
The alkyl group and -CH ₂ - contained in the cycloalkyl group may be substituted with -O-, -CO-, -NH- or -NR ⁶ -. The hydrogen atom contained in the heterocycle having 1 to 10 carbon atoms may be substituted with -R ⁶ , -OH or -Q.
Q represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a monovalent aromatic heterocyclic group having 5 to 10 member rings and the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is halogen An atom, -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH═CH ₂ or -CH═CHR ⁶ .
M represents a sodium atom or a potassium atom.
However, the number of + electric charges and the number of electric charges of the compound represented by formula (1) are the same.] The method according to claim 1,
Wherein the ratio of the content of the dye (A-1) to the content of the pigment (A-2) is from 1:99 to 99: 1. The method according to claim 1,
Wherein the pigment (A-2) is a pigment comprising CI Pigment Blue 15: 6. The method according to claim 1,
Wherein the solvent (E) is a solvent containing one kind of a hydroxyl group-containing solvent. A coloring pattern characterized by being formed using the composition according to claim 1. A color filter comprising the coloring pattern according to claim 5. The method according to claim 6,
Wherein the color filter is formed by photolithography. A liquid crystal display device comprising the color filter according to claim 6. delete