JP2020052071A - Photosensitive coloring composition for color filter, and color filter - Google Patents

Abstract

To provide: a photosensitive coloring composition for a color filter which realizes high resolution of a coloring pattern and can form pixels without a residue after development; and a color filter formed using the same.SOLUTION: The coloring composition contains, when an aluminum phthalocyanine pigment [A] represented by general formula (A-1) is used, a phthalocyanine dye derivative represented by general formula (103), and further contains a resin type dispersant, a binder resin, a polymerizable compound, a photoinitiator, and an organic solvent.SELECTED DRAWING: None

Description

  The present invention provides a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, a coloring composition used for manufacturing a color filter used for electronic paper and the like, and a photosensitive coloring composition. And a color filter including a filter segment formed using the same.

The color filter is formed by disposing two or more kinds of fine band-shaped filter segments having different hues in parallel (in a stripe shape) or crossing each other on a transparent substrate such as a glass substrate. Are arranged so that two or more types of fine filter segments different from each other are sequentially arranged in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of several microns to several hundreds of microns, and are arranged in a predetermined arrangement for each hue.
At present, as a method for producing a color filter, a method called a pigment dispersion method, which uses a pigment excellent in various resistances such as light resistance and heat resistance as a coloring material, is mainly used. In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and thereafter, if necessary, a treatment such as heating is performed. Thereby, the filter segment pattern of the first color is obtained. By performing the same operation as above, a filter segment pattern of another color is formed, and a color filter is completed.

  In recent years, high color reproduction of displays has become an important trend. Higher color reproduction of displays has been focused on improving the color reproducibility of the backlight, but it is necessary to use very dark colors for the color filters in order to improve the color reproducibility. In such a case, in the exposure step of forming the pattern of the color filter, the amount of light reaching the bottom of the coating film is weak, so that photocuring tends to be insufficient, and a problem that a pattern having a desired shape cannot be obtained occurs. I do.

  Specifically, the size of the pattern obtained in the color filter manufacturing process, when the exposure amount in the exposure process is varied, the photosensitive colored composition is required to have a dimensional stability that can be accommodated within a certain degree of variation. In a photosensitive coloring composition which realizes high color reproduction, such dimensional stability tends to be deteriorated. Similarly, in a photosensitive coloring composition that achieves high color reproduction, the linearity of the pattern tends to be deteriorated.

  Various methods have been studied so far to solve these problems. For example, in Patent Document 1, dimensional stability is ensured by adding a polymer having a specific structure to a photosensitive composition. In Patent Document 2, a pattern shape and dimensional stability are realized by providing an anchor layer on a substrate. In Patent Literature 3, stability of a pattern dimension at a low exposure amount is realized by adding a polymer having a specific structure to a photosensitive composition. In Patent Document 4, dimensional stability is achieved by using a polymerization initiator having a specific structure. In Patent Document 5, dimensional stability against development is ensured by using a thiol-based compound. However, high dimensional stability and linearity required for color filters have not been sufficiently achieved today, and further improvements are needed.

JP 2013-254407 A JP 2013-073115 A JP 2012-108227 A JP 2011-002796 A JP 2010-039475 A

An object of the present invention is to achieve the following objects.
That is, an object of the present invention is to provide a photosensitive composition for a color filter which can form a pixel having a high resolution of a colored pattern, a low yield of unexposed portions removed by development, and a good yield, and the use thereof. It is to provide a formed color filter.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, using an aluminum phthalocyanine pigment [A] represented by either the general formula (A-1) or the general formula (A-2). In such a case, it was found that the above problem could be solved by including the phthalocyanine dye derivative represented by the general formula (103), and the present invention was achieved.

That is, the present invention provides an aluminum phthalocyanine pigment [A] represented by the following general formula (A-1), a dye derivative (B), a resin dispersant (C), a binder resin (D), a polymerizable compound (F), A color composition comprising a photopolymerization initiator (G) and an organic solvent, wherein the dye derivative (B) contains a phthalocyanine-based dye derivative represented by the following general formula (103). The present invention relates to a photosensitive coloring composition for use.

General formula (A-1)

[In General Formula (A-1), X _{1 to} X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a group which may have a substituent. Good cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group Or an arylthio group which may have a substituent.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
Z represents a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxyl group which may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ each represent 0 to _4. 4 may be the same or different. ]

General formula (103)

In the general formula (103),
R ₁₀₆ and R ₁₀₇ are each independently a hydrogen atom, a hydroxyl group, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a phthalimidoalkyl group optionally having a substituent, An acyl group which may have a group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, a group represented by the general formulas (150) to (155), (158), or (159) is there. m and n each independently represent a positive integer. However, this excludes the case where R ₁₀₆ and R ₁₀₇ are simultaneously hydrogen atoms.

In the general formulas (150) to (155),
X ₁ is a direct bond, -SO2 -, - CO -, - CH2 -, - CH2NHCOCH2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a.
Y ₁ represents a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Y ₂ represents a direct bond, an arylene group which may have a substituent, or a heteroaromatic ring which may have a substituent, and these groups include —NR ₁₇₀ −, —O—, and —SO ₂ — Or CO— may be mutually connected by a divalent linking group selected from —CO—.
Y ₃ is a direct _{bond, -NR 170} - represents a or -O-.
o represents an integer of 0 to 20.
M ₁ is a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom, an iron atom, or a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , and —O—SiR ₃ R ₄ represents an aluminum compound having at least one substituent selected from the group consisting of R _5.
Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxyl group which may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring.
M ₂ represents a hydrogen atom, calcium atom, a barium atom, strontium atom, a manganese atom or an aluminum atom.
i represents the valence of _{M 2.}
R ₁₅₀ and R ₁₅₁ each independently represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a combination of R ₁₅₀ and R ₁₅₁ . Represents a heterocyclic ring which may have a substituent and further contains a nitrogen, oxygen or sulfur atom.
R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ each independently may have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , — represents Cl, -F, or _Y 3 _-Y 2 _-Y 1 _-Q, group one of _{R 157} and _{R 158} is represented by the following general formula (156) or (157), -O- (CH _{2) o -R 171, -OR 172} , or _NR 173 _{R 174.}
R ₁₇₀ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent.
R ₁₇₁ represents an optionally substituted heterocyclic residue, and R _{172 to} R ₁₇₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted substituent. It represents a good alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue.

General formula (156)

In General Formula (156), Z ₁ represents —NR ₁₇₀ —, —CONH—, or —O—, and Z ₂ represents an alkylene group optionally having a substituent or an alkenylene group optionally having a substituent. represents an arylene group which may have a substituent, these _{groups, -NR 170 -, - O -} , - SO 2 - or a divalent linking group selected from CO- be coupled to each other Is also good. _{However, R 170} has the same meaning as _{R 170} in formula (150) - (155).
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a phenyl group optionally having a substituent, or R ₁₅₀ and R ₁₅₁ . Represents a heterocyclic ring which may further have a substituent and further contains a nitrogen, oxygen or sulfur atom.

General formula (157)

In the general formula (157), _{Z 3} is a single bond linking the triazine ring and a nitrogen _{atom, -NR 175 -, - NR 175} -Z 4 -CO -, - NR 175 -Z 4 -CONR 176 -, -NR 175 _{-Z 4 -SO 2 -, - NR} 175 -Z 4 - SO 2 NR 176 -, - O-Z 4 -CO -, - O-Z 4 -CONR 175 -, - O-Z 4 -SO 2 -, Or O—Z ₄ —SO ₂ NR ₁₇₅ —, wherein R ₁₇₅ and R ₁₇₆ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or Represents a phenyl group which may have a substituent, and Z ₄ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent or an arylene group which may have a substituent. Represent.
R _{152 to} R ₁₅₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a polyoxyalkylene. Represents a group.

General formula (158)

General formula (159)

In the general formula _(159), X _{2 is, -SO 2 -, - CO -} , - NH -, - SO 2 NH -, - NHSO 2 -, - represents CONH- or _{-NHCO-, R} 163 ~R ₁₆₇ Is each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphate group or a group represented by any of the general formulas (150) to (155).

  Further, in the present invention, the resin-type dispersant (C) has a reaction product of a hydroxyl group of a polymer having a hydroxyl group with an acid anhydride group of a tricarboxylic anhydride or a tetracarboxylic dianhydride and / or a hydroxyl group. In the presence of a reaction product of a hydroxyl group of the compound and an acid anhydride group of a tricarboxylic anhydride or a tetracarboxylic dianhydride, the reaction product is characterized by being a reaction product of polymerizing an ethylenically unsaturated monomer. And a photosensitive coloring composition for a color filter.

  The present invention also relates to the photosensitive coloring composition for a color filter, wherein the binder resin (D) contains an alkali-soluble resin having an ethylenically unsaturated double bond.

  The present invention also relates to the photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (G) contains an oxime ester-based initiator.

  The present invention also relates to the photosensitive color composition for a color filter, which comprises an epoxy compound or an oxetane compound.

Further, the present invention relates to a cured film of the photosensitive coloring composition for a color filter.

Further, the present invention relates to a color filter comprising a substrate and a pre-cured film.

Further, the present invention relates to a liquid crystal display device including the above color filter.

Further, the present invention relates to a solid-state imaging device including the color filter.

Further, the present invention relates to an organic EL display device including the color filter.

    By using the photosensitive coloring composition of the present invention, each color filter segment having a small amount of unexposed portions removed by development and having excellent linearity, pattern shape, resolution, development resistance, and chemical resistance is formed. can do. Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

Hereinafter, each component of the photosensitive coloring composition of the present invention will be described.
In addition, in this application, especially described as "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide". Unless otherwise specified, "acryloyl and / or methacryloyl", "acryl and / or methacryl", "acrylic and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. Shall be represented.
In addition, “CI” described in this specification means a color index (CI).

<Colorant>
The coloring composition for a color filter of the present invention contains an aluminum phthalocyanine pigment [A] represented by the general formula (A-1) as a coloring agent.
The content of the coloring agent in the total solid content of the coloring composition according to the present invention is preferably from 10 to 50% by weight, more preferably from 15 to 45% by weight, from the viewpoint of sufficient color reproducibility.

(Aluminum phthalocyanine pigment [A])
The aluminum phthalocyanine pigment [A] is represented by the general formula (A-1), and is excellent in color characteristics and dispersibility.

General formula (A-1)

[In General Formula (A-1), X _{1 to} X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a group which may have a substituent. Good cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group Or an arylthio group which may have a substituent.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
Z represents a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxyl group which may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ each represent 0 to _4. 4 may be the same or different. ]

In the general formula (A-1), X _{1 to} X ₄ may be the same or different. When X _{1 to} X ₄ have a substituent, the substituents may be the same or different, and specific examples thereof include characteristics such as a halogen group such as fluorine, chlorine, and bromine, an amino group, a hydroxyl group, and a nitro group. In addition to the groups, examples include an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like. Further, these substituents may be plural.

  As the `` alkyl group '' of the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, Examples thereof include a linear or branched alkyl group such as an n-octyl group, a stearyl group, and a 2-ethylhexyl group. Examples of the “alkyl group having a substituent” include a trichloromethyl group, a trifluoromethyl group, 2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4 -Methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like. .

  Examples of the “aryl group” of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group and the like, and examples of the “aryl group having a substituent” include a p-methylphenyl group and a p-methylphenyl group. Bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl Groups, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and the like.

  Examples of the “cycloalkyl group” of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Examples of the “cycloalkyl group having a substituent” include 2,5 -Dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

  Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group. "Includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group and the like.

  Examples of the “alkoxyl group” of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, and , 3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and other straight-chain or branched alkoxyl groups. Examples of the "group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, Ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy, etc. And the like.

  Examples of the “aryloxy group” of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group and the like, and the “aryloxy group having a substituent” includes p-methyl Phenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like.

  Examples of the `` alkylthio group '' of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the “alkylthio group having a substituent” include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

  Examples of the `` arylthio group '' of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like, and the `` arylthio group having a substituent '' includes Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y _{1 to} Y ₄ include a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —), and a sulfamoyl group ( H ₂ NSO ₂ -) and the like. Further, a phthalimidomethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidomethyl group is substituted by a substituent, and a sulfamoyl group having a substituent means that a hydrogen atom in the sulfamoyl group is substituted by a substituent. Represents the structure shown. Preferred Y is a halogen atom and a sulfamoyl group. A phthalocyanine compound in which m _{1 to} m ₄ is 0 (that is, there is no Y _{1 to} Y ₄ ) can also be suitably used. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. The “substituent” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent have the same meaning as the substituents of X _{1 to} X ₄ .

Z is represented by a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ , wherein R ₁ and R ₂ are a hydrogen atom and a hydroxyl group, respectively. R ₁ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent; combines R ₂ to each other may form a ring.

Here, the alkyl group in R ₁ and R ₂ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. A stearyl group, a linear or branched alkyl group such as a 2-ethylhexyl group, and the like. When the alkyl group is an alkyl group having a substituent, examples of the substituent include chlorine, fluorine, and a halogen atom such as bromine. Examples include an alkoxyl group such as a methoxy group, an aromatic group such as a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and a 2-butoxyethyl group. , 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, etc. Is mentioned.

The aryl group in R ₁ and R ₂ includes a phenyl group, a naphthyl group, an anthryl group and the like. When the aryl group has a substituent, the substituent includes a halogen atom such as chlorine, fluorine and bromine, an alkyl group, There are an alkoxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. The aryl group having a substituent includes, for example, p-tolyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylamino Examples include a phenyl group, a 2-methyl-4-chlorophenyl group, a 4-methoxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, and an anthraquinonyl group.

Examples of the alkoxyl group in R ₁ and R ₂ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, and a 2,3-dimethyl-3- Pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, linear or branched alkoxyl group such as 2-ethylhexyloxy group, and the like, and as a substituent of the alkoxyl group having a substituent, Examples include a halogen atom such as chlorine, fluorine and bromine, an aryl group such as an alkoxyl group, a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2-ditrifluoro group. Examples include a methylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

The aryloxy group for R ₁ and R ₂ includes a phenoxy group, a naphthaloxy group, an anthryloxy group and the like. When the aryloxy group has a substituent, the substituent is a halogen atom such as chlorine, fluorine and bromine. , An alkyl group, an alkoxyl group, an amino group, a nitro group and the like. Further, there may be a plurality of substituents. The aryloxy group having a substituent includes, for example, p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, 2-methyl-4-chloro There is a phenoxy group and the like.

As the aluminum phthalocyanine pigment represented by the general formula (A-1) used in the present invention, at least one of R ₁ and R ₂ has a substituent from the viewpoint of dispersibility and color characteristics. And an aryloxy group which may have a substituent. More preferably, each of R ₁ and R ₂ is an aryl group or an aryloxy group. More preferably, both R ₁ and R ₂ are a phenyl group or a phenoxy group.

In Formula (A-1), R ₃ , R _4, and R ₅ are each independently an alkyl group having 1 to 18 carbon atoms or an aromatic group having 4 or less rings. When the number of carbon atoms in the alkyl group exceeds 18 or the number of aromatic rings exceeds 4, the molecular weight increases and the extinction coefficient per unit weight decreases, so that the pigment concentration in the coloring composition must be increased. It is not preferable because it cannot be obtained.

The alkyl group for R ₃ , R ₄ , and R ₅ may be linear, branched or cyclic, and has a functional group within a total number of 3 or less hetero atoms. May be. For example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl Group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group , 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and 3-nitrophenacyl group And the like.

As the aromatic group in R ₃ , R ₄ and R ₅ , an aromatic ring may contain a hetero atom, and each aromatic ring may have a functional group in a range of 2 or less hetero atoms. . For example, a phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9 -Fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, ternaphthalenyl group , Quarternaphthalenyl, heptalenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrenyl, phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthracenyl, quarteranthracenyl Nil group, anthraquinolyl group, phenanthryl Group, triphenylenyl group, a pyrenyl group, naphthacenyl group, pleiadenyl group, picenyl group, a perylenyl group, tetraphenylenyl les group, and coronenyl group and the like.

Among the phthalocyanine compounds represented by the general formula (A-1) used in the present invention, from the viewpoint of heat resistance and light resistance, Z is more preferably -OP (= O) R ₁ R ₂ .

(Other coloring agents)
The photosensitive coloring composition for a color filter of the present invention further contains a colorant such as another pigment or dye in addition to the phthalocyanine pigment in a range that does not impair the effects of the present invention, in order to further adjust the hue. Is also good.

As the pigment, a pigment having a high coloring property and a high heat resistance, particularly a pigment having a high thermal decomposition resistance is preferable, and an organic pigment is usually used. Hereinafter, specific examples of the organic pigment that can be used in the coloring composition for a color filter are shown by color index numbers.

  Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 , 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291 and the like. Further, examples thereof include diketopyrrolopyrrole pigments described in JP-A-2011-523433, azo pigments described in JP-A-2014-112527, and azo pigments described in JP-A-2013-161026. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291 and more preferably C.I. I. Pigment Red 177, 254, 291.

  The red coloring composition includes C.I. I. An orange pigment such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and / or a yellow pigment described later may be used in combination.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Further, a purple pigment described later may be used in combination with the blue coloring composition.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2: 2: 2, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, and more preferably C.I. I. Pigment Violet 23.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, etc. However, the present invention is not limited to these. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59.
Further, the green coloring composition may be used in combination with a yellow pigment described below.

  For the yellow pigment, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,192,193,194,196,198,199,213,214,231, and the like. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

The cyan coloring composition for forming the cyan filter segment includes, for example, C.I. I. Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 can be used alone or in combination.

The magenta coloring composition for forming the magenta color filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C.I. I. A violet pigment and a red pigment such as CI Pigment Red 144, 146, 177, 169, and 81 can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, navy blue, chromium oxide green, cobalt green, and amber. And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between saturation and lightness.

As the dye, any of an acid dye, a direct dye, a basic dye, a salt-forming dye, an oil-soluble dye, a disperse dye, a reactive dye, a mordant dye, a vat dye, a sulfur dye and the like can be used. In addition, these derivatives may be in the form of lake pigments obtained by lake dyes.

Further, an acid dye having an acid group such as sulfonic acid or carboxylic acid, in the case of a direct dye, an inorganic salt of the acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound or the like, or salt formation using a resin component having these functional groups to be used as a salt-forming compound, or sulfonamidation and use as a sulfonamide compound , And is excellent in durability, so that a colored composition having excellent fastness can be obtained, which is preferable.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in a side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with a pigment, and furthermore, a basic dye and an organic sulfonic acid, an organic sulfuric acid, and a fluorine group-containing phosphorus which are counter components serving as counter ions. It is possible to use an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt formed with an acid dye. More preferred.

  When the dye skeleton has a polymerizable unsaturated group, a dye having excellent resistance can be obtained, which is preferable.

  Examples of the chemical structure of the dye include azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyrromethene dyes, and quinone dyes (benzoquinone dyes, naphthoquinone dyes, and anthraquinone dyes). Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes Pigment structures derived from dyes selected from perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof can be given. .

  Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and squarylium, from the viewpoint of color characteristics such as hue, color separation, and color unevenness. Dyes, quinophthalone dyes, phthalocyanine dyes, dye structures derived from dyes selected from subphthalocyanine dyes are preferred, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A dye structure derived from a dye selected from system dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in “New Edition Dye Handbook” (edited by The Society of Synthetic Organic Chemistry, Maruzen, 1970), “Color Index” (The Society of Dysers and colors), “Dye Handbook” (Okawara et al.) (Kodansha, 1986).

(Pigment refinement)
When the colorant used in the photosensitive coloring composition of the present invention is a pigment, it is preferable to use it after making it finer. The method of micronization is not particularly limited. For example, any one of wet milling, dry milling, and dissolution precipitation can be used. And the like, and can be miniaturized. It is preferable that the pigment has an average primary particle diameter of 5 to 90 nm determined by TEM (transmission electron microscope). If it is smaller than 5 nm, dispersion in an organic solvent becomes difficult, and if it is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferred average primary particle size is in the range of 10 to 70 nm.

  Salt milling treatment is a batch or continuous method using a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, and a planetary mixer. This is a process of mechanically kneading while heating using a kneader, and then removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by utilizing the hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used in terms of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, and most preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, from both the processing efficiency and the production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) with water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling solvent having a boiling point of 120 ° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

  When the pigment is subjected to the salt milling treatment, a resin may be added as necessary. The type of the resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Dye derivative (B)>
The dye derivative (B) is added to the photosensitive coloring composition used in the present invention.

As the dye derivative used in the present invention, a known dye derivative having an acidic dye, a basic group, a neutral group, or the like in an organic dye residue can be used. For example, compounds having an acidic substituent such as a sulfo group, a carboxy group, and a phosphoric acid group and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at a terminal, a phenyl group or a phthalimide Compounds having a neutral substituent such as an alkyl group are exemplified.
As organic dyes, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzo Indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, sulene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo. It is.

Specifically, examples of diketopyrrolopyrrole-based dye derivatives include JP-A-2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, JP2017-156397, and phthalocyanine. JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, JP-A-5573266, and anthraquinone-based pigment derivatives include JP-A-63-264677, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325, Kina JP-A-48-54128, JP-A-H03-9961, JP-A-2000-273383, and JP-A-2011-162662, and thiazineindigo as dioxazine-based dye derivatives. JP-A-2007-314785 as a dye derivative, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003 JP-A-168208, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, and JP-A-2003-167112 as a quinophthalone-based dye derivative Gazette, JP 2006-291194 A JP-A-2008-31281, JP-A-2012-226110, and JP-A-2012-208329 and JP-A-2014-5439 as naphthol-based dye derivatives; JP-A-172520, JP-A-2012-172092, as the acidic substituent, JP-A-2004-307854, and as the basic substituent, JP-A-2002-201377, JP-A-2003-171594, Known dye derivatives described in JP-A-2005-181383 and JP-A-2005-213404 are exemplified. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, and the like. The compound having a substituent such as a sex group has the same meaning as the dye derivative.

These dye derivatives can be used alone or in combination of two or more.
More specifically, the following dye derivatives are preferred.

[Diketopyrrolopyrrole dye derivative]

[Phthalocyanine dye derivative]
General formula (103)

[Anthraquinone dye derivative]

[Quinacridone dye derivative]
General formula (108)

[Dioxazine dye derivative]

[Thiazine indigo dye derivative]
General formula (111)

[Triazine dye derivative]
General formula (112)

[Benzoisoindole dye derivative]
General formula (113)

[Quinophthalone dye derivative]

[Naphthol dye derivative]
General formula (129)

[Azo dye derivative]

General formula (133)

In the general formulas (101) to (112), (114) to (128), (130) to (133),
R _{101 to} R ₁₁₇ , R ₁₂₉ , R ₁₃₀ , and R _{141 to} R ₁₄₅ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, A phthalimidoalkyl group which may have a group, an acyl group which may have a substituent, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), and (158) ) Or (159). m and n each independently represent a positive integer. However, when one molecule has a plurality of substituents, one or more is a substituent other than a hydrogen atom. When only one substituent is present in one molecule, it is a substituent other than a hydrogen atom.

In Formula (113), R ₁₁₈ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, —SO ₂ R ₁₇₇ , or —NR ₁₇₈ R ₁₇₉ . Here, R ₁₇₇ is a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom, and R ₁₇₈ and R ₁₇₉ each independently represent a hydrogen atom represents an alkyl group having 1 to 12 carbon atoms, or a further nitrogen together with the R ₁₇₈ and R _179, a heterocyclic ring which may contain an oxygen or sulfur atom.
R ₁₁₉ represents a hydrogen atom, an alkyl group which may have a substituent, or an acyl group which may have a substituent.
R ₁₂₀ , R ₁₂₁ and R _{123 to} R ₁₂₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, a halogen atom, a cyano group, or a substituent. Or NR ₁₈₀ R ₁₈₁ . However, R ₁₈₀ and R ₁₈₁ may be, independently of each other, a hydrogen atom, an alkyl group which may have a substituent, or a further nitrogen, oxygen or sulfur atom integrated with R ₁₈₀ and R _181. Represents a good heterocycle.
R ₁₂₂ represents a hydrogen atom, an alkyl group which may have a substituent, an acyl group which may have a substituent, or a group represented by any of the general formulas (150) to (155).

In the general formula (129), R _{131 to} R ₁₄₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, or a group represented by the general formula (150), (153), or (159). Represents a group to be formed. Adjacent groups of R _{131 to} R ₁₄₀ may be linked by an —NHCONH— group to form a benzimidazolone ring. At least one of R _{131 to} R ₁₄₀ is a group represented by the general formula (150), (153) or (159).

In the general formulas (150) to (155),
X ₁ is a direct bond, -SO2 -, - CO -, - CH2 -, - CH2NHCOCH2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a.
Y ₁ represents a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Y ₂ represents a direct bond, an arylene group which may have a substituent, or a heteroaromatic ring which may have a substituent, and these groups include —NR ₁₇₀ −, —O—, and —SO ₂ — Or CO— may be mutually connected by a divalent linking group selected from —CO—.
Y ₃ is a direct _{bond, -NR 170} - represents a or -O-.
o represents an integer of 0 to 20.
M ₁ represents a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom, an iron atom, and an aluminum compound having a substituent.
As a substituent of the aluminum compound having a substituent, a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ is represented. Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxyl group which may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring.
M ₂ represents a hydrogen atom, calcium atom, a barium atom, strontium atom, a manganese atom or an aluminum atom.
i represents the valence of _{M 2.}
R ₁₅₀ and R ₁₅₁ each independently represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a combination of R ₁₅₀ and R ₁₅₁ . Represents a heterocyclic ring which may have a substituent and further contains a nitrogen, oxygen or sulfur atom.
R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ each independently may have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , — represents Cl, -F, or _Y 3 _-Y 2 _-Y 1 _-Q, group one of _{R 157} and _{R 158} is represented by the following general formula (156) or (157), -O- (CH _{2) o -R 171, -OR 172} , or _NR 173 _{R 174.}
R ₁₇₀ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent.
R ₁₇₁ represents an optionally substituted heterocyclic residue, and R _{172 to} R ₁₇₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted substituent. It represents a good alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue.

General formula (156)

In General Formula (156), Z ₁ represents —NR ₁₇₀ —, —CONH—, or —O—, and Z ₂ represents an alkylene group optionally having a substituent or an alkenylene group optionally having a substituent. represents an arylene group which may have a substituent, these _{groups, -NR 170 -, - O -} , - SO 2 - or a divalent linking group selected from CO- be coupled to each other Is also good. _{However, R 170} has the same meaning as _{R 170} in formula (150) - (155).
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a phenyl group optionally having a substituent, or R ₁₅₀ and R ₁₅₁ . Represents a heterocyclic ring which may further have a substituent and further contains a nitrogen, oxygen or sulfur atom.

General formula (157)

In the general formula (157), _{Z 3} is a single bond linking the triazine ring and a nitrogen _{atom, -NR 175 -, - NR 175} -Z 4 -CO -, - NR 175 -Z 4 -CONR 176 -, -NR 175 _{-Z 4 -SO 2 -, - NR} 175 -Z 4 - SO 2 NR 176 -, - O-Z 4 -CO -, - O-Z 4 -CONR 175 -, - O-Z 4 -SO 2 -, Or O—Z ₄ —SO ₂ NR ₁₇₅ —, wherein R ₁₇₅ and R ₁₇₆ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or Represents a phenyl group which may have a substituent, and Z ₄ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent or an arylene group which may have a substituent. Represent.
R _{152 to} R ₁₅₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a polyoxyalkylene. Represents a group.

General formula (158)

General formula (159)

In the general formula _(159), X _{2 is, -SO 2 -, - CO -} , - NH -, - SO 2 NH -, - NHSO 2 -, - represents CONH- or _{-NHCO-, R} 163 ~R ₁₆₇ Is each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphate group or a group represented by any of the general formulas (150) to (155).

As the alkyl group which may have a substituent, a linear alkyl group having 1 to 20 carbon atoms is preferable as the alkyl group, and a hydrogen or halogen group is preferable as the substituent which may have.
The phthalimidoalkyl group which may have a substituent is preferably an alkyl group having 1 to 3 carbon atoms as an alkyl group, and a hydrogen or halogen group is preferable as an optionally substituted substituent.
As the acyl group which may have a substituent, an alkyl group is preferably an acyl group having 1 to 10 carbon atoms, and a substituent which may be possessed is preferably hydrogen or a halogen group.
As the optionally substituted alkoxy group, an alkyl group is preferably a straight-chain alkoxy group having 1 to 5 carbon atoms, and the optionally substituted substituent is preferably hydrogen or a halogen group.
The alkenyl group or alkenylene group which may have a substituent is preferably hydrogen or a linear alkyl group having 1 to 10 carbon atoms.
The optionally substituted phenyl group is preferably a hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group.
The arylene group which may have a substituent is preferably a hydrogen, a halogen group, a straight-chain alkyl group having 1 to 10 carbon atoms, or an alkoxy group.
The heterocyclic ring which may have a substituent is preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, or tetrahydrothiopyran as the heterocyclic ring. And a linear alkyl group or alkoxy group having 1 to 10 carbon atoms.
The heteroaromatic ring which may have a substituent is preferably a pyrrole, pyridine, furan or thiophene as the heteroaromatic ring, and hydrogen, a halogen group or a straight chain having 1 to 10 carbon atoms as the substituent which may be possessed. Alkyl groups and alkoxy groups are preferred.

  In the photosensitive coloring composition of the present invention, a phthalocyanine-based dye derivative represented by the general formula (103) among the above-mentioned dye derivatives is essential, and other dye derivatives can be used in combination as needed.

  The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment.

  By adding a pigment derivative to the pigment and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the pigment derivative is adsorbed on the pigment surface and the pigment derivative is not added. In comparison, the primary particles of the pigment can be made finer.

  By adding a pigment derivative to the pigment and performing dispersion treatment such as wet dispersion using two-roll, three-roll, and beads, the pigment derivative is adsorbed on the pigment surface, and the pigment surface is polar and adsorbs the resin-type dispersant. Is promoted, the compatibility with pigments, dye derivatives, resin-type dispersants, solvents and other additives is improved, and the dispersion stability and viscosity stability over time when formed into a colored composition or a colored curable composition are improved. I do. In addition, since the compatibility is improved, the colored curable composition is excellent in stability over time when coated on a glass substrate or the like, and the waiting time from application of the colored curable composition to exposure (PCD: Post Coating). The stability and characteristic dependence of the pattern shape and the like on the delay time from exposure to heat treatment (PED: Post Exposure Delay) and the line width sensitivity stability are improved. Further, by adsorbing and coating the pigment surface with the dye derivative and the resin-type dispersant, it is possible to suppress aggregation of the pigment and crystal precipitation due to sublimation when the coating film is heated and fired. Further, variations in development time and development residues are also suppressed.

<Resin type dispersant (C)>
Known resin-type dispersants (C) can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant (C) has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and adsorbing to the additive colorant to provide the colorant carrier. Any substance can be used as long as it has a function of stabilizing the dispersion in urethane. Specifically, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, and polycarboxylic acid ( Part) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters and their modified products, free from poly (lower alkylene imine) Oily dispersants such as amides and salts thereof formed by the reaction with a polyester having a carboxyl group of (meth) acrylic acid-styrene Water-soluble resin or water-soluble polymer compound such as polymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified Polyacrylates, ethylene oxide / propylene oxide adducts, phosphates, and the like are used, and these can be used alone or as a mixture of two or more.
Examples of the polymer dispersant having a basic functional group include a nitrogen atom-containing graft copolymer and a nitrogen atom-containing graft group having a functional group containing a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocyclic ring in a side chain. Examples include an acrylic block copolymer and a urethane polymer dispersant.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by Big Chem Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bycumen, etc. OLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32,500, 32550, 33500, 32600, 34750, 35100, 36600, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 manufactured by BASF, such as 38500, 41000, 41090, 53095, 55000, 56000, and 76500. , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 53, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajispa-PA111, PB711, PB821, PB822 manufactured by Ajinomoto Fine-Techno. , PB824 and the like.

In the photosensitive coloring composition of the present invention, a resin type dispersant having a carboxyl group can be suitably used. Examples of the shape of the resin-type dispersant having a carboxyl group include a linear resin-type dispersant and a comb-type resin-type dispersant.

[Comb-shaped resin-type dispersant having carboxyl group (C1)]
The comb-shaped resin-type dispersant (C1) having a carboxyl group can be produced by a known method such as WO 2008/007776, JP-A-2008-029901, and JP-A-2009-155406.
For example, a hydroxyl group of a polymer having a hydroxyl group and a resin-type dispersant which is a reaction product of an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group, and a tetracarboxylic dianhydride A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride group of the product.

[Comb-shaped resin-type dispersant having carboxyl group (C2)]
The comb-type resin-type dispersant (C2) having a carboxyl group can be obtained by a known method such as WO2008 / 007776, JP2009-155406A, JP2010-185934A, and JP2011-157416A. Can be manufactured.
For example, in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tetracarboxylic dianhydride, a hydroxyl group, a t-butyl group or an oxetane skeleton, having a thermal crosslinking group such as a blocked isocyanate Resin-type dispersant obtained by reacting a resin-type dispersant having an ethylenically unsaturated monomer and a side chain obtained by polymerizing the other monomer and a thylene-type unsaturated monomer having an isocyanate group in the hydroxyl group of the side chain It is.

[Carboxyl group-containing linear resin dispersant]
The linear resin-type dispersant having a carboxyl group can be produced by a known method such as JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group is produced by adding a tricarboxylic anhydride to a hydroxyl group from a vinyl polymer having one hydroxyl group at one end as a raw material. Can be done.

  The resin-type dispersant is preferably used in an amount of about 3 to 200% by weight, and more preferably about 5 to 100% by weight, from the viewpoint of film formability.

<Binder resin (D)>
The coloring composition of the present invention contains a binder resin (D). As the binder resin (D), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm is used. Binder resins include thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc., classified according to their main curing methods. It may be a resin or a resin having a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. It may also contain a thermoplastic resin that is not curable by active energy rays, and it is preferable that the resin is also alkali-soluble. These can be used alone or in combination of two or more.

  The content of the binder resin in the coloring composition of the present invention is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on the total weight of the coloring agent (100 parts by mass). It is preferably used in an amount of 20 parts by mass or more because of good film formability and various resistances, and is preferably used in an amount of 400 parts by mass or less because the colorant concentration is high and good color characteristics can be exhibited. .

<Thermoplastic resin>
As the thermoplastic resin that can be used as the binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. Is mentioned.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include a resin having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the resin include an acrylic resin having an acidic group, an α-olefin / (anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, and an isobutylene / (Anhydrous) maleic acid copolymer and the like. Above all, an acrylic resin having an acidic group, and at least one resin selected from styrene / styrene sulfonic acid copolymers, particularly an alkali-soluble resin having an acidic group and / or a hydroxyl group, have developability, heat resistance, and transparency. Since it is high, it is preferably used.

<Alkali-soluble resin>
The coloring composition of the present invention preferably contains an alkali-soluble resin from the viewpoints of developability, heat resistance, and transparency. This is for imparting development solubility in an alkaline development step at the time of producing a color filter, and has an acid group and / or a hydroxyl group. In order to further improve photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

<Alkali-soluble resin having an ethylenically unsaturated double bond>
The alkali-soluble resin contained in the coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond is introduced by the following methods (i), (ii) and (iii), the resin becomes 3 when exposed to active energy rays to form a coating film. The dimensional cross-linking increases the cross-linking density and improves the chemical resistance.

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers may be used. The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction. There is a way to introduce it.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate And 3,4-epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl (meth) acrylic acid, alkoxyl, halogen, nitro and cyano-substituted products. Monocarboxylic acids may be used, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. I don't care. Increasing the number of carboxyl groups, etc., if necessary, using a tricarboxylic anhydride such as trimellitic anhydride, or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining anhydride Hydrolysis of the group can also be performed. When tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

  As a similar method to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers There is a method in which an ethylenically unsaturated monomer having an epoxy group is subjected to an addition reaction to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and another monomer of an unsaturated monobasic acid having a carboxyl group is copolymerized with another monomer. There is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
Or hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. May be used in combination. Also, polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate to which poly 12-hydroxystearic acid or the like has been added can also be used. From the viewpoint of suppressing paint film foreign matter, 2-hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use those having 2 to 6 hydroxyl groups. And glycerol mono (meth) acrylate is more preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. However, the present invention is not limited thereto, and two or more kinds can be used in combination.

The following are examples of the monomer constituting the alkali-soluble resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyether Glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or (meth) such as acryloylmorpholine Acrylamides Styrene, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, and fatty acid vinyls such as vinyl propionate And the like.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succin Midyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide, 9-maleimidoacridine,
A compound represented by the following general formula (1), specifically, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenol ethylene oxide (EO) -modified (meth) acrylate And EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

General formula (1)

(In the general formula (1), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon atom which may have a benzene ring. It is an alkyl group of numbers 1 to 20, and n is an integer of 1 to 15.)

  Further, a carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.

  Also, a hydroxyl group-containing ethylenically unsaturated monomer can be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane Examples include hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Also, polyether mono (meth) acrylates obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like has been added.

Further, a phosphoric ester group-containing ethylenically unsaturated monomer can also be used. Examples of the phosphate group-containing ethylenically unsaturated monomer include, for example, monomers obtained by reacting a hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.
[Method (iii)]
In the method (iii), an unsaturated ethylenic double bond and the like can be introduced by copolymerizing a side chain type cyclic ether-containing monomer with at least one other monomer.
The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and (meth) acrylic acid tetrahydrofuran-3-yl ester;
As the furan skeleton, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan -2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate -2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like;
As the pyran skeleton, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa-6-oxo-7-octenyl) -6 -Methyl-2-pyrone and the like;
As the lactone skeleton, 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2-yl Yl ester, 2-methyl-2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-methyl-2-propenoic acid 2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-methyl ester Le-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-methyl-2-propenoic acid 2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl 2-propenoate And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester.
Of these, tetrahydrofurfuryl (meth) acrylate is preferred in terms of coloring, pigment dispersibility, and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. By synthesizing by using at least one kind of carboxyl group-containing ethylenically unsaturated monomer and one or more other ethylenically unsaturated monomers and not giving an ethylenically unsaturated bond to a side chain, ethylene An alkali-soluble resin having no unsaturated unsaturated double bond can be obtained.

  The alkali-soluble resin in the present invention is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is from 2,000 to 40,000, preferably from 3,000 to 300,00, and more preferably 4,000, in order to impart solubility in alkali development. It is more preferably from 20,000 to 20,000. Further, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is reduced, and the exposure pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development decreases, residues are generated, and the linearity of the pattern deteriorates.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg / g), preferably from 70 to 180, more preferably from 90 to 170 in order to impart alkali development solubility. Range. If the acid value is less than 50, the solubility in alkali development decreases, residues are generated, and the linearity of the pattern deteriorates. If it exceeds 200, the adhesion to the substrate will be reduced, and the exposure pattern will not remain easily.

<Thermosetting compound (E)>
In the present invention, a thermosetting compound (E) can be further used in combination with a thermoplastic resin as a binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, the reaction occurs during firing of the filter segment to increase the crosslink density of the coating film, and therefore the heat resistance of the filter segment is increased. Thus, the effect of suppressing pigment aggregation at the time of firing the filter segment and improving the contrast ratio can be obtained.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound, but the present invention is not limited thereto. It is not something to be done. In the coloring composition for a color filter of the present invention, an epoxy compound and an oxetane compound are preferably used.

(Epoxy compound (E-1))
The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Phenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimethanol) Polycondensates with phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols with various aldehydes, alcohols Glycidyl Glycidyl ether-based epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin, etc. It is not limited. These may be used alone or in combination of two or more.

  As commercially available products, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (and above) Is a trade name; Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade name; Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (trade name; Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name) Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), JER152, JER154 (all above are commercial products) Name: Japan Epoxy Resin Co., Ltd. , EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (all are trade names, manufactured by Daicel Chemical Industries, Ltd.) , Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (the above are trade names; Nagase ChemteX Corporation) , TEPIC-L, TEPIC-H, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), but are not limited thereto.

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the coloring agent. If the amount is less than 0.5 part by mass, the effect of improving the contrast ratio and the heat resistance is small. If the amount is more than 300 parts by mass, a problem may occur when forming a filter segment by photolithography.

(Oxetane compound (E-2))
An oxetane compound is preferably added to the photosensitive coloring composition of the present invention. As the oxetane compound, a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include a compound having an oxetane group that is monofunctional, a compound having an oxetane group that is bifunctional, and a compound having an oxetane group that is bifunctional or more.

Examples of the monofunctional oxetane group include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl- 3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- ( [Triethoxysilyl) propoxy] methyl} oxetane.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

When the oxetane group is bifunctional, examples thereof include 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-E Tyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycosebis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl -3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl -3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) -modified bis Enol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

As the oxetane group having two or more functions,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, oxo Resin (e.g., Patent No. 3,783,462 No. oxetane-modified phenol novolak resin according) containing Tan group or above, such as OXE-30 (meth) polymers obtained by the acrylic monomer by radical polymerization. Such a polymer can be obtained by using a known polymerization method.

  The content of the oxetane compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass based on 100% by mass of the solid content of the coloring composition. It is preferable that the content of the oxetane compound is in the above range, since an excellent coating film having good water stain and high chemical resistance can be obtained.

(Melamine compound)
The melamine compound in the present invention refers to a compound having a melamine ring structure. The melamine compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Preferred in the present invention are melamine compounds of a methylol type or an ether type, wherein the number of methylol groups and / or ether groups per melamine ring is 5.0 or more on average. When the number of methylol groups and / or ether groups per melamine ring is less than 5.0 on average, the number of reaction points is small, and the crosslinked structure at the time of curing is not sufficiently dense. The effect of the improvement may be reduced.

  Commercially available products include, for example, two-karak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS -001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 (Manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries), but are not limited thereto.

  Above all, two-carac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW having an average number of methylol groups and / or ether groups per melamine ring of 5.0 or more. -22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co.), Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries) and the like. This is preferable in that a dense crosslinked structure can be obtained.

(Curing agent)
In addition, the coloring composition for a color filter of the present invention may contain a curing agent (curing accelerator) or the like as needed in order to assist the curing of the thermosetting compound. As a curing agent, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, and the like are effective, but are not particularly limited thereto, and can react with a thermosetting compound. Any curing agent may be used. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl- 4 Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S) -Triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct) and the like. . These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound.

<Polymerizable compound (F)>
The photosensitive coloring composition of the present invention contains a polymerizable compound (F). The polymerizable compound (F) includes a monomer or an oligomer which is cured by ultraviolet light or heat to form a transparent resin.

  Examples of monomers and oligomers which are cured by ultraviolet light or heat to produce a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Lopan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate (Meth) acrylates of methylolated melamine, epoxy (meth) acrylates, urethane acrylates and other acrylic and methacrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Examples include vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, but are not necessarily limited thereto.

  As these commercially available products, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO- manufactured by Nippon Kayaku Co., Ltd. 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Alonix M-303, M manufactured by Toagosei Co., Ltd. -305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403 , M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, screws manufactured by Osaka Organic Co., Ltd. Over preparative # 310HP, # 335HP, # 700, # 295, # 330, # 360, # GPT, # 400, # 405, can be preferably used by Shin-Nakamura Chemical Co., Ltd. NK Ester A-9300 and the like.

(Polymerizable compound having acid group)
The polymerizable compound (F) in the present invention may contain a photopolymerizable compound having an acid group. By using a photopolymerizable compound having an acid group, when the photosensitive coloring composition of the present invention is alkali-developed, the solubility of the formed coating film in an alkali developing solution can be increased, and the developing speed can be improved. Residue can be reduced. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

  Examples of the photopolymerizable compound having an acid group include, for example, an esterified product of a polyhydric alcohol-containing (meth) acrylic acid and a free hydroxyl group-containing poly (meth) acrylate, and a dicarboxylic acid; Examples thereof include an esterified product with an alkyl (meth) acrylate. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And a free carboxyl group-containing monoester of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid and benzene-1,3,5-tricarboxylic acid; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, monohydroxy monoacrylates such as 2-hydroxypropyl methacrylate or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like, The effects of the present invention are not limited to these.

  As these commercially available products, Viscoat # 2500P manufactured by Osaka Organic Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, etc. manufactured by Toagosei Co., Ltd. can be preferably used. .

(Polymerizable compound having urethane bond)
The photopolymerizable compound (F) in the present invention may contain a photopolymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. By containing a photopolymerizable compound having a urethane bond, deposition of a coloring material when the formed coating film is heated can be suppressed, and solvent resistance and adhesion to a substrate can be improved.

Examples of the polymerizable compound having a urethane bond include a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, and a polyfunctional isocyanate reacted with an alcohol, and further having a hydroxyl group (a ) Polyfunctional urethane acrylate obtained by reacting acrylate.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylolpropane tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy group The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

  As these commercially available products, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Shin-Nakamura Chemical Co., Ltd. manufactured by Kyoeisha Chemical Co., Ltd. UA-160TM, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry, and the like can be suitably used.

  The above photopolymerizable compounds can be used alone or as a mixture of two or more at an optional ratio as needed.

  The compounding amount of the photopolymerizable compound (F) is preferably 1 to 50 parts by mass based on the total solid content of the photosensitive coloring composition (100 parts by mass), and from the viewpoint of photocurability and developability. More preferably, it is 2 to 40 parts by mass.

<Photopolymerization initiator (G)>
The photosensitive composition of the present invention contains a photopolymerization initiator (G). By containing the photopolymerization initiator (G), the composition can be cured by irradiation with ultraviolet rays, and a filter segment can be formed by photolithography. It is preferable to add a photopolymerization initiator (G) to prepare in the form of a solvent development type or alkali development type photosensitive composition.

Examples of the photopolymerization initiator (G) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one. , 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) Phenyl] -2- (phenylmethyl) -1-butanone or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin-based compounds such as propyl ether or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, or 3, Benzophenone-based compounds such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4 -Thioxanthone compounds such as -diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2 Triazine compounds such as 1,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2 (O-benzoyl oxime) or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) A phosphine compound such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. Quinone compounds; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.
One of these photopolymerization initiators may be used alone, or two or more of them may be used in an optional ratio as needed.

  As commercial products, all acetophenone-based compounds are manufactured by IGM Resins and manufactured by "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), "Omnirad 369E "(2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone)," Omnirad 379EG "(2- (dimethylamino) -2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) and phosphine-based compounds manufactured by IGM Resins, Inc., “Omnirad 819” (bis (2,4,4 6-trimethylbenzoyl) -phenylphosphine oxide), "Omnirad TPO" Sulfonyl-2,4,6-trimethyl benzoyl phosphine oxide), and the like.

  In the present invention, among these, it is preferable to contain an oxime ester compound.

(Oxime ester compound)
The oxime ester-based compound absorbs ultraviolet rays to cause cleavage of the N—O bond of the oxime, thereby generating an iminyl radical and an alkyloxy radical. These radicals are further decomposed to generate highly active radicals, so that a pattern can be formed with a small exposure dose. When the colorant concentration of the photosensitive coloring composition is high, the UV transmittance of the coating film is low and the degree of curing of the coating film may be low, but the oxime ester compound is preferably used because it has a high quantum efficiency. You. More preferred is an oxime ester-based photopolymerization initiator represented by the general formula (2).

General formula (2)

(Oxime ester-based photopolymerization initiator represented by the general formula (2))
In the general formula (2),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent) And the like.

Examples of the alkenyl group which may have a substituent for Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms. May have a carbon double bond, and specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and a 1-pentenyl group. , 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

Examples of the alkyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms, and A linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by at least -O- is exemplified. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and octyl. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —CH ₂ —O—CH ₃ and —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 from a _{8), -} (CH 2 is _{-CH 2 -CH 2 -O) m -CH} 3 ( wherein m is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 - CH ₃ , —CH ₂ —CH— (OCH ₃ ) _{2 and the} like can be mentioned, but it is not limited to these.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include the following, but are not limited thereto. It is not something to be done.

The alkyloxy group which may have a substituent in Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. A straight-chain, branched-chain, monocyclic or condensed polycyclic alkyloxy group optionally interrupted by one or more —O— is mentioned. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group. Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy, tert-pentyloxy, tert-octyloxy, neopentyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, norbornyloxy, boronyl Alkoxy group, may be mentioned 4-decyl cyclohexyl group and the like, but is not limited thereto. Further, linear interrupted by one or more -O- optionally a 2 to 18 carbon atoms, and specific examples of the branched alkyl _{group, -O-CH 2 -O-CH} 3, _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3, -O-CH 2 -CH- (OCH 3) but ₂ and the like, but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include the following, but It is not limited.

Examples of the aryl group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples include a phenyl group, a 1-naphthyl group, and a 2-naphthyl. Group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, and the like, but are not limited thereto. Not something.

The aryloxy group which may have a substituent for Y ¹ includes a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples thereof include a phenoxy group, a naphthyloxy group, and a 2- Naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group which may have a substituent in Y ¹ include an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. , 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group , 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquino Ryl, quinolyl, phthalazinyl, naphthyridinyl, quinoxanilyl, quinazolinyl, cinnolinyl, pteridinyl, 4aH-carbazolyl, 2-carbazolyl, 3-carbazolyl, β-carbolinyl, phenanthridinyl, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenosadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, thioxanthryl 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the optionally substituted heterocyclic oxy group for Y ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples thereof include a 2-furanyloxy group, a 2-thienyloxy group, a 2-indolyloxy group, a 3-indolyloxy group, a 2-benzofuryloxy group, a 2-benzothienyloxy group, and a 2-carbazolyl group. Examples include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent for Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 20 carbon atoms, and specific examples include methylsulfinyl. Group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, pentylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decylsulfinyl group, dodecylsulfinyl group, octadecylsulfinyl Group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, and the like, but are not limited thereto.

The arylsulfanyl group which may have a substituent in Y ¹ includes a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, Examples include, but are not limited to, naphthylthio, 9-anthrylthio, 9-phenanthrylthio, and the like.

The arylsulfinyl group which may have a substituent in Y ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl, 2-methylphenylsulfinyl, 2-methyloxyphenylsulfinyl, 2-butyloxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl , 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methyloxyphenylsulfinyl, 4-methylsulfanylphenylsulfinyl, 4- Examples include a phenylsulfanylphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group, but are not limited thereto.

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group and the like. Examples include, but are not limited to:

The arylsulfonyl group which may have a substituent in Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methyloxyphenylsulfonyl, 2-butyloxyphenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl , 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyanophenylsulfonyl, 4-methyloxyphenylsulfonyl, 4-methylsulfanylphenylsulfonyl, 4-phenylsulfanylphenylsulfonyl Examples thereof include, but are not limited to, a phenyl group and a 4-dimethylaminophenylsulfonyl group.

Examples of the acyl group which may have a substituent for Y ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, A carbonyl group substituted with an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group having a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a carbonyl group having a substituted monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, Thearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl Group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl Group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxy Carbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl Although a group etc. can be mentioned, it is not limited to these.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group which may have a substituent in Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group and a dibenzylamino group. No.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  As the dialkylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  Examples of the arylamino group include an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, Examples include a biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like, but are not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino, N-methyl-2-pyridino, N-ethylanilino, N-propylanilino, N-butylanilino, N-isopropyl, N-pentylanilino, -Ethylanilino group, N-methyl-1-naphthylamino group, and the like, but are not limited thereto.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, and a dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, but are not limited thereto. It is not something to be done.

The carbamoyl group which may have a substituent in Y ¹ includes a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an N-propylcarbamoyl group. , N-butylcarbamoyl, N-hexylcarbamoyl, N-cyclohexylcarbamoyl, N-octylcarbamoyl, N-decylcarbamoyl, N-octadecylcarbamoyl, N-phenylcarbamoyl, N-2-methylphenylcarbamoyl Group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-Cyanoff Enylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Groups, N, N-dimethylcarbamoyl, N, N-dibutylcarbamoyl, N, N-diphenylcarbamoyl, and the like, but are not limited thereto.

Examples of the sulfamoyl group which may have a substituent for Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, and an N-arylsulfamoyl group. Group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. However, the present invention is not limited to this.

Y ² may have a substituent, alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group which may have a substituent in R1, an alkyl group which may have a substituent, a substituent An alkyloxy group which may have, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a heterocyclic group which may have a substituent, A heterocyclic oxy group, an alkylsulfanyl group optionally having a substituent, an arylsulfanyl group optionally having a substituent, An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, Synonymous with an optionally substituted acyloxy group and an optionally substituted amino group.

Examples of these substituents in Y ¹ and Y ² include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group and a p-tolyloxy group. Aryloxy group such as group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group An acyl group such as a methacryloyl group or a methoxalyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; a methylamino group Alkylamino group such as cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl Group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, alkyl group such as cyclooctadecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group , Anthryl group, aryl group such as phenanthryl group, furyl group, heterocyclic group such as thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino Group, nitro group, cyano group, trif Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammonium group, a dimethylsulfonium group, and a triphenylphenacylphosphonium group.
In addition, one or more of these substituents may be present, and a hydrogen atom of these substituents may be further substituted with another substituent.

  Among the oxime ester-based photopolymerization initiators represented by the general formula (2), the oxime ester-based photopolymerization initiators represented by the following general formula (3) or (4) are excellent in sensitivity and more preferable. is there.

[Oxime ester-based photopolymerization initiator represented by the general formula (3)]
General formula (3)

The general formula (3) corresponds to the case where Y ³ in the general formula (2) is a Ph-S-Ph- group, and Y ⁴ to Y ⁶ are a hydrogen atom or an alkyl which may have a substituent. A group, an aryl group, and an acyl group are preferred. The alkyl group which may have a substituent or the aryl group which may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or the aryl group in Y ¹ and Y ² .

[Oxime ester photopolymerization initiator represented by general formula (3a)]
General formula (3a)

In the general formula (3a), Z in the general formula (3) corresponds to a —CO— group. Further, Y ¹ is an aryl group which may have a substituent, Y ² is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ⁴ and Y ⁶ are hydrogen atoms. More preferably, Y ⁵ is a hydrogen atom or a Y ⁷ —CO— group.

As Y ⁷ , for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group, an aryloxy group such as a p-tolyloxy group, Methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group Alkylsulfanyl groups such as acyl group, methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; methylamino groups and cyclohexylamino groups. Killamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, etc. Alkyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, aryl group such as benzofuranyl group, furyl group, heterocyclic group such as thienyl group, etc., hydroxy group, Carboxy, formyl, mercapto, sulfo, mesyl, p-toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethylammonium Mill group, dimethylsulfonium group, And a triphenylphenacylphosphonium group.

More preferably, the substituent of Y ² is a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctadecyl group.

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (3a) include a photopolymerization initiator represented by the following chemical formula (3a-1) or (3a-2).

[Oxime ester-based photopolymerization initiator represented by the general formula (3b)]
General formula (3b)

General formula (3b) corresponds to the case where Z in general formula (3) is a direct bond. As the oxime ester-based photopolymerization initiator represented by the general formula (3b), as Y ¹ and Y ² , an alkyl group having 1 to 20 carbon atoms which may have a substituent is preferable, and at least one of Y ^{4 to} Y ⁶ is preferable. One is preferably an acyl group which may have a substituent. Specifically, it is a photopolymerization initiator represented by the following chemical formula (3a-1) or (3a-2).

[Oxime ester-based photopolymerization initiator represented by the general formula (4)]
General formula (4)

The general formula (4) corresponds to the case where Y ³ in the general formula (2) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y ^{1 It has the same} meaning as the substituent in ² .

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent or a substituent as Y ^2. aryl group, Y ⁷ to Y ¹⁴ as a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent is preferable.

  When Z in the general formula (4) is a direct bond, an oxime ester-based photopolymerization initiator represented by the following general formula (4a) is preferable.

"Oxime ester-based photopolymerization initiator represented by the general formula (4a)"
General formula (4a)

The general formula (4a) corresponds to the case where Z in the general formula (4) is a direct bond, and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent. Y ⁷ to Y ^10, and ^Y 12 ^{to Y 13} is a hydrogen atom.
Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ has the same meaning as the substituent for Y ¹ and Y ² , and is preferably an aryl group which may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group which may further have a substituent. More preferably, it is a benzoyl group or a nitro group which may have a substituent. As Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent is preferable.

Further, as the substituent in the benzoyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an alkyloxy group is preferable. Further, as the alkyl group, a methyl group or an ethyl group is preferable, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more -O-, A monocyclic or condensed polycyclic alkyloxy group is preferred, and a linear, branched, monocyclic or condensed polycyclic group having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— It has the same meaning as the alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, It is a cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, or a methoxy group, an ethoxy group, or a tert-butoxy group is preferable. And the like.

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (4a) include photopolymerization initiators represented by the following chemical formulas (4a-1) to (4a-6).

“Oxime ester photopolymerization initiator represented by general formula (4b)”
When Z in the general formula (4) is a —CO— group, an oxime ester-based photopolymerization initiator represented by the following general formula (4b) is preferable.

General formula (4b)

The general formula (4b) corresponds to a case where Z in the general formula (4) is a monovalent organic group containing a carbazole group and Y ³ is a monovalent organic group, and a keto-type carbazole group. Is an oxime ester-based photopolymerization initiator having Y ^{7 to} Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ may have a substituent. Preferably, it is a good aryl group. As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group is preferable, and a benzoyl group is more preferable.

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (4b) include photopolymerization initiators represented by the following chemical formulas (4b-1) to (4b-4).

  Commercial products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyl oxime) (IRGACURE OXE01), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE02) (all manufactured by BASF), N-1919 (made by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.) and the like are commercially available. In addition, oximes described in JP-A-2007-21091, JP-A-2009-79619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photopolymerization initiator.

  The content of the photopolymerization initiator (G) is preferably 0.1 to 20 parts by mass based on the total solid content of the photosensitive coloring composition (100 parts by mass), and is photocurable and developable. From the viewpoint, it is more preferably 0.5 to 10 parts by mass. If the amount is less than 0.1 part by mass, the adhesion of the formed pattern to the base material becomes poor, and if the amount exceeds 20 parts by mass, a problem may occur in the developability or a decrease in lightness after 230 ° C. heat treatment may occur. .

<Sensitizer (H)>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer (H).
Examples of the sensitizer (H) include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. , Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, etc., polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyline derivative, annulene derivative, spiropyran derivative, Spirooxazine derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone , Ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzof Enone, 4,4'-bis (diethylamino) benzophenone and the like.

  Among the above sensitizers, sensitizers that can sensitize particularly preferably include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

One of these sensitizers can be used alone, or two or more of them can be used in an optional ratio as needed.
Examples of commercially available products include “KAYACURE DETX-S” (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and “CHEMARK DEABP” (4,4′-bis (diethylamino) benzophenone manufactured by Chemmark Chemical).

  More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), edited by Chusaburo Ikemori, and others. Sensitizers described in "Specially Functional Materials" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near infrared region can be contained.

  The content when the sensitizer (H) is used is preferably 2 to 60 parts by mass with respect to 100 parts by mass of the photo-radical polymerization initiator contained in the coloring composition, and is photocurable and developable. Is more preferably 4 to 50 parts by mass from the viewpoint of.

<Thiol chain transfer agent (I)>
The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as the chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, a thiol radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated, so that the obtained coloring composition has high sensitivity. .

  Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as a methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having four or more SH groups. By increasing the number of functional groups, the function of initiating polymerization is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

  Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropiolate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu (Tylamino) -4,6-dimercapto-s-triazine and the like, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

  These thiol-based chain transfer agents can be used alone or as a mixture of two or more.

Further, the content of the thiol-based chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0%, based on the total solid content of the coloring composition. Within this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage, etc. are improved.

<Polymerization inhibitor (J)>
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in order to prevent exposure to light caused by diffracted light from the mask during exposure. The addition of the polymerization inhibitor has an effect of preventing the curing from progressing outside the desired pattern by the chain polymerization by exposure.

  Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkyl catechol-based compounds such as butyl catechol and 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol Alkyl resorcinol compounds such as sinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone-based compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; trioctylphosphine oxide; triphenylphosphine oxide; Phosphine compounds such as phosphine oxide compounds, triphenyl phosphite and trisnonylphenyl phosphite , Pyrogallol, and the like phloroglucinol. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, the wrinkle of the coating film, the pattern resolution, etc. are improved.

<Ultraviolet absorber (K)>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and is a benzotriazole organic compound, a triazine organic compound, a benzophenone organic compound, a salicylate organic compound, a cyanoacrylate organic compound, and a salicylate organic compound. Organic compounds and the like can be mentioned.

  The content of the ultraviolet absorber is preferably from 5 to 70% by mass in the total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is smaller than the above, the effect of the ultraviolet absorber is small, and the resolution cannot be ensured, and when the content is larger than the above, the sensitivity is lowered, the pixel peeling and the hole diameter become larger than the design values. May occur.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

  Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the photosensitive coloring composition. When the total content of the photopolymerization initiator and the ultraviolet absorber is smaller than the above, the adhesion is weakened and the pixel peels off. When the total content is larger than the above, the sensitivity is too high and the resolution may be deteriorated.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

  2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy -5'-t-octylphenyl) benzotriazole, 5% of 2-methoxy-1-methylethyl acetate and 95% of benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-(1,1- Mixture of dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazol-2-yl -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1 , 3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4 -(1,1,3,3-tetramethylbutyl) phenol], 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (5-chloro-2H-benzo) Liazol-2-yl) -6-t-butyl-4-methylphenol, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2 -(Methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

  More specifically, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, manufactured by BASF, and ADK STAB LA-29, LA-31RG, LA, manufactured by ADEKA Corporation. -32, LA-36, KEMIPROB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

  As the triazine-based organic compound, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy Reaction product of (phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester, 2,4-bis “2-hydroxy-4 -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- ( Hexyloxy) , 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2 -Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

  More specifically, KEMISORB 102 manufactured by Chemipro Kasei Co., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, ADK STAB LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. No.

  As the benzophenone-based organic compound, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  More specifically, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cipro Kasei Co., Ltd., ADK STAB 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sun Chemical Co., Ltd. No.

  Examples of the salicylate organic compound include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

<Antioxidant (L)>
The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and the thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by a heat process at the time of thermosetting or ITO annealing. Can be higher. In particular, when the colorant concentration of the coloring composition is high, the amount of the crosslinking component in the coating film is small, so the use of a high-sensitivity crosslinking component or the increase in the amount of the photopolymerization initiator causes the yellowing of the heating process to become strong. Can be seen. Therefore, by containing an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high transmittance of the coating film can be obtained.

  The "antioxidant" in the present invention may be any compound having a radical scavenging function or a peroxide decomposing function. Specifically, hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based antioxidants are used. And hydroxylamine-based compounds, and known antioxidants can be used. The antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of compatibility between the transmittance and the sensitivity of the coating film. Agents.

  Hindered phenolic antioxidants include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2-t -Butyl-5-methylphenol), stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-) (Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8, 1 -Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3,5 -Tris (3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2′thiodiethylbis- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,6-bis (dodecylthiomethyl) ) -O -Cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [3- (3-methyl- 4-hydroxy-5-t-butylphenyl) propionic acid] ethylene bisoxybisethylene, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2′-thio-bis- (6-t- Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis- (4, -Dimethyl-phenol), 2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol and the like. No. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  More specifically, Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation, KEMINOX101, 179, 76 manufactured by Chemiplo Corporation, 9425, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, manufactured by BASF, Cyanox CY-1790, CY-2777, manufactured by Sun Chemical Co., Ltd. Is mentioned.

  Hindered amine antioxidants include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetra Methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetra Methyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2 , 2,6,6-tetramethyl-4-piperidyl methacrylate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 Polycondensate with 6,6-tetramethylpiperidine, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl]-[(2 2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 4-hydroxy-2,2,6 Ester of 6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 2,6,6-pentamethyl-4-piperidyl) amino {-1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, bis (2,2,6 , 6-Tetramethyl-1- (octyloxy)- -Piperidinyl) ester, a reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-pyridyl) [[3,5-bis (1,1 dimethyl Ethyl) -4-hydroxyphenyl] methyl] butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyperidyl sebacate, poly [[6-morpholino-s-triazine-2,4-diyl ]-[(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2,2 6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6- Hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide and the like No. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

  More specifically, ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 manufactured by ADEKA Corporation. , LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 94 manufactured by Chemipura Kasei Co., Ltd., Tinuvin 249, TINUVIN 111FDL manufactured by BASF, 123, 144, 292, 5100, Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd., UV- 3529, UV-3853 and the like.

  Examples of the phosphorus-based antioxidants include di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2′-methylenebis (4,6- Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4′- Isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris (isodecyl) phosphite, triphenyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4-Biphenyldiphosphonite Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4′isopropylidenediphenolalkylphosphite, Trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, Phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) Phosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite Diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonite) Loxy) -benzene, ethyl bisphosphite (2,4-ditert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  More specifically, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF, and Hostanox P- manufactured by Clariant Chemicals Co., Ltd. EPQ and the like.

  Examples of the sulfur-based antioxidants include 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate] and 3,3′-thio. Ditridecyl bispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o-cresol , 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

More specifically, Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd. and the like can be mentioned.

  These antioxidants can be used alone or as a mixture of two or more at any ratio as needed.

  The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition, because transmittance, spectral characteristics, and sensitivity are good.

<Leveling agent (M)>
It is preferable to add a leveling agent to the photosensitive coloring composition of the present invention for the purpose of improving the coating property of the composition on a transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as a silicone-based surfactant, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used.

  Examples of the silicone-based surfactant include a linear polymer comprising a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378 manufactured by Big Chemie. , 3455, UV3510, 3570, Dow Corning Toray FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22-4272, X-22 6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341.

  Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain or a leveling agent.

More specifically, Surflon S-242, S-243, S-420, S-611, S-651, S-386, manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-577, manufactured by DIC Corporation. , F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS -21, FC-4430, FC-4432, manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd., and 602A manufactured by Neos Corporation.

  Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrster ether, and polyoxyethylene octyl dodecyl. Ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, Bitane monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Stearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbite tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolau Rate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene Glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl imidazolines, and the like.

  More specifically, Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Rheodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP -O30V, Super SP-L10, AS-10V, AO-10V AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50 , MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amyt 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704 manufactured by ADEKA Corporation. , 913R, Kyoeisha Chemical Co., Ltd. (meth) acrylic acid type Co) polymer Polyflow No. 75, no. 90, no. 95 and the like.

  Examples of the cationic surfactant include an alkylamine salt, an alkyl quaternary ammonium salt such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and an ethylene oxide adduct thereof.

  More specifically, there may be mentioned Acetamine 24, Coatamine 24P, 60W, 86P conc, etc., manufactured by Kao Corporation.

  Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, and monoethanolamine lauryl sulfate. And triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

  More specifically, Neogent Co., Ltd.'s Futuregent 100, 150, Adeka Co., Ltd. Adeka Hope YES-25, Adeka Coal TS-230E, PS-440E, EC-8600, etc. are mentioned.

Examples of the amphoteric surfactant include amide laurate betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkyl betaines such as alkyldimethylaminoacetate betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

  More specifically, examples include Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

When the photosensitive coloring composition of the present invention contains a surfactant, the amount of the surfactant is preferably 0.001 to 2.0% by mass based on the total solid content of the composition of the present invention, More preferably, it is 0.005 to 1.0% by mass. By being in this range, the balance between the coating properties of the coloring composition, the pattern adhesion, and the transmittance is improved.
The photosensitive coloring composition of the present invention may include only one type of surfactant, or may include two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<Storage stabilizer (N)>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time of the composition. As the storage stabilizer, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, organic acids such as oxalic acid and its methyl ether, t-butyl pyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

<Adhesion improver (O)>
The photosensitive coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to enhance the adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

  Examples of the adhesion improver include vinyltrimethoxysilane, vinylsilanes such as vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth) acryl silanes such as methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyl Tyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl Mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; bis (triethoxysilylpropyl) tetrasulfide and the like Sulfide , Silane coupling agents such as isocyanates such as 3-isocyanate propyl triethoxysilane and the like. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition. Within this range, the effect is greater, and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Method for producing photosensitive composition>
The photosensitive coloring composition included in the present invention contains a colorant in a dispersant, a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersing aid (a dye derivative or a surfactant), It can be manufactured by finely dispersing using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). . At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of a coloring agent such as a dye is high, specifically, the solubility in a solvent to be used is high, and the mixture is dissolved by stirring, if the foreign matter is not confirmed, the fine dispersion as described above is produced. No need.

  When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent-developing or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent and other dispersing aids and additives. And the like can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a dye derivative, a dispersant, and a surfactant can be appropriately contained. Since the dispersing agent has a large effect of preventing re-aggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing agent has a lightness, a contrast, and a storage stability. The property becomes good. The dye derivative and the dispersant are as described above.

<Surfactant>
Examples of the surfactant include those described above for the leveling agent, and these can be used alone or in combination of two or more, but are not necessarily limited thereto.

  When a surfactant is added, the amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. If the amount of the surfactant is less than 0.1 part by mass, it is difficult to obtain the added effect, and if the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

<Solvent>
The coloring composition of the present invention contains a solvent for facilitating formation of a colored film by coating on a substrate such as glass so as to have a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of the good coating properties of the coloring composition, the solubility of each component of the coloring composition, and the safety.

As the solvent, a solvent commonly used in the art can be used, and considering the properties such as the boiling point, the SP value, the evaporation rate, the viscosity, and the like, appropriately or separately according to the application conditions (speed, drying conditions, etc.) Used mixed.

Examples of the solvent used include ester solvents (solvents containing -COO- in the molecule and containing no -O-), ether solvents (solvents containing -O- in the molecule and containing no -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (OH in the molecule) Solvent containing no -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

  Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl -n- propyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. And the like.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and the like.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, it is preferable to include an organic solvent having a boiling point at 1 atm of 120 ° C. or more and 180 ° C. or less from the viewpoint of applicability and drying property. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N, N-dimethylformamide, N-methylpyrrolidone, and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

<Removal of coarse particles>
The colored dispersion or the photosensitive composition of the present invention is subjected to centrifugal separation, filtration using a sintering filter or a membrane filter, or the like, to give coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm. It is preferable to remove the coarse particles and the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

<Production method of color filter>
The color filter can be manufactured by a printing method or a photolithography method.
Since the formation of the filter segment by the printing method can be performed by repeating the printing and drying of the coloring composition prepared as the printing ink, the patterning can be performed at low cost and excellent in mass productivity as a color filter manufacturing method. Further, fine patterns having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the composition be such that the ink does not dry and solidify on a printing plate or on a blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or extender.

  When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. According to the method, coating is performed so that the dry film thickness becomes 0.2 to 5 μm. The film dried as necessary is exposed (irradiation of radiation) through a mask having a predetermined pattern provided in contact or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove an uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developer.
In order to increase the exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkali-water-soluble resin, for example, a polyvinyl alcohol or a water-soluble acrylic resin, etc., is coated and dried to form a film that prevents polymerization inhibition by oxygen. Exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink-jet method or the like in addition to the above-mentioned methods, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of producing a color filter by forming each color filter segment on a transparent conductive film by electrophoresis of colloid particles using a transparent conductive film formed on a substrate. . The transfer method is a method in which a filter segment is previously formed on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

  Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a transparent conductive film or the like is formed as necessary.

  The color filter of the present invention is bonded to a counter substrate using a sealant, injects liquid crystal from an injection port provided in a seal portion, and then seals the injection port.If necessary, a polarizing film or a retardation film is formed on the substrate. A color liquid crystal display device is manufactured by laminating to the outside. The color liquid crystal display device includes a twisted nematic (TN), a super twisted nematic (STN), an in-plane switching (IPS), a vertical alignment (VA), an optically-convened bend (OCB). ) Can be used in a liquid crystal display mode for performing colorization using a color filter.

  Further, the color filter of the present invention can be used for manufacturing a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like, in addition to the color liquid crystal display device.

<Liquid crystal display device>
A liquid crystal display device including the color filter of the present invention will be described.
A liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. However, in the present invention, it is preferable to use a white LED from the viewpoint that the red reproduction region is widened. FIG. 1 is a schematic sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to face each other, and a liquid crystal LC is sealed between them.

  The liquid crystal LC is aligned according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), and the like. On the inner surface of the first transparent substrate 11, a TFT (thin film transistor) array 12 is formed, on which a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Further, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

  On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

  A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is further formed thereon. Is provided.

  A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

  Examples of the white LED light source include a light source in which a fluorescent filter is formed on the surface of a blue LED, and a light source in which a phosphor is contained in a resin package of a blue LED, and a wavelength at which the emission intensity is maximized within a range of 430 nm to 485 nm ( λ3), has a wavelength (λ4) at which the emission intensity is maximum in the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and has a wavelength. The ratio (I4 / I3) of the emission intensity I3 at λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at the wavelength λ3 to the emission intensity I5 at the wavelength λ5 (I5 / I3 ) Having a spectral characteristic of 0.1 or more and 1.3 or less and a wavelength (λ1) at which the emission intensity becomes maximum within a range of 430 nm to 485 nm. And has a second emission intensity peak wavelength (λ2) in the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 to 0. A white LED light source (LED2) having a spectral characteristic of 0.7 or less is preferable.

  Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

  Specific examples of the LED 2 include NSSW440 (manufactured by Nichia), NSSW304D (manufactured by Nichia), and the like.

  Hereinafter, the present invention will be described with reference to examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively. "PGMEA" means propylene glycol monomethyl ether acetate.

  First, the calculation method of the method for measuring the average primary particle diameter of the pigment, the weight average molecular weight of the resin, and the acid value of the resin will be described.

(Average primary particle diameter of pigment)
The average primary particle size of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was defined as the particle diameter of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was determined by approximating the cube of the determined particle size, and the volume average particle size was defined as the average primary particle size.

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was calculated using a TSKgel column (manufactured by Tosoh Corporation), GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and a polystyrene equivalent measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Acid value of resin)
To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant, and an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.) ), And the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content of the resin solution.

  Subsequently, a method for producing the dispersant, the binder resin solution, the treated pigment, and the colorant dispersion used in the examples and the comparative examples will be described.

<Production of resin type dispersant (C)>

<(S1) Resin dispersant>
(Production Example 1)
A reaction vessel equipped with a gas inlet tube, a temperature, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate. Was replaced.
The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the mixture was reacted for 7 hours while adding a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was added to 90 parts of propylene glycol monomethyl ether acetate. The solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was added at 100 ° C. The reaction was performed for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the solid content to 40% by solid measurement. A resin-type dispersant (S1-1) having a value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

(Production Examples 2 to 10)
Synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and the charged amounts shown in Table 1 were used, and resin-type dispersants (S1-2 to S1-10) were obtained.

(Tetracarboxylic anhydride)
・ Pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
(Esterification reaction catalyst)
.Mono-n-butyltin (IV) oxide [ethylenically unsaturated monomer having a hydroxyl group]
・ HEMA: hydroxyethyl methacrylate [ethylenically unsaturated monomer having no hydroxyl group]
-MMA: methyl methacrylate-MAA: methacrylic acid-N-MAM: N-methylol acrylamide ("N-MAM" manufactured by Yushi Yushi Co., Ltd.)
・ NBM: Nn-butoxymethylacrylamide (“Amide NBM” manufactured by Yushi & Fat Products Co., Ltd.)
MOI-BM: 2-[(1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (“Karenz MOI-BM” manufactured by Showa Denko)
[Compound having two hydroxyl groups and one thiol group in the molecule]
.3-mercapto-1,2-propanediol [radical polymerization initiator]
・ AIBN: 2,2′-azobisisobutyronitrile [organic solvent]
・ Cyclohexanone ・ Propylene glycol monomethyl ether acetate

<(S2) Resin-type dispersant: hydroxyl group introduced into side chain>
(Production Example 11)
6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone were placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer. Mono-n-butyltin (IV) oxide was charged in an amount of 0.01 part, and was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate were charged. A solution prepared by dissolving 0.1 part of 2'-azobisisobutyronitrile in 26.2 parts of cyclohexanone was added, and the mixture was reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed to 95%, and the reaction was terminated. After completion of the reaction, the nonvolatile content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (S2-11) having a weight average molecular weight of 9,500.
(Production Examples 12 to 16)
Synthesis was performed in the same manner as in Production Example 11 except that the raw materials and the charged amounts shown in Table 2 were used, and resin-type dispersants (S2-12 to S2-16) were obtained.

<(S2) resin-type dispersant: introduction of thermal crosslinking group into side chain>
(Production Example 21)
160 parts of n-butyl acrylate, 40 parts of Karenz MOI-BM (manufactured by Showa Denko), 50 parts of propylene glycol monomethyl ether acetate, and 50 parts of cyclohexanone were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer. The atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added and reacted for 12 hours. The solid content measurement confirmed that 95% had reacted. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 100 ° C. for 7 hours. Was. Measurement of the acid value confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a resin dispersant (S2-21) having an acid value of 42 mgKOH / g and a weight average molecular weight of 9000.

(Production Examples 22, 25 to 28)
Synthesis was carried out in the same manner as in Production Example 21 except that the raw materials and the charged amounts shown in Table 3 were used to obtain a resin-type dispersant (S2-22, S2-25 to S2-28).

(Production Example 23)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 40 parts of Karenz MOI-BM (manufactured by Showa Denko), 50 parts of propylene glycol monomethyl ether acetate, and cyclohexanone 50 parts were charged and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. The solid content measurement confirmed that 95% had reacted. Next, 26 parts of BPDA [3,3 ', 4,4'-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation)], 11 parts of neopentyl glycol, 238 parts of cyclohexanone, and 1,8-diazabicyclo- as a catalyst. 0.40 parts of [5.4.0] -7-undecene was added and reacted at 100 ° C. for 7 hours. Measurement of the acid value confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a resin dispersant (S2-23) having an acid value of 40 mgKOH / g and a weight average molecular weight of 9100.

(Production Example 24)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko), 20 parts of ETERNACOLL OXMA (Ube 20 parts) and 100 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 14 parts of 2-mercapto-2-methyl-1,3-propanediol was added. And reacted for 10 hours. The solid content measurement confirmed that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N) (Hydroxyl value 112 mgKOH / g, manufactured by Kuraray Co., Ltd.) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo- [5.4.0] -7-undecene 0.40 as a catalyst An additional portion was added and reacted at 100 ° C. for 7 hours. Measurement of the acid value confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a resin dispersant (S2-24) having an acid value of 94 mgKOH / g and a weight average molecular weight of 25,000.

(Production Example 29)
Synthesis was performed in the same manner as in Production Example 24 except that the raw materials and the charged amounts shown in Table 3 were used, to obtain a resin-type dispersant (S2-29).

(Production Example 30)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 25 parts of 3-mercapto-1,2-propanediol, 40 parts of pyromellitic dianhydride, 66 parts of cyclohexanone, and monobutyltin oxide as a catalyst were added in an amount of 0.2 parts. After adding 06 parts, the mixture was reacted at 100 ° C. for 7 hours, and it was confirmed by an acid value measurement that 98% or more of the acid anhydride was half-esterified. Next, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of 2-hydroxypropyl methacrylate, and 40 parts of Karenz MOI-BM (manufactured by Showa Denko) were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 200 parts of a cyclohexanone solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved was added, and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement, and the reaction was completed. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a resin dispersant (S2-30) having an acid value of 77 mgKOH / g and a weight average molecular weight of 8,200.

(Production Examples 31 to 34)
Synthesis was carried out in the same manner as in Production Example 30 except that the raw materials and the charged amounts shown in Table 4 were used, and resin-type dispersants (S2-31 to S2-34) were obtained.

-Karenz MOI-BM: 2-([1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, (Showa Denko)
・ ETERNACOLL OXMA: ((3-ethyloxetane-3-yl) methyl methacrylate, manufactured by Ube Industries)
T-BMA: t-butyl methacrylate PMA: pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
-BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation)
BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, (manufactured by JFE Chemical Corporation)
C-1015N: bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N, (hydroxyl value 112 mgKOH / g, manufactured by Kuraray Co., Ltd.)
-DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene, (manufactured by San Apro Corporation)
<(S2) Resin dispersant: Photo group introduced into side chain>
(Production Example 41)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, 650 parts of mono as a catalyst After charging 0.2 parts of butyltin oxide and purging with nitrogen gas, the mixture was reacted at 120 ° C. for 5 hours (first step). The measurement of the acid value confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of solid content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate 200 Parts, 50 parts of methacrylic acid and 663 parts of propylene glycol monomethyl ether acetate, and the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added. For 12 hours (second step). The solid content measurement confirmed that 95% had reacted. Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were charged, and the isocyanate was measured by IR. The reaction was continued until the disappearance of the peak at 2270 cm-1 based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (S2-41) having a solid content of 40%. The resulting dispersant had an acid value of 68, an equivalent weight of unsaturated double bond of 1593, and a weight average molecular weight of 13,000.

(Production Examples 42 to 50)
Synthesis was carried out in the same manner as in Production Example 41 except that the raw materials and the charged amounts shown in Table 5 were used, and resin-type dispersants (S2-42 to S2-50) having a solid content of 40% were obtained.

· 1,6-HD: 1,6-hexanediol · PMA: pyromellitic dianhydride · BTA: 1,2,3,4-butanetetracarboxylic dianhydride · BPDA: 3,3 ', 4 4'-biphenyltricarboxylic anhydride / TMEG: Ethylene glycol ditrimellitic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: RIKACID TMEG-100)
BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydrideDSDA: 3,3', 4,4'-biphenylsulfonetetracarboxylic dianhydrideBPAF: 9,9-bis ( 3,4-Dicarboxyphenyl) fluorene dianhydride TMA: trimellitic anhydride / HEMA: 2-hydroxyethyl methacrylate / 2HPMA: 2-hydroxypropyl methacrylate / 4HBA: 2-hydroxybutyl acrylate / FM-3: terminal Hydroxyl group polycaprolactone-modified methacrylate (Daicel Chemical: Praxel FM-3)
· EA: ethyl acrylate · t-BA: t-butyl acrylate · 2MTA: 2-methoxyethyl acrylate · MMA: methyl methacrylate · BMA: n-butyl methacrylate · BzMA: benzyl methacrylate · St: styrene · MAA: methacrylic acid · MOI : 2-methacryloyloxyethyl isocyanate (Showa Denko: Karenz MOI)
AOI: 2-acryloyloxyethyl isocyanate (Showa Denko: Karenz AOI)
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate (Karenz BEI, manufactured by Showa Denko)
-MOI-EG: 2-methacryloyloxyethoxyethyl isocyanate (Showa Denko: Karenz MOI-EG)

<Production of binder resin (D)>
(Preparation of binder resin (F-1))
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From a tube, 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (“Aronix manufactured by Toagosei Co., Ltd.) M110 "), and a mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin.
After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Ether acetate was added to prepare a binder resin (F-1) solution. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (F-2))
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask. From a tube, 20 parts of methacrylic acid, 20 parts of benzyl methacrylate, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 25 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, A mixture of 1.33 parts of 2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, nitrogen gas was stopped with respect to the total amount of the obtained copolymer solution, and the mixture was stirred while injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK) A mixture of 6.5 parts (MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After the completion of the dropwise addition, the reaction was continued for another hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Thus, a binder resin (F-2) solution was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (F-3))
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, the atmosphere in the flask was changed from air to nitrogen, and then heated to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 136 g of propylene glycol monomethyl ether acetate, and a solution obtained by adding 3.6 g of azobisisobutyronitrile was dropped into the flask over 2 hours from a dropping funnel, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate (0.25 mol, (50 mol% based on the carboxyl group of methacrylic acid used in this reaction)), and 0.1 g of trisdimethylaminomethylphenol were added. 9 g and 0.145 g of hydroquinone were put into the flask, and the reaction was continued at 110 ° C. for 6 hours. Then, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Cyclohexanone was added to the synthesized resin solution so that the nonvolatile content was 20% by mass to obtain a binder resin (F-3) solution. The weight average molecular weight was 13,000, the molecular weight distribution (Mw / Mn) was 2.1, and the nonvolatile acid value was 79 mgKOH / g.

(Preparation of binder resin (F-4))
100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable four-necked flask, and heated to 120 ° C. while pouring nitrogen gas into the vessel. At a temperature, a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped from the dropping tube over 2.5 hours to polymerize. The reaction was performed.
Next, the atmosphere in the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours, and the nonvolatile acid value = 0. The reaction was terminated when the pH reached 8.8, and a resin solution having a weight average molecular weight of about 12,000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile content became 20%, and the binder resin (F-4) A solution was prepared.

<Structure of dye derivative>
Tables 6 to 8 show the dye derivatives (B) used in the examples.

<Method for producing colorant>
(Production of green processing pigment 1)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. After stirring at 40 ° C. for 3 hours, the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (5).

Equation (5)

In a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the formula (5) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, and the mixture was heated to 40 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (6).
100 parts of the obtained aluminum phthalocyanine pigment represented by the formula (6), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. . The kneaded material was put into 3,000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol. A treated pigment 1 was obtained. The average primary particle size was 31.2 nm.

Equation (6)

(Production of green treated pigment 2)
In a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the formula (5) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, and the mixture was heated to 40 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following formula (7).
The obtained aluminum phthalocyanine pigment represented by the formula (7) was subjected to the same salt milling treatment as in the case of the blue colorant (PB-1) to obtain a green-treated pigment 2. The average primary particle size was 29.5 nm.

Equation (7)

(Production of green treated pigment 3)
According to the synthesis method described in JP-A-2010-79247, an aluminum phthalocyanine pigment represented by the following formula (8) was obtained.
The obtained aluminum phthalocyanine pigment represented by the formula (8) was subjected to the same salt milling treatment as in the case of the blue colorant (PB-1) to obtain a green treated pigment 3. The average primary particle size was 33.0 nm.

Equation (8)

(Production of green processing pigment 4)
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (9), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) are added, and the mixture is stirred. The reaction was performed at 20 ° C. for 4 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker were added 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration, followed by stirring at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 8.0 bromine atoms were substituted on the phthalocyanine ring on average.

Next, into a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which 8.0 bromine atoms were substituted on the obtained phthalocyanine ring on average, and 18.2 parts of diphenyl phosphate were added, and 90 parts were added. C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a green treated pigment 4 represented by the following formula (10). The obtained colorant had a volume average primary particle size of 27 nm.

Equation (9)


Equation (10)

(Production of green processing pigment 5)
Next, in a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment obtained by substituting an average of 8.1 bromine atoms in the phthalocyanine ring prepared with green-treated pigment 4, and 13.8 parts of diphenylphosphinic acid Was added, and the mixture was heated to 90 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried to obtain a green treated pigment 5 represented by the following formula (11). The obtained colorant had a volume average primary particle size of 31 nm.

Equation (11)

(Production of green processing pigment 6)
Next, in a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which 8.0 bromine atoms were substituted on the phthalocyanine ring prepared by the green treatment pigment 4 on average, and bis (4-nitrophosphate) were added. (Phenyl)), and the mixture was heated to 90 ° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a green treated pigment 6 represented by the following formula (12). The volume average primary particle diameter of the obtained colorant was 32 nm.

Equation (12)

(Production of green processing pigment 7)
500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the formula (9) and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) are added to a three-necked flask, and the mixture is stirred. The reaction was performed at 6 ° C. for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker were added 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration, followed by stirring at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 10.1 bromine atoms were substituted on the phthalocyanine ring on average.

Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which 10.1 bromine atoms were substituted on the obtained phthalocyanine ring on average and 13.9 parts of diphenyl phosphate were added to a three-necked flask, and 90 parts were added. C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried to obtain a green treated pigment 7 represented by the following formula (13). The obtained colorant had a volume average primary particle size of 27 nm.

Equation (13)

(Production of green treated pigment 8)
203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and at 140 ° C., 50 parts of a phthalocyanine pigment represented by the formula (9) were added. The mixture was reacted at 160 ° C. for 7 hours while heating to 160 ° C. and blowing 215.4 parts of bromine. The reaction mixture was poured into 2500 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. The residue was washed with a 1% aqueous hydrochloric acid solution, hot water, a 1% aqueous sodium hydroxide solution and hot water in that order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Thereafter, the sulfuric acid solution was poured into 9800 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. Next, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue obtained by filtration were added to a beaker, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 15.0 bromine atoms were substituted on the phthalocyanine ring on average.

Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 11.9 bromine atoms substituted on the obtained phthalocyanine ring and 10.8 parts of diphenyl phosphate were added to a three-necked flask, and 90 parts of the resulting mixture were added. C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a green treated pigment 8 represented by the following formula (14). The obtained colorant had a volume average primary particle size of 31 nm.

Equation (14)

(Production of green processing pigment 9)
250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added to a three-neck flask and stirred at 150 ° C. for 30 minutes. Thereto was added 50 parts of an aluminum phthalocyanine pigment represented by the formula (5), and the mixture was stirred at 155 ° C. for 30 minutes to be dissolved. Further, 58.5 parts of trichloroisocyanuric acid was added, and the mixture was stirred at 190 ° C. for 5 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker were added 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration, followed by stirring at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 8.1 chlorine atoms were substituted on the phthalocyanine ring on average.

Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which 11.9 bromine atoms were substituted on the obtained phthalocyanine ring on average and 22.6 parts of diphenyl phosphate were added to a three-necked flask, and 90 parts of the mixture were added. C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a green treated pigment 9 represented by the following formula (15). The volume average primary particle diameter of the obtained colorant was 29 nm.

Equation (15)

(Production of red treated pigment 1)
C. I. Pigment Red 254 (110 parts), sodium chloride (salt) (800 parts), and diethylene glycol (100 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded material was poured into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C. all day and night. Thus, a red treated pigment 1 was obtained.

(Production of red treated pigment 2, yellow treated pigments 1 to 6, and blue treated pigments 1 to 3)
Except that the raw materials used for the red treated pigment 1 were changed to the compositions shown in Table 9, the same operation as in the production of the red treated pigment 1 was performed, and the red treated pigment 2, the yellow treated pigments 1 to 6, and the blue treated pigments 1 to 1 were produced. 3 was obtained.

PR254: C.I. I. Pigment Red 254
PR177: C.I. I. Pigment Red 177
PY150: C.I. I. Pigment Yellow 150
PY138: C.I. I. Pigment Yellow 138
PY139: C.I. I. Pigment Yellow 139


PY185: C.I. I. Pigment Yellow 185
PB15: C.I. I. Pigment Blue 15
PB15: 3: C.I. I. Pigment Blue 15: 3
PB15: 6: C.I. I. Pigment Blue 15: 6

<Production method of pigment dispersion>
(Colorant dispersion (DG1-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. To prepare a colorant dispersion (DG1-1). The pigment derivative and the resin-type dispersant were used in the following mass ratio.

Pigment (green-treated pigment 1): 12.0 parts Dye derivative (dye derivative 1 / dye derivative 2 / dye derivative 3 = 1/1/1): 1.0 part resin-type dispersant solution (S1-1 / S2- 11 / S2-21 = 1/1/1): 5.0 parts Solvent (propylene glycol monomethyl ether acetate): 52.0 parts

(Colorant dispersions (DG1-2-40, DG2-1-39, DG3-1-39, DG4-1-39, DG5-1-39, DG6-1-39, DG7-1-39, DG8- 1-39, DG9-1-39, DG10, DY1-6, DR1-2, DB1-3,))
Except that the pigments, dye derivatives, and resin-type dispersants were changed to the types shown in Tables 10 to 17, the colorant dispersions (DG1-2 to 40, DG2- DG3-1 to 39, DG4-1 to 39, DG5-1 to 39, DG6-1 to 39, DG7-1 to 39, DG8 to 39, DG9-1 to 39, DG10, DY1 6, DR 1-2, DB 1-3,).

Abbreviations in Tables 10 to 17 are shown below.
EFKA4300: "EFKA-4300" manufactured by BASF (acrylic polymer dispersant)
PG58: C.I. I. Pigment Green 58

<Production of photosensitive coloring composition>
The following adjustments were made in the production of the photosensitive coloring composition.
-Resin binder solution A: A mixed solution prepared by mixing resin binder (F-1) (F-2) (F-3) (F-4) solutions at a mass ratio of 1: 1: 1: 1.
Polymerizable compound A: Alonix M402 and Aronix M520 manufactured by Toagosei Co., Ltd., KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd., and UA-510H manufactured by Kyoeisha Chemical Co., Ltd. were mixed and adjusted at a mass ratio of 1: 1: 1: 1. Mixture / photopolymerization initiator A: A mixed solution obtained by dissolving 1 part of Omnirad 907 manufactured by IGM Resins, 1 part of Omnirad 369E manufactured by IGM Resins, and 1 part of Omnirad 819 manufactured by IGM Resins, in 100 parts of propylene glycol monomethyl ether acetate.
-Photopolymerization initiator B: 0.6 parts of the oxime ester-based photopolymerization initiator of the chemical formula (3a-1), 0.6 parts of the oxime ester-based photopolymerization initiator of the chemical formula (3b-1), and the chemical formula (4a- 0.6 parts of the oxime ester-based photopolymerization initiator of 1), 0.6 parts of the oxime ester-based photopolymerization initiator of the chemical formula (4a-3), and 0.1 parts of the oxime ester-based photopolymerization initiator of the chemical formula (4b-1) A mixed solution in which 6 parts are dissolved in 100 parts of propylene glycol monomethyl ether acetate.
-Sensitizer A: a mixed solution in which 1 part of KAYACURE DETX-S manufactured by Nippon Kayaku and 1 part of CHEMARK DEABP manufactured by Chemmark Chemical are dissolved in 100 parts of propylene glycol monomethyl ether acetate.
Epoxy compound A: A mixture prepared by mixing 1: 1: 1 of jER E157S70 manufactured by Mitsubishi Chemical Corporation, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.
Oxetane compound A: OXT-221 manufactured by Toagosei Co., Ltd.
-UV absorber A: a mixed solution in which 1 part of "TINUVIN P" manufactured by BASF, 1 part of "TINUVIN 405", and 1 part of "KEMISORB 10" manufactured by Chemipura Kasei are dissolved in 100 parts of propylene glycol monomethyl ether acetate.
Polymerization inhibitor A: A mixed solution in which 1 part of “3-methylcatechol”, 1 part of “methylhydroquinone”, and 1 part of “tert-butylhydroquinone” are dissolved in 100 parts of propylene glycol monomethyl ether acetate.
-Antioxidant A: 1 part of "IRGANOX1010" manufactured by BASF, 1 part of "ADEKA STAB LA-52" manufactured by ADEKA, 1 part of "ADEKA STAB PEP-36" manufactured by ADEKA, 1 part of "ADEKA STAB AO-412S" manufactured by ADEKA Is dissolved in 100 parts of propylene glycol monomethyl ether acetate.
Thiol chain transfer agent A: Pentaerythritol tetrakisthiopropionate Silane coupling agent A: KBM-403, KBM-5103, KBM-1003, KBM-573, KBM-803 manufactured by Shin-Etsu Silicone Co., Ltd. A mixture prepared by mixing at a ratio of 1: 1: 1.
-Leveling agent A: 1 part of "BYK-330" manufactured by BYK Chemie, 1 part of "Megafac F-551" manufactured by DIC, and 1 part of "Emulgen 103" manufactured by Kao Corporation were dissolved in 100 parts of propylene glycol monomethyl ether acetate. Mixed solution.
-Solvent A: Propylene glycol monomethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 1,3-butylene glycol diacetate, 3-methoxy-1-butanol are mixed in a ratio of 3: 1: 1: 1: 1, Adjusted mixed solution.

[Example 1]
(Photosensitive coloring composition (R-1))
After the mixture having the following composition was stirred and mixed so as to be uniform, the mixture was filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (R-1).
Colorant dispersion 1 (DG1-1): 23.0 parts Colorant dispersion 2 (DY2-1): 17.0 parts Resin binder solution A: 6.0 parts Polymerizable compound A: 1.0 part Photopolymerization Initiator A: 8.0 parts Sensitizer A: 1.0 parts Epoxy compound A: 1.0 parts Oxetane compound A: 1.0 parts Ultraviolet absorber A: 1.0 parts Polymerization inhibitor A: 1.0 Part antioxidant A: 1.0 part thiol chain transfer agent A: 1.0 part silane coupling agent A: 1.0 part leveling agent A: 1.0 part solvent A: 36.0 parts

[Examples 2 to 513, Comparative Example 1]
(Photosensitive coloring composition (R-2 to 513, 676))
Except that the colorant dispersions 1 and 2 and the photopolymerization initiator were changed to the compositions shown in Tables 18 to 28, the mixture was made uniform in the same manner as the photosensitive coloring composition (R-1). After stirring and mixing, the mixture was filtered through a 1 μm filter to obtain a photosensitive resin composition (R-2 to 513, 676).

(Photosensitive coloring composition (R-514))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (R-514).
Colorant dispersion 1 (DG1-1): 21.0 parts Colorant dispersion 2 (DY2): 16.0 parts Colorant dispersion 3 (DG10): 3.0 parts Resin binder solution A: 6.0 parts Polymerizable compound A: 1.0 part Photopolymerization initiator A: 4.0 parts Photopolymerization initiator B: 4.0 parts Sensitizer A: 1.0 parts Epoxy compound A: 1.0 parts Oxetane compound A: 1.0 part UV absorber A: 1.0 part Polymerization inhibitor A: 1.0 part Antioxidant A: 1.0 part Thiol chain transfer agent A: 1.0 part Silane coupling agent A: 0 parts Leveling agent A: 1.0 parts Solvent A: 36.0 parts

[Examples 515 to 675]
(Photosensitive coloring composition (R-515 to 675))
After stirring and mixing the mixture so as to be uniform, in the same manner as the photosensitive coloring composition (R-1), except that the colorant dispersions 1, 2, and 3 were changed to the compositions shown in Tables 29 to 32. The mixture was filtered through a 1 μm filter to obtain a photosensitive resin composition (R-515 to 675).

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring compositions (R-1 to R-676) were evaluated by the following methods. The results are shown in Tables 18 to 32.

[Filter segment pattern formation]
The obtained photosensitive coloring composition was applied on a glass substrate of 10 cm × 10 cm by spin coating, and then heated at 70 ° C. for 5 minutes in a clean oven to remove the solvent, thereby obtaining a coating film of about 2 μm. . Next, the substrate was cooled to room temperature, and exposed to light with an exposure amount of 50 mJ / cm ² through a 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) stripe pattern photomask using an ultra-high pressure mercury lamp. Thereafter, the substrate was spray-developed with a 23 ° C. aqueous sodium carbonate solution, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 20 minutes. Spray development was performed for each photosensitive colored composition coating film for 1.5 times the shortest possible time for forming a pattern without residual development, and this was defined as an appropriate development time. The thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Engineering Co., Ltd.).

[Resolution evaluation (pattern resolution)]
With respect to the pattern at the 25 μm photomask portion of the filter segment formed by the above method, the resolution was visually evaluated using an optical microscope, and evaluated according to the following criteria. X is a level that cannot be used.
〇: The stripe pattern is completely independent, and no residue is seen between the lines. △: The adjacent stripe patterns are partially connected. X: The adjacent stripe patterns are connected.

[Development residue evaluation]
The obtained photosensitive coloring composition was applied on a 10 × 10 cm silicone wafer substrate by spin coating, and dried by heating at 80 ° C. for 1 minute on a hot prelate to form a coating film having a thickness of 2 μm. This coating film was exposed at 50 mJ / cm ² with a high-pressure mercury lamp using a pattern mask having a line width of 50 μm, and then spray-developed for 60 seconds using a 0.05% aqueous potassium hydroxide solution kept at 25 ° C. The film was sufficiently washed with ion-exchanged water and dried with clean air to obtain a coating film for evaluation. Spray development was performed for each photosensitive colored composition coating film for 1.5 times the shortest possible time for forming a pattern without residual development, and this was defined as an appropriate development time. On the substrate from which the coating film was removed by development, the presence or absence of a residue was observed with a 50-fold optical microscope. The case where no residue was confirmed at all was evaluated as ○, the case where the residue was confirmed in the number of 1 or more to less than 10 was evaluated as Δ, and the case where 10 or more residues were confirmed was evaluated as ×. X is a level that cannot be used.

As shown in Tables 18 to 32 above, when the photosensitive coloring composition of the present invention was evaluated as a cured film, it was excellent in pattern resolution and residue. Further, the same evaluation was performed on the color filter produced using the cured film. As a result, favorable results were obtained with respect to the pattern resolution and the residue, and high-yield production could be performed. As a result, the liquid crystal display device, the solid-state imaging device, and the organic EL display device using the color filter can be suitably used.

Claims (10)

Aluminum phthalocyanine pigment [A] represented by the following general formula (A-1), dye derivative (B), resin-type dispersant (C), binder resin (D), polymerizable compound (F), photopolymerization initiator ( G) and a coloring composition containing an organic solvent, wherein the dye derivative (B) is a phthalocyanine-based dye derivative represented by the following general formula (103) (provided that the dye derivative (B) has the general formula (A- Excluding the case where the aluminum phthalocyanine pigment (A) represented by 1) is present).

General formula (A-1)


[In General Formula (A-1), X _{1 to} X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or a group which may have a substituent. Good cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group Or an arylthio group which may have a substituent.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
Z represents a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxyl group which may have a substituent. Or an aryloxy group which may have a substituent, wherein R ₁ and R ₂ , or R _3, R _{4 and} R ₅ may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represent an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ each represent 0 to _4. 4 may be the same or different. ]

General formula (103)

[In general formula (103),
R ₁₀₆ and R ₁₀₇ are each independently a hydrogen atom, a hydroxyl group, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a phthalimidoalkyl group optionally having a substituent, An acyl group which may have a group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, a group represented by the general formulas (150) to (155), (158), or (159) is there. m and n each independently represent a positive integer. However, this excludes the case where R ₁₀₆ and R ₁₀₇ are simultaneously hydrogen atoms.
M ₁ is a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom, an iron atom, or a hydroxyl group, a chlorine atom, —OP (＝ O) R ₁ R ₂ , and —O—SiR ₃ R ₄ represents an aluminum atom having at least one substituent selected from the group consisting of R _5. R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or Represents an aryloxy group which may have a substituent, wherein R ₁ and R ₂ , or R _3, R _{4 and} R ₅ may be bonded to each other to form a ring; ]



[In general formulas (150) to (155),
X ₁ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 -, - CH2NHCOCH 2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a.
Y ₁ represents a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Y ₂ represents a direct bond, an arylene group which may have a substituent, or a heteroaromatic ring which may have a substituent, and these groups include —NR ₁₇₀ −, —O—, and —SO ₂ — Or CO— may be mutually connected by a divalent linking group selected from —CO—.
Y ₃ is a direct _{bond, -NR 170} - represents a or -O-.
o represents an integer of 0 to 20.
M ₂ represents a hydrogen atom, calcium atom, a barium atom, strontium atom, a manganese atom or an aluminum atom.
i represents the valence of _{M 2.}
R ₁₅₀ and R ₁₅₁ each independently represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent, and R ₁₅₀ and R ₁₅₁ And may further have a substituent containing a nitrogen, oxygen or sulfur atom.
R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ each independently may have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , — represents Cl, -F, or _Y 3 _-Y 2 _-Y 1 _-Q, group one of _{R 157} and _{R 158} is represented by the following general formula (156) or (157), -O- (CH _{2) o -R 171, -OR 172} , or _NR 173 _{R 174.}
R ₁₇₀ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent.
R ₁₇₁ represents an optionally substituted heterocyclic residue, and R _{172 to} R ₁₇₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted substituent. It represents a good alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue. ]

General formula (156)

[In the general formula (156), _{Z 1} is _-NR 170 -, - CONH- or represents -O-, _{Z 2} is an optionally substituted alkylene group, an optionally substituted alkenylene group, an arylene group which may have a substituent, these _{groups, -NR 170 -, - O -} , - SO 2 - or a divalent linking group selected from CO- be bonded to each other Is also good. _{However, R 170} has the same meaning as _{R 170} in formula (150) - (155).
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a phenyl group optionally having a substituent, or R ₁₅₀ and R ₁₅₁ . Represents a heterocyclic ring which may further have a substituent and further contains a nitrogen, oxygen or sulfur atom. ]

General formula (157)

[In the general formula (157), _{Z 3} is a direct _{bond, -NR 175 -, - NR 175} -Z 4 -CO -, - NR 175 -Z 4 -CONR 176 -, -NR 175 -Z 4 -SO 2 —, —NR ₁₇₅ —Z ₄ —SO ₂ NR ₁₇₆ —, —O—Z ₄ —CO—, —O—Z ₄ —CONR ₁₇₅ —, —O—Z ₄ —SO ₂ —, or O—Z ₄ — SO ₂ NR ₁₇₅ - _{represents, R 175} and _{R 176} are each independently a hydrogen atom, an optionally substituted alkyl group, a an alkenyl group or a substituted group may have a substituent Z ₄ represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent.
R _{152 to} R ₁₅₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a polyoxyalkylene. Represents a group. ]

General formula (158)

General formula (159)

[In the general formula _(159), X _{2 is, -SO 2 -, - CO -} , - NH -, - SO 2 NH -, - NHSO 2 -, - CONH- or represents _{-NHCO-, R} 163 to R ₁₆₇ is each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphate group, or a group represented by any of the general formulas (150) to (155). ]
The resin-type dispersant (C) is a reaction product of a hydroxyl group of a polymer having a hydroxyl group with an acid anhydride group of a tricarboxylic anhydride or a tetracarboxylic dianhydride and / or a hydroxyl group of a compound having a hydroxyl group, and tricarboxylic acid. The photosensitive material for a color filter according to claim 1, which is a reaction product obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride group of an acid anhydride or a tetracarboxylic dianhydride. Coloring composition. The photosensitive coloring composition for a color filter according to claim 1 or 2, wherein the binder resin (D) contains an alkali-soluble resin having an ethylenically unsaturated double bond. The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, wherein the photopolymerization initiator (G) contains an oxime ester-based initiator. The photosensitive coloring composition for a color filter according to any one of claims 1 to 4, further comprising an epoxy compound (E-1) or an oxetane compound (E-2). A cured film, which is a cured product of the photosensitive coloring composition for a color filter according to claim 1. A color filter comprising a substrate and the cured film according to claim 6. A liquid crystal display device comprising the color filter according to claim 7. A solid-state imaging device comprising the color filter according to claim 7. An organic EL display device comprising the color filter according to claim 7.