CN101930176B - Coloring photosensitive composition - Google Patents

Abstract

A colored photosensitive composition containing a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant is a colorant containing a compound represented by formula (2). [In the formula (2), G ¹ represents an alkylene group with 2 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group can be substituted by an alkyl group with 1 to 4 carbon atoms, and the alkylene group contained in the alkylene group -CH ₂ - may be substituted by -O-, J ¹ represents a hydrogen atom, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- , R ^a and R ^b each independently represent a hydrogen atom or a carbon atom number of 1 to 1 8 alkyl group, Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- , X and Y each independently represent a monovalent organic group, n ^a represents an integer of 1 to 4].

Description

Colored photosensitive composition

technical field

The present invention relates to a colored photosensitive composition and a color filter using the colored photosensitive composition.

Background technique

Color filters used in display devices such as liquid crystal display panels, electroluminescence (elements), and plasma display panels are produced using colored photosensitive compositions. As the colorant contained in the colored photosensitive composition, a dye or a pigment is used.

Such a colored photosensitive composition is known to be a composition containing a xanthene dye, a pigment, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent (Patent Document 1).

Non-Patent Document 1: "Korega Diesupurei's Panorama! (Display Panorama)" p.114 (Izumiya Shibu et al.; Kanki Publishing, April 18, 2005)

Patent Document 2: Japanese Patent Laid-Open No. 2010-32999

Contents of the invention

Furthermore, in order to achieve high contrast of a color filter, development of a new coloring photosensitive composition is desired.

The inventors of the present invention conducted studies in order to solve the above-mentioned problems, and as a result, completed the present invention.

That is, the present invention provides the following [1] to [10].

[1]. A colored photosensitive composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant is a colorant comprising a compound represented by formula (2),

[In the formula (2), G ¹ represents an alkylene group with 2 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group can be substituted by an alkyl group with 1 to 4 carbon atoms, and the alkylene group contained in the alkylene group -CH ₂ - can be replaced by -O-,

J ¹ represents a hydrogen atom, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- ,

R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

Q ^- means halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- ,

X and Y each independently represent a monovalent organic group,

n ^a represents an integer of 1-4. ]

[2]. The colored photosensitive composition according to [1], wherein J ¹ is -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- .

[3]. The colored photosensitive composition according to any one of [1] or [2], wherein the colorant further contains a compound represented by formula (1),

[In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group with 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by 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 , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ replaced,

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ,

m represents an integer of 0-5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same or different,

X represents a halogen atom, a represents an integer of 0 or 1,

R ⁶ represents a saturated hydrocarbon group with 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group with 1 to 10 carbon atoms may be replaced by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ¹⁰ -substituted,

R ¹⁰ represents a hydrogen atom or a saturated hydrocarbon group with 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, the -CH ₂ - contained in the saturated hydrocarbon group is replaced by -O- or -CO-,

R ⁸ and R ⁹ each independently represent an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Q ¹ , and the hydrogen atoms contained in the alkyl group and the cycloalkyl group can be replaced by a hydroxyl group. , halogen atom, -Q ¹ , -CH═CH ₂ or -CH═CHR ⁶ , the -CH ₂ - contained in the alkyl group and the cycloalkyl group can be replaced by -O-, -CO- or -NR ¹⁰ - Substitution, R ⁸ and R ⁹ can be bonded to each other to form a heterocyclic ring with 1 to 10 carbon atoms, and the hydrogen atoms contained in the heterocyclic ring can be replaced by R ⁶ , -OH or -Q ¹ ,

Q ¹ represents an aromatic hydrocarbon group with 6 to 10 carbon atoms or an aromatic heterocyclic group with 3 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group and aromatic heterocyclic group can be replaced by -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or halogen substitution,

M represents a sodium atom or a potassium atom,

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

[4]. The colored photosensitive composition according to any one of [1] to [3], wherein the colorant further contains an organic pigment.

[5]. The colored photosensitive composition according to [4], wherein the organic pigment is an organic pigment containing C.I. Pigment Blue 15:6.

[6]. The colored photosensitive composition according to any one of [1] to [5], wherein the content of the compound represented by the formula (2) is 1 to 50% by mass relative to the colorant.

[7]. The colored photosensitive composition according to any one of [1] to [6], wherein the photopolymerization initiator is a compound having an oxime structure.

[8]. A coating film formed using the colored photosensitive composition according to any one of [1] to [7].

[9]. A color filter formed using the colored photosensitive resin composition according to any one of [1] to [7].

[10]. The color filter according to [9], which is formed by photolithography.

Description of drawings

1 is a schematic diagram illustrating a method of manufacturing a color filter of the present invention;

2 is a schematic diagram illustrating a method of manufacturing a color filter of the present invention;

3 is a schematic diagram illustrating a method of manufacturing a color filter of the present invention;

FIG. 4 is a schematic diagram illustrating a method of manufacturing a color filter of the present invention.

Detailed ways

The colored photosensitive composition of the present invention contains a colorant (hereinafter, sometimes referred to as "colorant (A)"), and the colorant (A) contains a compound represented by formula (2),

[In the formula (2), G ¹ represents an alkylene group with 2 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group can be substituted by an alkyl group with 1 to 4 carbon atoms, and the alkylene group contained in the alkylene group -CH ₂ - can be replaced by -O-,

J ¹ represents a hydrogen atom, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- ,

R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

Q ^- means halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- ,

X and Y each independently represent a monovalent organic group,

n ^a represents an integer of 1-4. ]

Examples of the alkylene group having 2 to 12 carbon atoms include methylene group, ethylene group, propanediyl group (propylene group), butanediyl group (butylene group), and the like.

-CH ₂ -The alkylene group having 2 to 12 carbon atoms which may be substituted by -O- includes a group represented by formula (G-1) and a group represented by formula (G-2).

[In formula (G-1) and formula (G-2), G ² to G ⁵ each independently represent an alkylene group having 1 to 8 carbon atoms.

n ¹ represents an integer of 1-3.

n ² represents an integer of 0-3.

Wherein, the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-1) is 3 to 12, and the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-2) are respectively 2 to 12.

* indicates the bonding position with -NH-. ]

The alkyl group having 1 to 4 carbon atoms is exemplified by methyl group, ethyl group, propyl group, butyl group and the like.

-SO ₂ -NH-G ¹ -J ¹ is, for example, a group represented by the following formula.

When G ¹ is a group represented by formula (G-1), -SO ₂ -NH-G ¹ -J ¹ is, for example, a group represented by the following formula.

When G ¹ is a group represented by formula (G-2), -SO ₂ -NH-G ¹ -J ¹ is, for example, a group represented by the following formula. .

When J ¹ is -NR ^a R ^b , -SO ₂ -NH-G ¹ -J ¹ is, for example, a group represented by the following formula.

When J ¹ is -NR ^a R ^b H ⁺ Q ^- , -SO ₂ -NH-G ¹ -NR ^a R ^b H ⁺ is, for example, a group represented by the following formula.

Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- .

X and Y represent a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a combination thereof.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, hexyl, decyl and the like.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclodecyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl and phenanthrenyl.

X-CO ₂ ^- is an organic compound anion containing a CO ₂ ^- group, Y-SO ₃ ^- is an organic compound anion containing a SO ₃ ^- group, for example, anions represented by formula (Q-1) to formula (Q-4) .

[R ^y represents an alkyl group having 1 to 20 carbon atoms.

m represents an integer of 0-5. ]

Q ^- is preferably X-CO ₂ ^- and Y-SO ₃ ^- , more preferably an anion represented by formula (Q-4). These anions tend to increase the solubility of the compound represented by the formula (2) in a solvent.

The compound represented by formula (2) includes, for example, compounds represented by formula (2-1) to formula (2-92).

For example, more specific examples of the compound represented by formula (2-24) include compounds represented by formula (2-24-1) and formula (2-24-2).

The content of the colorant (A) is preferably 10 to 70% by mass, more preferably 15 to 55% by mass, and even more preferably 20 to 50% by mass relative to the solid content in the colored photosensitive composition. Here, solid content means the total of components other than a solvent in a colored photosensitive composition.

When the content of the coloring agent (A) is within the above range, the color concentration is sufficient when forming a color filter, and the composition can contain a necessary amount of binder resin, and a pattern with sufficient mechanical strength can be formed, which is preferable.

The content of the compound represented by the formula (2) in the colorant (A) is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 2 to 30% by mass.

When the content of the compound represented by the formula (2) in the colorant (A) is within the above range, it is easy to achieve optimization of the transmission spectrum, and a high-contrast and high-brightness color filter can be obtained.

The coloring agent (A) is selected according to the color of the objective color filter, and may contain several kinds of dyes or pigments.

The coloring agent (A) is preferably a coloring agent containing a xanthene dye in addition to the compound represented by the formula (2).

Specific examples of xanthene dyes include, for example, rhodamine B, sulforhodamine 101, sulforhodamine B, rhodamine 6G,

C.I. Acid Red 51, 91, 92, 289

C.I. Acid Violet 102

C.I. Solvent Red 49, 72

C.I. Basic Red 1 etc.

The xanthene dye is preferably a compound represented by formula (1).

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group with 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by 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 , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ replaced,

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ,

m represents an integer of 0-5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same or different,

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

R ⁶ represents a saturated hydrocarbon group with 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group with 1 to 10 carbon atoms may be replaced by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ¹⁰ -substitution.

R ¹⁰ represents a hydrogen atom or a saturated hydrocarbon group with 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- .

R ⁸ and R ⁹ each independently represent an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Q ¹ , and the hydrogen atoms contained in the alkyl group and the cycloalkyl group can be replaced by a hydroxyl group. , halogen atom, -Q ¹ , -CH=CH ₂ or -CH=CHR ⁶ substituted, the -CH ₂ - contained in the alkyl and cycloalkyl can be substituted by -O-, -CO- or -NR ¹⁰ - . Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms, and hydrogen atoms contained in the heterocyclic ring may be substituted by R ⁶ , -OH or -Q ¹ .

Q ¹ represents an aromatic hydrocarbon group with 6 to 10 carbon atoms or an aromatic heterocyclic group with 5 to 10 carbon atoms, and the hydrogen atoms contained in the above aromatic hydrocarbon group and aromatic heterocyclic group can be replaced by -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or halogen substitution,

M represents a sodium atom or a potassium atom.

However, the compound represented by formula (1) has the same number of + charges and - charges. )

^R is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl , octyl, 2-ethylhexyl, cyclooctyl, nonyl, decyl (decanyl), tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethyl Hexyloxypropyl, methoxyhexyl, ethoxypropyl, etc.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl, naphthyl and the like.

Examples of the halogen atom as the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms include fluorine, chlorine, bromine and the like.

-SO ₃ R ⁶ is exemplified by methoxysulfonyl, ethoxysulfonyl, hexyloxysulfonyl, decyloxysulfonyl and the like.

-CO ₂ R ⁶ is exemplified by methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, Neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyl oxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxy Propoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl and the like.

-SO ₂ NHR ⁸ is exemplified by sulfamoyl, N-(methyl)sulfamoyl, N-(ethyl)sulfamoyl, N-(propyl)sulfamoyl, N-(isopropyl)sulfamoyl Acyl, N-(butyl)sulfamoyl, N-(isobutyl)sulfamoyl, N-(pentyl)sulfamoyl, N-(isopentyl)sulfamoyl, N-(neopentyl) )sulfamoyl, N-(cyclopentyl)sulfamoyl, N-(hexyl)sulfamoyl, N-(cyclohexyl)sulfamoyl, N-(heptyl)sulfamoyl, N-(cycloheptyl)sulfamoyl Base) sulfamoyl, N-(octyl) sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethylhexyl) sulfamoyl, N-(cyclooctyl) Base) sulfamoyl, N-(nonyl)sulfamoyl, N-(decyl)sulfamoyl, N-(tricyclodecanyl)sulfamoyl, N-(methoxypropyl)sulfamoyl , N-(ethoxypropyl)sulfamoyl, N-(propoxypropyl)sulfamoyl, N-(isopropoxypropyl)sulfamoyl, N-(hexyloxypropyl) Sulfamoyl, N-(2-ethylhexyloxypropyl)sulfamoyl, N-(methoxyhexyl)sulfamoyl, N-(3-phenyl-1-methylpropyl)sulfamoyl Acyl etc.

Examples of -SO ₂ NHR ⁸ and -SO ₂ NR ⁸ R ⁹ include groups represented by the following formulae.

In the above formula, X ¹ represents a halogen atom. Examples of the halogen atom in ^X1 include a fluorine atom, a chlorine atom and a bromine atom.

In the above formula, ^X3 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the hydrogen atoms of the alkyl group and alkoxy group may be replaced by halogen atoms.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom include methyl group, ethyl group, propyl group, isopropyl group and trifluoromethyl group.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom include methoxy, ethoxy, propoxy, fluoromethoxy and the like.

In the above formula, ^X2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atoms of the alkyl and alkoxy groups may be substituted by halogen atoms.

Examples of the halogen atom in ^X2 include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom include methyl group, ethyl group, propyl group, isopropyl group and trifluoromethyl group.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom include methoxy, ethoxy, propoxy, fluoromethoxy and the like.

In the above formula, ^X2 has the same meaning as above.

In the above formula, the meaning represented by ^X3 is the same as above.

R ⁸ and R ⁹ contained in -SO ₂ NR ⁸ R ⁹ are preferably a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, and a branched alkyl group having 8 carbon atoms. Aralkyl groups having ∼10 carbon atoms, hydroxy-containing alkyl groups and aryl groups having 2-8 carbon atoms, and alkoxy-containing alkyl or aryl groups having 2-8 carbon atoms, particularly preferably 2-ethylhexyl.

The substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably ethyl, propyl, phenyl, dimethylphenyl, -SO ₃ R ⁶ or -SO ₂ NHR ⁸ .

Examples of substituent aromatic hydrocarbon groups having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decylphenyl, and fluorophenyl , chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, trifluoromethylphenyl wait.

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 optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.

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

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

^R is preferably carboxyl, ethoxycarbonyl, sulfo, N-(2-ethylhexyloxypropyl)sulfamoyl, N-(1,5-dimethylhexyl)sulfamoyl, N-( 3-phenyl-1-methylpropyl)sulfamoyl, N-(isopropoxypropyl)sulfamoyl.

The compound represented by formula (1) is preferably a compound represented by formula (1-1),

[In formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group with 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by 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 , -SO ₂ NHR ⁸ or - SO ₂ NR ⁸ R ⁹ substituted,

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ,

R ¹⁶ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ,

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

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

The compound represented by formula (1) is preferably a compound represented by formula (1-2),

[(In formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group with 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by 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 with 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group can be replaced by -OR ²⁷ or a halogen atom,

R ²⁷ represents a saturated hydrocarbon group having 1 to 10 carbon atoms.

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

The meanings represented by m, X, and a are the same as above.

However, the compound represented by formula (1-2) has the same number of + charges and - charges. ]

The compound represented by formula (1) is preferably a compound represented by formula (1-3),

[In formula (1-3), R ³¹ and R ³² each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group can be replaced by a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ substituted,

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

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

R ²⁶ , R ²⁸ , X and a have the same meanings as above.

However, the compound represented by formula (1-3) has the same number of + charges and - charges. ]

The compound represented by formula (1) is preferably a compound represented by formula (1-4),

[In formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and the hydrogen atoms contained in the phenyl group may be replaced by -R ²⁶ or -SO ₂ NHR ²⁸ ,

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

R ²⁶ , R ²⁸ , X and a represent the same meanings as above.

However, the compound represented by formula (1-4) has the same number of + charges and - charges. ]

The compound represented by formula (1) includes, for example, compounds represented by formula (1a) to formula (1f).

[In formula (1a), R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. The meanings represented by X and a are the same as above. ]

[In the formula (1b), R ^b has the same meaning as above. ]

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

[In the formula (1b-1), the meanings represented by R ^b , X and a are the same as above. ]

[In formula (1c) and formula (1d), R ^d , R ^c and R ^f each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. ]

[In formula (1e) and formula (1f), R ^g , ^Rh and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. ]

Among the compounds represented by formula (1), the compound with -SO ₂ NHR ⁸ can be obtained by the following method, for example, by conventional methods, the pigment with -SO ₃ H or the pigment intermediate is chlorinated, and then the obtained compound with -SO ₂ Cl pigment or pigment intermediate reacts with amine represented by R ⁸ -NH ₂ . It can also be obtained by such a method that a pigment is produced by the method described in the upper right column to the lower left column of the third page of Japanese Patent Laid-Open No. 3-78702, and the pigment is chlorinated in the same way as above, and then reacted with an amine reaction.

The colorant (A) is preferably a colorant further containing an organic pigment.

Specific examples of organic pigments include blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. purple paint etc. Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15:3 or 15:6 are preferred, and C.I. Pigment Blue 15:6 is particularly preferred. These pigments may be used alone or in combination of two or more.

Among the above-mentioned pigments, organic pigments may be subjected to rosin treatment, surface treatment using pigment derivatives introduced with acidic groups or basic groups, etc., grafting treatment on the surface of pigments with polymer compounds, micronization with sulfuric acid, etc. A micronization treatment by the method, etc., a cleaning treatment using an organic solvent or water for removing impurities, a removal treatment of removing ionic impurities by an ion exchange method, or the like.

Preferably, the particle size of the organic pigment is uniform. By adding a pigment dispersant and carrying out a dispersion treatment, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. One type may be used alone, or two or more types may be used in combination.

When a pigment dispersant is used, the amount used is preferably not more than 1 part by mass, more preferably not less than 0.05 part by mass and not more than 0.5 part by mass, per 1 part by mass of the pigment. When the usage-amount of a pigment dispersant is in the said range, there exists a tendency for the pigment dispersion liquid in a uniformly dispersed state to be obtained.

In particular, the mass ratio of C.I. Pigment Blue 15:6 to the compound represented by formula (1) is preferably 97:3 to 50:50.

When the content of the organic pigment in the colorant (A) is within the above-mentioned range, the transmission spectrum is easy to optimize, and because high contrast and high brightness are obtained, it is good, and heat resistance and chemical resistance are good, so it is relatively ideal.

The colored photosensitive composition of this invention contains a binder resin (B). As the binder resin, known ones can be used.

The binder resin is a resin having alkali solubility, and contains structural units derived from the compound (B0) (hereinafter sometimes referred to as "(B0)") and compounds derived from the compound (B2) (hereinafter sometimes referred to as "(B2)"). A copolymer of constituent units. The compound (B0) has a carbon-carbon unsaturated double bond and a cyclic ether structure, and the compound (B2) is at least one selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.

As a cyclic ether structure of (B0), an epoxy structure, an oxetane structure, and a tetrahydrofuran structure are mentioned, for example.

The epoxy structure includes a structure obtained by epoxidizing a chain olefin, a structure obtained by epoxidizing a monocyclic cycloalkene, and a structure obtained by epoxidizing a polycyclic cycloalkene. Preferably, the polycyclic cycloalkene is epoxidized get the structure.

(B0) is preferably a compound containing a carbon-carbon unsaturated double bond and an epoxy structure, more preferably a compound having a carbon-carbon unsaturated double bond and a structure obtained by epoxidizing a polycyclic cycloolefin. When (B0) is these compounds, the solvent resistance and heat resistance of the coating film and color filter obtained are excellent.

Specific examples of compounds containing a carbon-carbon unsaturated double bond and a structure obtained by epoxidizing a chain olefin include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β- Ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, a compound represented by the following formula (IV) described in JP-A-7-248625, and the like.

[In formula (IV), R ⁶¹ to R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m1 is an integer of 1 to 5. ]

The compound represented by the above formula (IV) includes, for example, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl o-vinylbenzyl glycidyl ether, Glyceryl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diecidyloxypropoxymethylstyrene, 2,4-bicyclo Oxypropoxymethylstyrene, 2,5-Diglycidoxymethylstyrene, 2,6-Diglycidoxymethylstyrene, 2,3,4-Triglycidoxypropoxy Triglycidoxymethylstyrene, 2,3,5-triglycidoxymethylstyrene, 2,3,6-triglycidoxymethylstyrene, 3,4,5-triglycidoxypropylene oxymethylstyrene and 2,4,6-triglycidoxymethylstyrene.

The compound having a carbon-carbon unsaturated double bond and a structure obtained by epoxidizing a monocyclic cycloalkene is preferably a compound having a (meth)acryloyloxy group and a structure obtained by epoxidizing a monocyclic cycloalkene. Examples of the aforementioned monocyclic cycloolefin include cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like.

Containing the compound of carbon-carbon unsaturated double bond and the structure obtained by epoxidizing monocyclic cycloalkene, for example, vinyl cyclohexene monooxidized 1,2-epoxy-4-vinyl cyclohexane ( For example, Cyroxide 2000, manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cycromer-A400, manufactured by Daicel Chemical Industry Co., Ltd.), methacrylic acid-3,4 - Epoxycyclohexylmethyl ester (for example, Cycromer M100, manufactured by Daicel Chemical Industry Co., Ltd.) and the like.

Here, the "(meth)acryloyloxy group" in this specification represents at least 1 sort(s) of an acryloyloxy group and a methacryloyloxy group. Expressions such as "(meth)acrylic acid ... ester" and "(meth)acrylic acid" have the same meaning.

A compound (B1) having a carbon-carbon unsaturated double bond and a structure obtained by epoxidizing a polycyclic cycloalkene (hereinafter sometimes referred to as "(B1)") preferably has a (meth)acryloyloxy group and a polycyclic A compound of the structure obtained by epoxidation of a cycloalkene. Examples of the polycyclic cycloolefins include dicyclopentene, tricyclodecene, norbornane, isonorbornene, bicyclooctene, bicyclononene, bicycloundecene, and tricycloundecene. , Bicyclododecene, Tricyclododecene, etc.

(B1) includes, for example, 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, compounds represented by formula (B1-1), and compounds represented by formula (B1-2) The compound represented is preferably at least one compound selected from compounds represented by formula (B1-1) and compounds represented by formula (B1-2).

[In formula (B1-1) and formula (B1-2), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms whose hydrogen atom may be substituted by a hydroxyl group.

X ¹ and X ² each independently represent a single bond, an alkylene group having 1 to 6 carbon atoms, or *-(CH ₂ ) _s -X ³ -(CH ₂ ) _t - .

^X3 represents -S-, -O- or -NH-.

s represents the integer of 1-6, and t represents the integer of 0-6. where s+t≤6.

* indicates the bonding position with O. ]

Specific examples of an alkyl group having 1 to 4 carbon atoms that may be substituted with a hydroxyl group include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and hydroxyl group. Methyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1- Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc., preferably methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, Methyl is more preferred.

R ⁷¹ and R ⁷² are preferably 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.

The heteroatoms of the C 1-6 alkylene group which may contain heteroatoms include oxygen atom, sulfur atom and nitrogen atom. In addition, the number of heteroatoms is not included in the number of carbon atoms.

Examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, propane-1,2-diyl (i.e., 1,2-propylene), propane-1,3-diyl ( That is, 1,3-propylene), butane-1,4-diyl (that is, 1,4-butylene), pentane-1,5-diyl (that is, 1,5-pentylene), hexa Alkane-1,6-diyl (i.e. 1,6-hexylene),

X ¹ and X ² are preferably a single bond, methylene, ethylene, -O-CH ₂ -, or -O-(CH ₂ ) ₂ -, more preferably a single bond or -O-(CH ₂ ) ₂ -.

Compounds represented by formula (B1-1) include compounds represented by formula (B1-1-1) to formula (B1-1-15), preferably formula (B1-1-1), formula (B1-1- 3), compounds represented by formula (B1-1-5), formula (B1-1-7), formula (B1-1-9), formula (B1-1-11) to formula (B1-1-15) , more preferably a compound represented by formula (B1-1-1), formula (B1-1-7), formula (B1-1-9), or formula (B1-1-15).

Examples of the compound represented by formula (B1-2) include compounds represented by formula (B1-2-1) to formula (B1-2-15), preferably formula (B1-2-1), formula (B1 -2-3), Formula (B1-2-5), Formula (B1-2-7), Formula (B1-2-9), Formula (B1-2-11) ~ Formula (B1-2-15) The compound represented is more preferably a compound represented by formula (B1-2-1), formula (B1-2-7), formula (B1-2-9), or formula (B1-2-15).

At least one compound selected from the compound represented by formula (B1-1) and the compound represented by formula (B1-2) can be used alone. Furthermore, they can also be mixed in any ratio. When mixing, its mixing ratio is formula (B1-1): the molar ratio of formula (B1-2), preferably 5:95～95:5, more preferably 10:90～90:10, particularly preferably 20:80～80 : 20.

The compound having the aforementioned carbon-carbon unsaturated double bond and oxetane structure is preferably a compound having an oxetanyl group and a (meth)acryloyloxy group.

Specific examples of compounds having a carbon-carbon unsaturated double bond and an oxetane structure include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyl Oxymethyloxetane, 3-Ethyl-3-methacryloyloxymethyloxetane, 3-Ethyl-3-acryloyloxymethyloxetane, 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methylpropene Acyloxyethyloxetane or 3-ethyl-3-acryloyloxyethyloxetane.

The compound having the aforementioned carbon-carbon unsaturated double bond and the tetrahydrofuran structure is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group.

Specific examples of compounds having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure include tetrahydrofurfuryl acrylate (for example, Bisucoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate wait.

(B2) Examples include 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-tetrahydrogenation Unsaturated dicarboxylic acids such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, etc.;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]-2-heptene, 5,6-dicarboxybicyclo[2.2.1]-2-heptene ene, 5-carboxy-5-methylbicyclo[2.2.1]-2-heptene, 5-carboxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-carboxy-6- Bicyclic unsaturated compounds containing carboxyl groups such as methylbicyclo[2.2.1]-2-heptene and 5-carboxy-6-ethylbicyclo[2.2.1]-2-heptene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]-2-heptene anhydride (norbornene Anhydrides of unsaturated dicarboxylic acids such as dianhydrides);

Not applicable to divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate. Saturated mono[(meth)acryloxyalkyl]esters;

Unsaturated acrylates such as acrylate-α-(hydroxymethyl)ester containing a hydroxyl group and a carboxyl group in the same molecule, and the like.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. They can be used alone or in combination.

The binder resin (B) is a copolymer containing a structural unit derived from (B0) and a structural unit derived from (B2), and the ratio of the structural unit derived from (B0) to the structural unit derived from (B2) relative to When the total of the constituent units is in the following range, it is preferable because the storage stability, heat resistance, and mechanical strength tend to be good.

Structural unit derived from (B0): 2 to 98 mol%

Structural unit derived from (B2): 2 to 98 mol%

Moreover, when the ratio of the said structural unit exists in the following range, it is more preferable from a viewpoint of developability and solvent resistance.

Structural unit derived from (B0): 40 to 85 mol%

Structural unit derived from (B2): 15 to 60 mol%

The manufacture of the above-mentioned adhesive resin (B) can refer to, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition, 1st Printing, March 1, 1972) and references cited in this document.

Specifically, a certain amount of (B0) and (B2), a polymerization initiator, and a solvent are loaded into a reaction vessel, nitrogen is replaced by oxygen, and in the absence of oxygen, stirring, heating, and heat preservation are carried out to obtain a copolymer. In addition, for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) may be taken out by reprecipitation or the like and used.

In addition, the adhesive resin (B) contains, in addition to the constituent units derived from (B0) and the constituent units derived from (B2), compounds derived from compounds copolymerizable with (B0) and (B2) (However, (B1) and (B2) ) (excluding )) (B3) (hereinafter sometimes referred to as "(B3)") constituent units.

The aforementioned (B3) includes methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate Alkyl (meth)acrylates such as esters;

Alkyl acrylates such as methyl acrylate and isopropyl acrylate;

Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[ ^5.2.1.02,6 ]decane-8-yl (meth)acrylate (in this technical field , the common name is (meth) dicyclopentyl acrylate (jithic cropentyl (Meta) Acrylet)), (meth) acrylate dicyclopentyl oxyethyl Cyclic alkyl esters of (meth)acrylate such as (meth)acrylite), isobornyl (meth)acrylate;

Aryl (meth)acrylates such as phenyl (meth)acrylate;

Aralkyl (meth)acrylates such as benzyl (meth)acrylate;

Dicarboxylic acid diesters of diethyl maleate, diethyl fumarate, diethyl itaconate, etc.;

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

Bicyclo[2.2.1]-2-heptene, 5-methylbicyclo[2.2.1]-2-heptene, 5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxy Bicyclo[2.2.1]-2-heptene, 5-hydroxymethylbicyclo[2.2.1]-2-heptene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]-2 -heptene, 5-methoxybicyclo[2.2.1]-2-heptene, 5-ethoxybicyclo[2.2.1]-2-heptene, 5,6-dihydroxybicyclo[2.2 .1]-2-heptene, 5.6-bis(hydroxymethyl)bicyclo[2.2.1]-2-heptene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1] -2-heptene, 5,6-dimethoxybicyclo[2.2.1]-2-heptene, 5,6-diethoxybicyclo[2.2.1]-2-heptene, 5- Hydroxy-5-methylbicyclo[2.2.1]-2-heptene, 5-hydroxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl Bicyclo[2.2.1]-2-heptene, 5-tert-butoxycarbonylbicyclo[2.2.1]-2-heptene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]-2-heptene ene, 5-phenoxycarbonylbicyclo[2.2.1]-2-heptene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]-2-heptene, 5-6- Bicyclic unsaturated compounds such as bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]-2-heptene;

N-phenylmaleic anhydride imide, N-cyclohexylmaleic anhydride imide, N-benzylmaleic anhydride imide, N-succinimidyl-3-maleic anhydride imide benzene Formate, N-succinimidyl-4-maleic imide butyrate, N-succinimidyl-6-maleic imide caproate, N-succinimidyl- Dicarbonyl imide derivatives such as 3-maleic anhydride imide propionate and N-(9-acridyl)maleic anhydride imide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide , methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among them, benzyl acrylate, styrene, N-phenylmaleic anhydride imide, N-cyclohexylmaleic anhydride imide, N-benzylmaleic anhydride imide, bicyclo[2.2.1] -2-heptene etc.

The above-mentioned (B3) can be used alone or in combination.

When (B3) is contained, it is preferable that the ratio of the structural unit derived from (B0)-(B3) is the following range with respect to the total number of moles of the structural unit which comprises the said copolymer.

Structural unit derived from (B0): 2 to 97 mol% (more preferably 10 to 48 mol%)

Structural unit derived from (B2): 2 to 97 mol% (more preferably 10 to 48 mol%)

Structural unit derived from (B3): 1 to 96 mol% (more preferably 4 to 80 mol%)

The binder resin (B) containing said (B0)-(B3) can be manufactured as mentioned above.

In addition, as the structural unit in the above-mentioned adhesive resin (B), macromonomers containing an acryloyl group or a monomethacryloyl group at the end, a structural unit represented by the formula (II), and a structural unit represented by the formula (III) are included. etc., it is excellent in pattern adhesion and solvent resistance.

(In formula (II) and formula (III), R ⁵³ and R ⁵⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

The adhesive resin (B) having the structural unit represented by the formula (II) can be obtained as follows: (B2), (B3) are copolymerized to obtain a copolymer, and the obtained copolymer and the compound represented by the formula (III-1) are mixed in (B2) obtained by reacting the carboxyl group or acid anhydride contained therein.

(In formula (II-1) and formula (III-1), R ⁵⁴ and R ⁵⁶ are the same as above).

The adhesive resin having the constituents represented by the formula (III) can be obtained as follows: (B2) and (B3) are copolymerized to obtain a copolymer, and the obtained copolymer and the compound represented by the formula (III-1) are obtained by, for example, combining with Japanese Patent It can be obtained by reacting in the same way as described in JP-A-2005-189574.

The polystyrene equivalent weight average molecular weight of the binder resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight-average molecular weight of the binder resin (B) is within the above range, the applicability tends to be good, film loss is less likely to occur during development, and the removability of non-pixel parts during development tends to be good.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, it tends to be excellent in developability.

The content of the binder resin (B) is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, based on the solid content in the colored photosensitive composition. When the content of the binder resin (B) is within the above range, the solubility in the developer tends to be sufficient, the development residue is less likely to appear on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion during development tends to be less likely to appear. Reduction, the removal of non-pixel parts is good.

The colored photosensitive composition of this invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by active radicals, acids, etc. generated by the photopolymerization initiator (D) when it is irradiated with light, for example, a compound having a polymerizable carbon-carbon unsaturated bond, etc. .

The photopolymerizable compound (C) is preferably a polyfunctional photopolymerizable compound having three or more functional groups. Examples of photopolymerizable compounds having three or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, di Pentaerythritol hexamethacrylate, etc. The above-mentioned photopolymerizable compound (C) may be used alone or in combination of two or more, and its content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass. When the content of the photopolymerizable compound (C) is in the above range, the curing is sufficient, the film thickness ratio before and after image development is improved, the undercut (undercut) is difficult to enter the pattern, and the adhesion tends to be good.

The colored photosensitive resin composition of this invention contains a photoinitiator (D). The photopolymerization initiator is a compound capable of polymerizing the polymerizable compound (C) by generating active radicals, acids, etc. when irradiated with light, and is preferably a compound that generates radicals by ultraviolet rays. Examples of the photopolymerization initiator (D) include active radical generators, acid generators, and the like.

The active radical generating agent generates active radicals by light irradiation. Examples of the active radical generating agent include acetophenone-based compounds, benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, triazine-based compounds, and oxime-based compounds.

From the viewpoint of sensitivity, the photopolymerization initiator (D) is preferably a compound having an oxime structure.

The above-mentioned oxime compounds include, for example, O-acyl oxime compounds, and specific examples thereof include N-benzoyloxy-1-(4-phenylsulfamoylphenyl)-1-butanone-2-imine , N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone-2-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl-4- (3,3-dimethyl-2,4-dioxocyclopentyl (pentanil) methoxy) benzoyl) -9H-carbazol-3-yl] ethane-1-imine, etc., preferably N-benzoyloxy-1-(4-phenylsulfamoylphenyl)-1-octanone-2-imine. When the oxime compound is N-benzoyloxy-1-(4-phenylsulfamoylphenyl)-1-octanone-2-imine, a color filter with high brightness can be obtained.

As the oxime-based compound, commercially available products such as Irugakiyua OXE01, Irugakuyua OXE02 (the above are manufactured by Ciba Japan Co., Ltd.), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used.

The aforementioned acetophenone-based compounds include, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylsulfonylphenyl)-1-propanone, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzyl-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzyldimethyl Ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methanone Oligomers of -1-[4-(1-methylvinyl)phenyl]-1-propanone, etc., preferably 2-methyl-2-morpholino-1-(4-methylsulfonamide Acylphenyl)-1-propanone.

Examples of the above-mentioned azoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

The aforementioned benzophenone-based compounds include, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3 , 3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

The aforementioned thioxanthone-based compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-Chloro-4-propoxythioxanthone, etc.

The aforementioned triazine compounds are exemplified by 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-(4-methoxystyryl)-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3, 4-dimethoxyphenyl)vinyl]-1,3,5-triazine and the like.

Active radical generators other than those exemplified above can also be used such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, dibenzoyl, 9,10-phenanthrenequinone, camphor Quinone, methyl phenylglyoxylate, titanocene compound, etc.

Examples of the aforementioned acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium Sulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, di Onium salts such as phenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, or nitrobenzyl toluenesulfonate (or ester), benzoin toluenesulfonate ( or esters) etc.

In addition, among the above-mentioned active radical generators, there are compounds that generate active radicals and also generate acids. For example, a triazine photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator (D) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the binder resin (B) and the photopolymerizable compound (C). When content of a photoinitiator exists in the said range, sensitivity becomes high, exposure time is shortened, and productivity improves.

The photopolymerization start adjuvant (F) may be contained further in the colored photosensitive composition of this invention. A photopolymerization start adjuvant (F) is usually used in combination with a photopolymerization initiator (D), and is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound whose polymerization is initiated by a photopolymerization initiator.

As a photopolymerization start adjuvant (F), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, etc. are mentioned.

Examples of the aforementioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Amylaminobenzoic acid isoamyl ester, benzoic acid-2-dimethylaminoethyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl ester, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino) Among them, benzophenone and the like are preferably 4,4'-bis(diethylamino)benzophenone.

Examples of the aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2- Ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the above-mentioned thioxanthone-based compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Ketones, 1-chloro-4-propoxythioxanthone, etc.

A photopolymerization start adjuvant (F) may be used individually or in combination of 2 or more types. In addition, a commercially available product can also be used as a photopolymerization start adjuvant (F), and a commercially available photopolymerization start adjuvant (F) is exemplified, for example, a brand name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) wait.

Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation adjuvant (F) in the colored photosensitive composition of the present invention include diethoxyacetophenone/4,4'-bis(diethyl Amino)benzophenone, 2-methyl-2-morpholino-1-(4-methylsulfonylphenyl)-1-propanone/4,4'-bis(diethylamino)diphenyl Methanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone/4,4'-bis(diethylamino)benzophenone, benzyl dimethyl ketal/4,4' -Bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone/4,4'-bis( Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone/4,4'-bis(diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4 -Oligomers of (1-methylvinyl)phenyl]-1-propanone/4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-1-butanone/4,4'-bis(diethylamino)benzophenone, etc., preferably 2-methyl-2-morpholino-1 -(4-Methylsulfonylphenyl)-1-propanone/4,4'-bis(diethylamino)benzophenone.

When using these photopolymerization start adjuvant (F), it is preferable that the usage-amount is 0.01-10 mol with respect to 1 mol of photopolymerization initiator (D), and it is more preferable that it is 0.01-5 mol.

The colored photosensitive composition of this invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethylsulfoxide, and the like.

Examples of the aforementioned ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethyl Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl Ether Acetate, Propylene Glycol Monomethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Ethyl Carbitol Acetate, Butyl Carbitol Acetate, Anise Ether (anisole), phenetole, methyl anisole, etc.

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

Examples of the aforementioned ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl- 2-pentanone, cyclopentanone, cyclohexanone, etc.

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

Examples of the above-mentioned esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate esters, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxypropionate Methyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl ester, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetate Methyl ester, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , γ-butyrolactone, etc.

Examples of the aforementioned amides include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among them, ethers, ketones, and esters are preferable. More preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and 4-hydroxy-4-methyl-2-pentanone, and it is more desirable to use these in combination.

Moreover, the said solvent may be used individually, and may use it in combination of 2 or more types.

The content of the solvent (E) in the colored photosensitive composition is preferably 70 to 95% by mass, more preferably 75 to 90% by mass based on the colored photosensitive composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density does not become insufficient when forming a color filter, and the display characteristics tend to be good.

The colored photosensitive resin composition of this invention may contain surfactant (G) further. Examples of the surfactant (G) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom.

As said polysiloxane type surfactant, the surfactant etc. which have a siloxane bond are mentioned. Concretely, there are トレシリコン DC3PA, TOSH7PA, TODC11PA, TOSH21PA, TOSH28PA, TOSH29PA, TOSH30PA, polyether modified silicone oil SH8400 (trade name: トレシリコン; Toray Dowco NINGE Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by MOMENTIBU PAFO-MANS MATERIALS JAPAN CO., LTD.) and the like.

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain are mentioned. Concretely, there are Fluorado (trade name) FC430, TO FC431 (manufactured by SUMIMEM Co., Ltd.), Megaface (registered trademark) F142D, TO F171, TO F172, TO F173, TO F177, TO F183, TO R30. (manufactured by DIC Co., Ltd.), Eftop (trade name) EF301, same as EF303, EF351, EF352 (manufactured by Mitsubishi Material Electron Chemicals Co., Ltd.), Surflon (trade name) S381, same as S382, same as SC101, same as SC105 ( manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Phaein Chemical Research Institute Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie Co., Ltd.), and the like.

Examples of the above-mentioned polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, DIC BL20, DID F475, DID F477, DID F443 (manufactured by DIC Corporation) and the like.

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

The content of the surfactant (G) is preferably 0.00001 to 0.1% by mass, more preferably 0.00005 to 0.01% by mass, based on the colored photosensitive composition. When the content of the surfactant (G) is within the above range, flatness tends to be favorable.

As a method of forming a pattern of a color filter using the colored photosensitive composition of the present invention, the following method and a method using an inkjet machine that does not require photolithography, etc. are exemplified. The above-mentioned method is to combine the colored photosensitive composition of the present invention coating on the substrate or another resin layer (for example, another colored photosensitive composition layer formed on the substrate earlier), remove volatile components such as solvents to form a colored layer, and expose the colored layer through a photomask. Colorize the layer and develop.

Several TFTs 22 are formed on the glass substrate 21 for each pixel by a known method such as photolithography (see FIG. 1 ). The TFT 22 is composed of a gate electrode 22a, a gate insulating film 22b, a polysilicon film 22c formed on the gate insulating film 22b, and a laminate film such as an oxide film (SiO ₂ ) and a nitride film (SiN _x ). Formed protective film 22d, the gate electrode 22a is formed on the glass substrate 21 by, for example, molybdenum (Mo), and constitutes a part of the gate (gate) line; the gate insulating film 22b is formed on the gate electrode 22a, for example, by nitride Film (SiN _x ) and oxide film (SiO ₂ ) laminated film configuration. A region of the polysilicon film 22c facing the gate electrode 22a is a channel region of the TFT 22, and regions on both sides of the channel region are source regions or drain regions. The source region of the polysilicon film 22c is electrically connected to a signal line 27 formed of, for example, aluminum through a contact hole provided on the protective film 22d. In addition, the drain region of the polysilicon film 22 c is electrically connected to the pixel electrode 24 through a contact hole 201 described later.

For each pixel, when several TFTs 22 are formed on the glass substrate 21 , calibration symbols (not shown) are formed while the TFTs 22 are formed on the glass substrate 21 . This calibration mark is used as a reference for positioning in the process of forming the color filter layer 23 described later. In addition, these alignment symbols may also be used as symbols for laminating the drive substrate and the counter substrate. The calibration marks can be formed when forming a metal layer such as wiring or a polysilicon layer in the manufacturing process of the TFT 22 , and can be formed in the same process using at least one layer thereof.

Next, a colored photosensitive composition layer 23A having a film thickness of 0.5 to 5.0 μm, for example, 1.0 μm is formed on the TFT 22 and the glass substrate 21 on which the calibration marks are formed by spin coating or other methods. This colored photosensitive composition layer 23A corresponds to the color filter of the present invention.

Next, the coloring photosensitive composition layer 23A is dried by heat-processing at the temperature in the range of 30-120 degreeC, Preferably it is 60-110 degreeC. In order to dry 23 A of coloring photosensitive composition layers, it can perform combining drying under reduced pressure and drying with heat. Next, the colored photosensitive composition layer 23A is irradiated with ultraviolet light through a photomask (not shown), and then the unnecessary portion (that is, the non-exposed portion) is selectively removed by a developer to form a connection to the drain region of the polysilicon film 22c. The contact hole 201 is then washed with water. Then, in order to reflow the colored photosensitive composition layer 23A and to cure the curable components contained in the colored photosensitive composition layer 23A, the temperature ranges from 100°C to 300°C, preferably 150°C to 230°C. down for heating.

Thereby, 23 A of coloring photosensitive composition layers become the color filter layer 23 (refer FIG. 2) containing the red filter 23a, the green filter 23b, and the blue filter 23c corresponding to each pixel column. The area between the filters of the color filter layer 23 is a mixed area of adjacent colors, but these areas are light-shielding areas facing the signal line 27, so there is no problem especially in terms of quality. In addition, the regions between these respective filters may not be colored.

Next, a protective film photosensitive resin film 29 having a film thickness of, for example, 0.3 to 2.0 μm is formed by, for example, a spin coating method to cover the color filter layer 23 (see FIG. 3 ). Next, the photosensitive resin film 29 is irradiated with ultraviolet light through a photomask (not shown), and then the region corresponding to the connection hole 201 and unnecessary parts are selectively removed by a developer to form a connection to the drain region of the polysilicon film 22c. hole (contact hole) 202, and then washed with water. Then, in order to reflow (reflow) the photosensitive resin film 29, it heats at the range temperature of 100 degreeC - 300 degreeC, for example, 200 degreeC. Next, etching is performed with oxygen plasma in order to remove residues and organic matter accumulated in the connection hole 202, and etching is performed with, for example, dilute hydrofluoric acid in order to remove the oxide film formed by the oxygen plasma.

Next, a transparent conductive material such as ITO (Indium-TinOxide: an oxide mixed film of indium and tin) is formed on the photosensitive resin film 29 by, for example, sputtering, and the ITO film is patterned by photolithography and etching. , forming a transparent pixel electrode 24 (see FIG. 4 ). The pixel electrode 24 may be formed of metal such as aluminum (Al) or silver (Ag) depending on the manufacturing method. Then, after forming an alignment film by a known method, the drive substrate and the counter substrate are bonded together to manufacture a liquid crystal display device.

According to the colored photosensitive composition of this invention, the coating film with high contrast can be obtained.

Example

Hereinafter, the present invention will be described in more detail based on examples. "%" and "part" in an example are mass % and a mass part, unless there is special mention.

Synthesis Example 1

[Synthesis example of compound represented by formula (2)]

<Synthesis of Compound Represented by Formula (2-24-1a)>

Put 75 parts of 4-nitrophthalonitrile and 375 parts of N,N-dimethylacetamide into a flask with a cooling tube and a stirring device, and slowly add 68.9 parts while maintaining the temperature below 20°C under stirring Sodium carbonate. Further, 68.9 parts of methyl 3-mercaptopropionate were dropped while maintaining the temperature below 20° C. under stirring. After dripping, stir at room temperature for 3.5 hours, filter the reaction solution, inject the filtrate into 2250 parts of 1 N hydrochloric acid, filter and separate the precipitate, wash carefully with ion-exchanged water, and dry under reduced pressure at 50°C to obtain 104.4 A compound represented by the formula (2-24-1a).

<Synthesis of Compound Represented by Formula (2-24-1b)>

52.0 parts of compound (2-24-1a) and 104.0 parts of N,N-dimethylformamide were put into a flask equipped with a cooling tube and a stirring device, and 40.2 parts of 1 were dropped while maintaining the temperature below 20°C under stirring, 8-diazabicyclo[5.4.0]-7-undecene (DBU). After completion of the dropping, the mixture was stirred at room temperature for 2.5 hours. The reaction solution was poured into 208.0 parts of water, and then concentrated hydrochloric acid was added until the pH was below 2. The precipitate was filtered off, carefully washed with ion-exchanged water, and dried under reduced pressure at 50°C to obtain 33.6 parts of compound (2-24-1b).

<Synthesis of Compound Represented by Formula (2-24-1c)>

33.0 parts of compound (2-24-1b) and 396 parts of acetic acid were charged into a flask equipped with a cooling tube and a stirring device, and 4.2 parts of sodium tungstate was added while stirring at room temperature. While maintaining the temperature below 30° C. under stirring, 87.5 parts of 30% hydrogen peroxide was added dropwise. After completion of the dropping, the temperature was raised to 50° C. and stirred for 2 hours. The reaction solution was cooled to room temperature, and the reaction solution was poured into a solution obtained by dissolving 60.7 parts of potassium acetate in 396 parts of methanol, followed by stirring for 1 hour. The precipitate was filtered off, washed with methanol, and dried under reduced pressure at 50°C to obtain 35.0 parts of the compound represented by the formula (2-24-1c).

<Synthesis of Compound Represented by Formula (2-24-1d)>

5.0 parts of compound (2-24-1c), 0.82 parts of copper chloride, 0.40 parts of ammonium molybdate, and 19.1 parts of quinoline were charged into a flask equipped with a cooling tube and a stirring device. The flask was placed in an oil bath previously set at 100°C, and the temperature was raised to 160°C while stirring. Stirring was continued for another 3 hours, cooled to 100°C, and 66.5 parts of methanol were added. The precipitate was filtered off, washed with methanol, and dried under reduced pressure at 50°C to obtain 2.0 parts of the compound represented by the formula (2-24-1d).

<Synthesis of Compound Represented by Formula (2-24-1)>

57.6 parts of anhydrous N,N-dimethylacetamide and 1.5 parts of anhydrous N,N-dimethylformamide were put into a flask equipped with a cooling tube and a stirring device. Cool to 0°C, add 2.3 parts of thionyl chloride dropwise, and continue stirring at 0°C for 1 hour. Further, 1.8 parts of compound (2-24-1d) was added, and stirred at room temperature for 30 minutes, at 50°C for 1.5 hours, and at 80°C for 4 hours. After cooling to 0°C, a mixed solution of 2.8 parts of N,N-dimethyl-1,3-propylenediamine and 4.2 parts of triethylamine was added dropwise. After stirring at room temperature for 15 minutes and at 80° C. for 4 hours, 506.9 parts of methanol were added. The precipitate was filtered off, carefully washed with methanol, and dried under reduced pressure at 50°C to obtain 1.6 parts of the compound represented by the formula (2-24-1).

Synthesis example 2

<Synthesis example of compound represented by formula (1)>

In a flask with a cooling tube and a stirring device, drop into a mixture of 15 parts of the compound represented by the formula (A0-1) and the compound represented by the formula (A0-2) (manufactured by Zhongwai Huacheng), 150 parts of chloroform and 8.9 parts of N, N -Dimethylformamide, 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature below 20° C. under stirring. After completion of the dropping, the temperature was raised to 50°C, and the temperature was maintained for 5 hours to react, and then cooled to 20°C. A mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise while maintaining the cooled reaction solution at 20° C. or lower with stirring. Then, stirring was carried out at the same temperature for 5 hours to make it react. Next, after distilling off the solvent in the obtained reaction mixture with a rotary evaporator, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were filtered out, carefully washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 11.3 parts of a mixture of compounds represented by formula (A1-a) and compounds represented by formula (A2-b) (formula (A1-b) 1) A mixture of compounds represented by the formula (A1-8); dye A1)

[In formula (A1-a) and formula (A1-b), R ^g , ^Rh and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or N-(2-ethylhexyl) Sulfamoyl].

[In the above formula, * represents the bonding position with -NH-. ]

Synthesis example 3

Into a 1L flask with a reflux cooling tube, a dropping funnel, and a stirrer, nitrogen gas was introduced at 0.02 L/min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxyl were added. butyl butyl acetate, heated to 70°C while stirring. Next, dissolve 60 parts by mass of methacrylic acid, 240 parts by mass of 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (compound represented by formula (B1-1-1) and formula (B1-2- 1) The compound represented by 1) was mixed at a molar ratio of 50:50) and 140 parts by mass of 3-methoxybutyl acetate, and the solution was dropped into a flask kept at 70°C over 4 hours using a dropping funnel. On the other hand, 30 parts by mass of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate, and the solution was Another dropping funnel was added dropwise to the flask over 4 hours. After the addition of the polymerization initiator was completed, it was kept at 70°C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3×10 ⁴ , a molecular weight distribution (Mw/Mn) of 2.5, a solid content of 33% by mass, and an acid value of Resin solution B1 of 34 mg-KOH/g (acid value of solution).

<Measurement of Molecular Weight>

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of obtained resin B1 was performed on the following conditions using the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

(Chromatography) column: TSK-GELG2000HXL

(Chromatography) column temperature : 40°C

Solvent: THF

Flow rate : 1.0mL/min

Concentration of detected liquid and solid components: 0.001 to 0.01% by mass

Injection volume : 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500,

A-500 (manufactured by Tosoh Corporation)

Example 1

Mix the following materials, and use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 27 parts

Acrylic pigment dispersant 9.1 parts

Propylene Glycol Monomethyl Ether Acetate 196 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Coloring agent: 27 parts of the compound represented by formula (2-24-1)

(A) colorant: compound represented by formula (1): dye A1 6.0 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

Keto-2-imine 15 parts

(Manufactured by イルガキユアOXE01 Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 376 parts

Example 2

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 27 parts

Acrylic pigment dispersant 9.1 parts

Propylene glycol monomethyl ether acetate 196 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Coloring agent: 27 parts of salt of C.I. Direct Blue 264 and dodecylbenzenesulfonic acid

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 6.0 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

                                                                               

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 376 parts

Example 3

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 31 parts

Acrylic pigment dispersant 11 parts

Propylene glycol monomethyl ether acetate 226 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Colorant: C.I. Direct Blue 264 and salt of dodecylbenzenesulfonic acid 13 parts

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 5.0 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

-2-imine 15 parts

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 312 parts

Example 4

The following substances were mixed to obtain a colored photosensitive composition.

(A) Colorant: C.I. Direct Blue 264 and salt of dodecylbenzenesulfonic acid 57 parts

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 5.0 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

-2-imine 15 parts

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 526 parts

Reference example 1

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 18 parts

(A) Colorant C.I. Pigment Violet 23 5.7 parts

Acrylic pigment dispersant 6.1 parts

Propylene Glycol Monomethyl Ether Acetate 154 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(B) Resin: resin solution B1 136 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 55 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

-2-imine 15 parts

(イルガキユアOXE01; manufactured by Chiba Japan Corporation)

(E) Solvent: propylene glycol monomethyl ether acetate 319 parts

[pattern formation]

After the colored photosensitive composition was coated by spin coating on a glass substrate with a side length of 2 inches (Igel 2000; manufactured by Corninge Co., Ltd.), it was prebaked at 100° C. for 3 minutes. After cooling, the coated photosensitive composition The distance between the substrate of the colored photosensitive composition and the photomask made of quartz glass with a pattern was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at a temperature of 150 mJ/cm ² . Exposure amount (365nm standard) carries out light irradiation. After light irradiation, the above-mentioned coating film is immersed in the aqueous developing solution containing nonionic surfactant 0.12% and potassium hydroxide 0.04% at 23 ℃ for 80 seconds, and develops. After washing with water, post-baking was performed in an oven at 220° C. for 20 minutes. After standing to cool, the film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 2.0 μm.

[Chromatic evaluation]

For the pattern on the obtained glass substrate, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and xy in the XYZ colorimetric system of CIE was measured using the equichromatic function of the C light source. Chromaticity coordinates (Bx, By) and brightness. The results are shown in Table 1.

[Contrast evaluation]

Except for exposing without using a photomask, other operations were performed in the same manner as pattern formation, and a contrast colorimeter (CT-1; manufactured by Tsubusaka Electric Co., Ltd., detector, BM-5A, light source; F-10), set the blank value as 10000, and measure the contrast. The coating film on the glass substrate was sandwiched between polarizing films (POLAX-38S; manufactured by Lukeo Co., Ltd.), and this was used as a sample. The results are shown in Table 1.

Table 1

Example 1 Example 2 Example 3 Example 4 Reference example 1 Bx 0.141 0.141 0.141 0.143 0.143 By 0.085 0.085 0.085 0.085 0.085 Brightness 9.4 9.2 9.4 8.8 8.8 Contrast 6900 6740 6960 7020 5150

Example 5

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 17 parts

Acrylic pigment dispersant 5.7 parts

Propylene Glycol Monomethyl Ether Acetate 122 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Coloring agent: 3.6 parts of salt of C.I. Direct Blue 264 and dodecylbenzenesulfonic acid

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 3.6 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

                                                                               

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 320 parts

Example 6

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 15 parts

Acrylic pigment dispersant 5.2 parts

Propylene Glycol Monomethyl Ether Acetate 111 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Colorant: C.I. Direct Blue 264 and salt of dodecylbenzenesulfonic acid 6.4 parts

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 3.8 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

                                                                               

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 320 parts

[pattern formation]

The same operation as in Example 1 was carried out to prepare a pattern. When the film thickness of the obtained pattern was measured using a film thickness measuring device, it was 3.0 μm.

[Chromatic evaluation]

The same operation as in Example 1 was carried out to measure xy chromaticity coordinates (Bx, By) and brightness. The results are shown in Table 2.

[Contrast evaluation]

The same operation as in Example 1 was performed, and the contrast of the coating film on the obtained glass substrate was measured. The results are shown in Table 2.

Table 2

Example 5 Example 6 Bx 0.144 0.145 By 0.085 0.085 Brightness 9.6 9.6 Contrast 6200 6450

Synthesis Example 4

In the flask with stirrer, thermometer, reflux cooling pipe, dropping funnel and nitrogen gas introduction pipe, import 182g propylene glycol monomethyl ether acetate, after making the atmosphere in the flask change from air to nitrogen, be warming up to 100 ℃, then, Add a solution dropwise and continue stirring at 100°C. The solution is made of 70.5g (0.40 mole) benzyl methacrylate, 43.0g (0.5 mole) methacrylic acid, 22.0g (0.10 mole) tricyclodecane 3.6 g of 2,2'-azobisisobutyronitrile was added to a mixture of alkane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 g of propylene glycol monomethyl ether acetate . Then, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g [0.25 mol, (50 mol % relative to the carboxyl group of methacrylic acid used in this reaction)] glycidyl methacrylate, 0.9 g Tris(dimethylaminomethyl)phenol and 0.145 g of hydroquinone were continuously reacted at 110° C. to obtain a resin solution B2 with a solid content of 32% and a solid acid value of 79 mgKOH/g. The polystyrene equivalent weight average molecular weight measured by GPC was 30,000.

Example 7

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 27 parts

Acrylic pigment dispersant 9.1 parts

Propylene glycol monomethyl ether acetate 196 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Colorant: C.I. Direct Blue 264 and salt of dodecylbenzenesulfonic acid 1.1 parts

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 4.8 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

-2-imine 15 parts

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: ethyl lactate 280 parts

Example 8

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 25 parts

Acrylic pigment dispersant 8.4 parts

Propylene Glycol Monomethyl Ether Acetate 181 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) Colorant: C.I. Direct Blue 264 and salt of dodecylbenzenesulfonic acid 2.3 parts

(Manufactured by Orihent Chemical Industry Co., Ltd.)

(A) colorant: compound represented by formula (1): dye A1 4.8 parts

(B) Resin: resin solution B1 152 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

-2-imine 15 parts

(イルガキユアOXE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: ethyl lactate 308 parts

Comparative example 1

Mix the following materials, use a porous glass bead mill to fully disperse the pigment,

(A) Colorant C.I. Pigment Blue 15:6 20 parts

Acrylic pigment dispersant 5 parts

Propylene Glycol Monomethyl Ether Acetate 137 parts

Next, the following substances were mixed to obtain a colored photosensitive composition.

(A) colorant: compound represented by formula (1): dye A1 3.5 parts

(B) Resin: resin solution B1 157 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate 50 parts

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

(D) Photopolymerization initiator: N-benzoyloxy-1-(4-phenylsulfonylphenyl)-1-octanone

                                                     

(イルガキユア0XE01; manufactured by Chiba Jiyapan Corporation)

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 289 parts

[pattern formation]

The same operation as in Example 1 was carried out to prepare a pattern. When the film thickness of the obtained pattern was measured using a film thickness measuring device, it was 2.2 μm.

[Chromatic evaluation]

The same operation as in Example 1 was carried out to measure xy chromaticity coordinates (Bx, By) and brightness. The results are shown in Table 3.

[Contrast evaluation]

The same operation as in Example 1 was performed, and the contrast of the coating film on the obtained glass substrate was measured. The results are shown in Table 3.

table 3

Example 7 Example 8 Comparative Example 1 Bx 0.141 0.141 0.141 By 0.085 0.085 0.085 Brightness 9.7 9.7 9.7 Contrast 6360 6420 5750

High contrast was confirmed in the coating film formed using the colored photosensitive composition of an Example.

Industrial availability

According to the present invention, it is possible to manufacture a high-contrast color filter suitable for forming a colored image constituting a color filter used in a liquid crystal display element or a solid-state imaging element.

Symbol Description

21 glass substrate

22TFT (switching element)

22a Gate electrode

22b gate insulating film

22c polysilicon film

22d protective film 23 color filter layer

23A colored photosensitive composition layer (color filter)

23a red filter

23b green filter

23c blue filter

24 pixel electrodes

27 signal line

29 photosensitive resin film (protective film)

201, 202 connecting holes

Claims (9)

1. A colored photosensitive composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant is a colorant containing a compound represented by formula (2) , In formula (2), G ¹ represents an alkylene group having 2 to 12 carbon atoms, the hydrogen atoms contained in the alkylene group may be substituted by an alkyl group having 1 to 4 carbon atoms, and J ¹ represents -NR ^a R ^b H ⁺ Q ^- , R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Q ^- means Y - SO ₃ , Y represents a monovalent organic group, n ^a represents an integer of 1-4. 2. The colored photosensitive composition according to claim 1, wherein the colorant is a colorant further comprising a compound represented by formula (1), In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group with 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ are substituted, R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ , m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different, X represents a halogen atom, a represents an integer of 0 or 1, R ⁶ represents a saturated hydrocarbon group with 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group with 1 to 10 carbon atoms may be replaced by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, - CO - or - NR ¹⁰ - replaces, R ¹⁰ represents a hydrogen atom or a saturated hydrocarbon group with 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O- or -CO- , R ⁸ and R ⁹ each independently represent an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Q ¹ , and the hydrogen atoms contained in the alkyl group and the cycloalkyl group can be replaced by a hydroxyl group. , a halogen atom, -Q ¹ substitution, the -CH ₂ - contained in the alkyl group and the cycloalkyl group may be substituted by -O-, -CO- or -NR ¹⁰ -, R ⁸ and R ⁹ may be bonded to each other to form A heterocyclic ring with 1 to 10 carbon atoms is formed, and the hydrogen atoms contained in the heterocyclic ring can be replaced by R ⁶ , -OH or -Q ¹ , Q ¹ represents an aromatic hydrocarbon group with 6 to 10 carbon atoms or an aromatic heterocyclic group with 3 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group and aromatic heterocyclic group can be replaced by -OH, -R ⁶ , -OR ⁶ or halogen atom substitution, M represents a sodium atom or a potassium atom, However, the compound represented by formula (1) has the same number of + charges and - charges. 3. The colored photosensitive composition according to claim 1, wherein the colorant further contains an organic pigment. 4. The colored photosensitive composition according to claim 3, wherein the organic pigment is an organic pigment containing C.I. Pigment Blue 15:6. 5. The colored photosensitive composition according to claim 1, wherein the content of the compound represented by formula (2) is 1 to 50% by mass relative to the colorant. 6. The colored photosensitive composition according to claim 1, wherein the photopolymerization initiator is a compound having an oxime structure. The coating film formed using the coloring photosensitive composition of Claim 1. The color filter formed using the coloring photosensitive composition of Claim 1. 9. The color filter according to claim 8, which is formed by photolithography.