JP2020101622A - Photosensitive colored composition, color filter, and liquid-crystal display - Google Patents

Abstract

To provide: a photosensitive colored composition that is so sensitive as to realize good pattern shape (linearity, cross-sectional shape) and has high solvent resistance, even if containing a high concentration of a colorant; and a color filter and a liquid-crystal display.SOLUTION: A photosensitive colored composition for a color filter contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photoinitiator (D). The colorant (A) contains one or more organic pigments (A1) selected from the group consisting of pigments represented by the general formulas (1) to (3). The photoinitiator (D) includes a photoinitiator [D1] represented by the general formula (4) and/or a photoinitiator [D2] represented by the general formula (5).SELECTED DRAWING: Figure 1

Description

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

The liquid crystal display device is equipped with a member in which a substrate, a color filter, a transparent electrode, and an alignment film are sequentially stacked. Since a specific organic solvent having a high dissolving power such as N-methylpyrrolidone is often used for the alignment film, the color filter partly elutes due to contact with the organic solvent, resulting in poor light distribution or color. In some cases, unevenness occurs, and a display defect occurs in the liquid crystal display device. Therefore, improvement of solvent resistance to a specific organic solvent has been demanded.

Liquid crystal display devices are widely used in liquid crystal color televisions, car navigation systems, personal computers, smartphones, etc., and are required to be even thinner. Therefore, the photosensitive coloring composition used for forming the pixel pattern of the color filter (hereinafter, simply referred to as a pattern) needs to contain a coloring agent in a high concentration so that a desired color tone can be obtained even if the color filter is a thin film. was there. However, there is a problem that it is difficult to form a good pattern because increasing the concentration of the pigment hinders photocurability.

Patent Document 1 discloses a colorant, a photopolymerizable compound dipentaerythritol hexaacrylate, a photopolymerization initiator 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and the like. A photosensitive coloring composition comprising is disclosed. In Patent Document 2, a colorant, a photopolymerizable compound is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate, and a photopolymerization initiator is an acetophenone compound or biimidazole. Coloration containing at least one selected from the group of acetophenone compounds and triazine compounds, or at least one selected from the group of acetophenone compounds and triazine compounds in addition to the biimidazole compound as a photopolymerization initiator Compositions are disclosed.

JP, 2009-098594, A JP 2001-154013 A

However, the conventional photosensitive coloring composition uses a highly curable photopolymerizable compound and a specific photopolymerization initiator, so the solvent resistance is improved, but it is difficult to form a pattern with a good shape. There was a problem.

INDUSTRIAL APPLICABILITY The present invention provides a photosensitive coloring composition and a color filter which are capable of obtaining a highly sensitive and favorable pattern shape (linearity, cross-sectional shape) even when the coloring agent is contained in a high concentration and which has high solvent resistance. , And a liquid crystal display device.

The photosensitive coloring composition of the present invention is a coloring composition for a color filter containing a colorant (A), a binder resin (B), a photopolymerizable compound (C) and a photopolymerizable initiator (D). The colorant (A) contains at least one organic pigment (A1) selected from the group consisting of pigments represented by the following general formulas (1) to (3), and the photopolymerizable initiator (D) contains at least one of the photopolymerization initiator [D1] represented by the following general formula (4) and the photopolymerization initiator [D2] represented by the following general formula (5).

General formula (1)

In formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{1 to} X ₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfo group. Represents a halogen atom.

General formula (2)

In formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{5 to} X ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group or a halogen atom. A represents a direct bond or a divalent linking group. Examples of the divalent linking group include an alkylene group which may have a substituent, —O—, —S—, —CO—, —SO ₂ —, —COO—, —CONH—, and —SO ₂ NH—. Represent

General formula (3)

[In the general formula (3), A′ represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , Alternatively, it represents —SO ₂ NHR ^12, and at least one of R ^{2 to} R ⁶ represents a trifluoromethyl group. R ^{7 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

General formula (4)

In the general formula (4), X ¹ , X ³ and X ⁶ each independently represent R ¹³ , OR ¹³ , COR ¹³ , SR ¹³ , CONR ¹⁴ R ¹⁵ or CN, and X ² has a substituent. An alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may have a substituent, and 7 carbon atoms which may have a substituent. 30 arylalkyl group, or the number of carbon atoms which may have a substituent group represents a heterocyclic group of 2 to 20, X ⁴ and X ⁵ are each ^{independently, R 13, oR 13, SR} 13 , COR ¹³ , CONR ¹⁴ R ¹⁵ , NR ¹⁴ COR ¹³ , OCOR ¹³ , COOR ¹³ , SCOR ¹³ , COSR ¹³ , COSR ¹³ , CSOR ¹³ , CN, a halogen atom or a hydroxyl group. R<^13> , R<^14> and R< ¹⁵ > each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent; Represent a and b are each independently an integer of 0 to 3.

General formula (5)

In the general formula (5), R ₇ , R ₈ , R ₉ , and R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or It represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

According to the present invention described above, it is possible to obtain a high-sensitivity and good pattern shape (linearity, cross-sectional shape) even when the colorant is contained in a high concentration or the colorant is contained in a high concentration, and It is possible to provide a photosensitive coloring composition having a high solvent property, a color filter, and a liquid crystal display device.

FIG. 1 is a schematic sectional view of a liquid crystal display device.

First, the terms used in this specification are defined. “(Meth)acryloyl” is “acryloyl and methacryloyl”. "(Meth)acrylic" is "acrylic and methacrylic". , "(Meth)acrylic acid" is "acrylic acid and methacrylic acid". "(Meth)acrylate" is "acrylate and methacrylate". The monomer is an ethylenically unsaturated group-containing monomer. Further, “C.I.” means a color index (C.I.).

The photosensitive coloring composition of the present invention is a coloring composition for a color filter containing a coloring agent (A), a binder resin (B), a photopolymerizable compound (C) and a photopolymerization initiator (D). The colorant (A) contains at least one organic pigment (A1) selected from the group consisting of pigments represented by the general formulas (1) to (3), and the photopolymerizable initiator ( D) contains at least one of the photopolymerization initiator [D1] represented by the general formula (4) and the photopolymerization initiator [D2] represented by the general formula (5).
The photosensitive coloring composition of the present invention will be described below with reference to preferred embodiments.

<Colorant (A)>
The colorant (A) constituting the photosensitive coloring composition of the present invention is one or more selected from the group consisting of pigments represented by the following general formulas (1) to (3). Of the organic pigment (A1).

<Organic pigment (A1)>
General formula (1)

In formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{1 to} X ₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfo group. Represents a halogen atom.

Examples of the “halogen atom” for R ₁ include fluorine, bromine, chlorine and iodine, and among these, chlorine is preferable.

Examples of the “alkyl group which may have a substituent” in R ₁ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group, etc. Among these, a methyl group and a trifluoromethyl group are preferable.

Examples of the “alkoxy group which may have a substituent” in R ₁ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, Examples thereof include a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, and a 2-(diethylamino)ethoxy group. Among these, a methoxy group and a trifluoromethoxy group are preferable, and a methoxy group is particularly preferable.

Examples of the “aryloxy group which may have a substituent” in R ₁ include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2-methylphenyloxy group. Group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, and the like. Among these, a phenoxy group is preferable.

In R ₂ and R ₃ , the “alkyl group which may have a substituent(s)” is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a tert. -Amyl group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, Examples thereof include a cyclohexyl group and a dimethylcyclohexyl group, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group and a 2-hydroxyethyl group are preferable.

In R ₂ and R ₃ , the substituent of the “phenyl group which may have a substituent” is a halogen atom in R _1, an alkyl group which may have a substituent, or a substituent which may have a substituent. Examples thereof include an alkoxy group and an aryloxy group which may have a substituent. In addition to these, a hydroxy group, an amino group, —NR ₁₁ R ₁₂ , a sulfo group, —SO ₂ NR ₁₃ R ₁₄ , and —COOR _{15 are also included.} , -CONR ₁₆ R ₁₇ , a nitro group, and a cyano group.

R _{11 to} R ₁₇ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and the “alkyl group which may have a substituent” is an amino group, a monoalkylamino group, Alternatively, an alkyl group substituted with a dialkylamino group is preferable.

In X _{1 to} X ₄ , the “alkyl group which may have a substituent” has the same meaning as in R ₁ and is preferably a methyl group, an ethyl group or a trifluoromethyl group.

In X _{1 to} X ₄ , the “alkoxy group which may have a substituent(s)” has the same meaning as in R ₁ .

General formula (2)

In formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{5 to} X ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group or a halogen atom. A represents a direct bond or a divalent linking group. Examples of the divalent linking group include an alkylene group which may have a substituent, —O—, —S—, —CO—, —SO ₂ —, —COO—, —CONH—, and —SO ₂ NH—. Represent

In R ₄ , as “halogen atom”, “alkyl group optionally having substituent(s)”, “alkoxy group optionally having substituent(s)”, and “aryloxy group optionally having substituent(s)” Is as defined in R ₁ .

In R ₅ and R ₆ , the “alkyl group which may have a substituent” and the “phenyl group which may have a substituent” have the same meanings as those in R ₂ and R ₃ .

In X _{5 to} X ₁₂ , the “alkyl group which may have a substituent” and the “alkoxy group which may have a substituent” have the same meanings as those in R ₁ .

In A, the alkylene group which may have a substituent is a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group or an n-dodecylene group. Examples of the substituent include a “alkyl group which may have a substituent” represented by R ₁ .

The A in the general formula (2), substituents alkylene group which may have a, -O -, - S -, - CO -, - SO ₂ - is preferably, -SO ₂ among them - is Particularly preferred.

General formula (3)

In the general formula (3), A'represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or It represents -NHCOR ¹² or -SO ₂ NHR ¹³ . R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Formula Among naphthol azo pigment represented by (3), ^preferably, the azo pigment at least one is a trifluoromethyl group of R 2 to R ^6, or at least one of ^R 2 to R ⁶ -NHCOR ^The azo pigment of No. ¹² is preferable because it is easy to make the pigment particles fine and the contrast ratio is excellent.

Examples of the naphthol azo pigment represented by the general formula (3) include C.I. I. Pigment Red 31, 32, 146, 147, 150, 184, 187, 188, 210, 238.245.247, 266, 268, 269, C.I. I. Violet 25, 50, etc. are mentioned. Among these, from the viewpoint of hue and brightness, C.I. I. Pigment Red 150, 170, 187, 266, 268, 269 is preferable.

In the general formula (3), in A′, as the “substituent” of the phenyl group which may have a substituent, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Monovalent acidic group selected from cyano group, trifluoromethyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group. To trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.) and the like. Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group and an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group and the like. However, it is not limited thereto.

Further, in A′, the “substituent” of the heterocyclic group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a tri group. Monovalent to trivalent acid groups selected from fluoromethyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group. Examples thereof include metal salts (eg, sodium salt, potassium salt, aluminum salt, etc.). Further, the “heterocycle” means one in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a monocycle or a condensed ring. Therefore, the heterocycle includes a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an isoxazole ring, and an isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent free radical derived by removing a hydrogen atom from these heterocycles, and therefore, specific examples of the heterocyclic group which may have a substituent include 2- Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2- Oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, Examples thereof include N-carbazolyl group.

Further, examples of the halogen atom in R ^{2 to} R ⁶ include fluorine, chlorine, bromine, and iodine.

The alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹³ may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. , Sec-butyl group and tert-butyl group.

From the viewpoint of lightness, it is preferable that A′ is a phenyl group which may have a substituent. Further, from the viewpoint of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁷ , and more preferably R ¹ is a methyl group or a methoxy group.

When the pigment represented by the general formula (3) is used as the colorant (A) used in the present invention, it may be a tautomer thereof or a pigment having any crystal form. It may be a mixed crystal of pigments having any crystal form called a shape. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement and X-ray crystal structure analysis.

The colorant (A) in the photosensitive coloring composition of the present invention contains an organic pigment (A2) other than the above organic pigment (A1) within a range that does not impair the effects of the present invention, such as for adjusting chromaticity. Other colorants such as dyes (AS) can be used in combination. These colorants can be used alone or as a mixture of two or more kinds at an arbitrary ratio as needed.

<Organic pigment (A2)>
Preferred examples of the organic pigment (A2) include C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, a pigment represented by the following general formula (7), or a pigment represented by the following general formula (6).

General formula (7)

In formula (7), A ^1's each independently represent a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In A ¹ , the “substituent” of the phenyl group which may have a substituent and the “substituent” of the heterocyclic group which may have a substituent are the same as the “substitution” in A′ of the general formula (3). The same as "group".

The alkyl group having 1 to 4 carbon atoms in R ⁵¹ , R ⁵⁷ and R ⁵⁸ may be linear or branched, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group and butyl group. , Isobutyl group, sec-butyl group, and tert-butyl group.

In the pigment, from the viewpoint of brightness, it is preferable that A ¹ is a phenyl group which may have a substituent. Further, from the viewpoint of lightness and dispersibility, R ⁵¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁵⁷ , and more preferably R ⁵¹ is a methyl group or a methoxy group.

When the pigment represented by the general formula (7) is used as the colorant (A) used in the present invention, it may be a tautomer thereof or a pigment having any crystal form. It may be a mixed crystal of pigments having any crystal form called a shape. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement and X-ray crystal structure analysis.

Examples of the naphthol azo pigment represented by the general formula (7) include C.I. I. Pigment Red 176 and the like.

General formula (6)

In formula (6), Z _{1 to} Z ₁₃ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Optionally an aryl group, —SO ₃ H, —COOH, and a monovalent to trivalent metal salt of these acidic groups, an alkylammonium salt, an optionally substituted phthalimidomethyl group, or an optionally substituted group. The optional sulfamoyl group is shown.
The adjacent groups of Z _{1 to} Z ₄ and/or Z _{10 to} Z ₁₃ may be combined together to form an aromatic ring which may have a substituent.

Examples of the halogen atom in Z _{1 to} Z ₁₃ include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group which may have a substituent in Z _{1 to} Z ₁₃ include 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, and an n-hexyl group. , N-octyl group, stearyl group, 2-ethylhexyl group and other linear or branched alkyl groups, trichloromethyl group, trifluoromethyl group, 2,2,2-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 And alkyl groups having a substituent such as 4-methoxybenzyl group, 4-nitrobenzyl group and 2,4-dichlorobenzyl group.

The alkoxy group which may have a substituent in Z _{1 to} Z ₁₃ is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group. , 2,3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and other linear or branched alkoxy groups, trichloromethoxy group, trifluoro group Methoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, Examples thereof include an alkoxy group having a substituent such as a 2-nitropropoxy group and a benzyloxy group.

Examples of the aryl group which may have a substituent in Z _{1 to} Z ₁₃ include an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, a p-methylphenyl group, a p-bromophenyl group and a p-nitrophenyl group. Group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2- Examples thereof include an aryl group having a substituent such as a naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

Examples of the acidic group in Z _{1 to} Z ₁₃ include —SO ₃ H and —COOH, and examples of the monovalent to trivalent metal salt of these acidic groups include sodium salt, potassium salt, magnesium salt, calcium salt and iron. Examples thereof include salts and aluminum salts. Examples of the alkylammonium salt of an acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. Ammonium salts may be mentioned.

Z ₁ to Z may have a substituent in ₁₃ phthalimidomethyl group _{(C 6 H 4 (CO)} 2 N-CH 2 -), and which may have a substituent sulfamoyl group _(H 2 NSO ₂ Examples of the "substituent" in -) include the above halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and the like. To be

Adjacent groups of Z _{1 to} Z ₄ and/or Z _{10 to} Z ₁₃ of the general formula (6) may be combined together to form an aromatic ring which may have a substituent. The aromatic ring as used herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and a heteroaromatic ring includes pyridine. Examples thereof include ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, and carbazole ring.

Specific examples of the organic pigment represented by the general formula (6) used in the present invention include the quinophthalone compounds (a) to (r) shown below, but the present invention is not limited thereto. .. The quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent No. 2930774, but the present invention is not limited thereto.

Examples of the organic pigment (A2) other than those mentioned above include C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 41, 48:1, 48:2, 48:3, 48: 4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 95, 112, 114, 119, 122, 136, 144, 164, 166, 168, 169, 170, 171, 175, 178, 179, 185, 200, 202, 208, 213, 214, 220, 221, 246, 253, 255, 256, 258, 264, 270, 272, 273, 274, 276, 277, 278, 279. 280, 281, 282, 283, 284, 285, 286, 287, 291, C.I. I. Pigment Orange 1, 4, 15, 16, 22, 24, 38, 43, 71, 73, 74, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 49, 53, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124, 126, 127, 128, 129, 130, 147, 151, 152, 153, 154, 155, 156, 161, 162, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193, 194, 198, 199, 205, 214, 213, 218, 219, 220, 221 and the like can also be preferably used.

<Dye (AS)>
Examples of the dye (AS) include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Further, as the dye, a derivative thereof or a lake pigment obtained by lakeizing the dye can also be used.

The acidic dye preferably has an acidic group such as sulfonic acid or carboxylic acid. The direct dye may form an inorganic salt of an acid dye or a salt-forming compound of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. preferable. Further, a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye is also preferable. In addition, the salt-forming compound is easily converted into a sulfonamide and modified into a sulfonic acid amide compound to easily obtain a photosensitive coloring composition having excellent resistance (light resistance and solvent resistance).
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent resistance (light resistance and solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

The basic dye may be used as it is, but a salt-forming compound that forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferable. Salt forming compounds of basic dyes are preferable because of their excellent resistance (light resistance, solvent resistance) and affinity with pigments. Further, in the salt-forming compound of a basic dye, the anion component acting as a counter ion is an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, a halogenated carbonized compound. An anion compound having a conjugate base of an organic acid having a hydrogen group and a salt-forming compound prepared by salting an acid dye are preferable. The salt-forming compound has further improved resistance when it contains a polymerizable unsaturated group in the molecule.

Examples of dyes include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, anthraquinone dyes Pyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes Dyes (oxonol dye, merocyanine dye, arylidene dye, styryl dye, cyanine dye, squarylium dye, croconium dye, etc.), quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, perinone dye, indigo System dyes, thioindigo system dyes, quinoline system dyes, nitro system dyes, nitroso system dyes, rhodamine system dyes, and metal complex system dyes thereof. Among these, from the viewpoint of color characteristics such as hue, color separation difficulty, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium. Dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. The specific compounds of the dyes are "New Edition Dye Handbook" (Organized by Synthetic Organic Chemistry, Maruzen, 1970), "Color Index" (The Society of Dyers and colors), "Dye Handbook" (Okawara et al.; Kodansha, 1986) and the like.

<Refinement of pigment>
The pigment in the colorant (A) of the present invention is preferably blended with other materials after being made fine. Examples of the refining method include wet grinding, dry grinding, and dissolution precipitation method. In the present specification, salt milling treatment by a kneader method, which is one type of wet grinding, is preferable.
The average primary particle diameter of the pigment is preferably 5 to 90 nm, more preferably 10 to 70 nm. When the average primary particle size is appropriate, the dispersibility is improved and the contrast ratio is also improved. The average primary particle diameter is obtained by averaging about 20 particles from an enlarged image of a TEM (transmission electron microscope).

The salt milling treatment is a batch process of 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, or a planetary mixer. Alternatively, it is a treatment of mechanically kneading with heating using a continuous kneader and then washing with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high 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 size, a narrow distribution range, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like. Of these, inexpensive sodium chloride (salt) is preferable. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, more preferably 300 to 1000% by mass, relative to 100% by mass of the pigment.

The water-soluble organic solvent can wet the pigment and the water-soluble inorganic salt. Any water-soluble organic solvent may be used as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. In the present specification, a solvent having a high boiling point of 120° C. or higher is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent is easily evaporated. The water-soluble organic solvent is, 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, etc. Can be mentioned. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and more preferably 50 to 500% by mass, based on 100% by mass of the pigment.

When the salt is subjected to the salt milling treatment, a resin can be added if necessary. Examples of the type of resin include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. The resin is preferably solid at room temperature (25° C.) and water-insoluble. In addition, it is also preferable that the resin is partially soluble in an organic solvent in some embodiments. The amount of the resin used is preferably 5 to 200 mass% with respect to 100 mass% of the pigment.

<Dispersant (E)>
A known resin-type dispersant can be used as the dispersant (E) in the photosensitive coloring composition. The resin-type dispersant has a colorant-affinitive site that adsorbs to the colorant (A) and a relaxation site that has a high affinity for components other than the colorant and that causes three-dimensional repulsion between dispersed particles.
Examples of the dispersant (E) include urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid ammonium salts. Carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester and modified products thereof; formed by reaction of poly(lower alkyleneimine) and polyester having a free carboxyl group Amide or a salt thereof; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc.; Examples thereof include polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, and phosphoric acid ester-based compounds.
Further, the polymer dispersant having a basic functional group is a nitrogen atom-containing graft copolymer, a nitrogen atom-containing graft copolymer having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in its side chain. Examples thereof include acrylic block copolymers and urethane polymer dispersants.

Commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by Big Chemie 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 Bykumen, etc. 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403. 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502. , 1503 and the like, Azisper-PA111, PB711, PB821, PB822, PB824 and the like manufactured by Ajinomoto Fine-Techno Co., Inc.

The photosensitive coloring composition preferably uses a resin type dispersant having a carboxyl group (=acidic dispersant). Examples of the acidic dispersant include a comb-shaped resin dispersant and a linear resin dispersant.

[Comb-shaped acidic dispersant]
The comb-shaped acidic dispersant can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406, and JP 2011-157416.
For example, a resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic acid dianhydride, or a hydroxyl group of a compound having a hydroxyl group, and a tetracarboxylic acid dianhydride. In the presence of a reaction product with an acid anhydride group of a product, a resin-type dispersant which is a polymer obtained by polymerizing a monomer, or a hydroxyl group of a compound having a hydroxyl group, and an acid anhydride of a tetracarboxylic dianhydride. In the presence of a reaction product with a physical group, a hydroxyl group, a t-butyl group or an oxetane skeleton, a monomer having a thermal crosslinking group such as blocked isocyanate and a resin type dispersant having a side chain obtained by polymerizing the other It is a resin-type dispersant obtained by reacting a silenic unsaturated monomer having an isocyanate group with a hydroxyl group of its side chain.

[Linear acidic dispersant]
The linear acidic dispersant 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 acid anhydride to a hydroxyl group from a vinyl polymer having one hydroxyl group at one end as a raw material. Can be done.

The dispersant (E) has a carboxyl group formed by reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A polyester portion (X1), a monomer (b1) having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group and a blocked isocyanate group, and a monomer having a carboxyl group. A dispersant containing an acidic dispersant (E1) having a vinyl polymer portion (X2) obtained by radical polymerization of a monomer (b2) and having such a crosslinkable functional group is preferable because of excellent solvent resistance. ..
Further, the dispersant (E) preferably contains a vinyl resin type dispersant (E2) (=basic resin type dispersant) having a piperidyl skeleton.

<Vinyl resin type dispersant having a piperidyl skeleton (E2)>
The vinyl resin dispersant (E2) having a piperidyl skeleton (hereinafter referred to as a dispersant (E2)) is a dispersant synthesized by using a monomer having a piperidyl skeleton represented by the general formula (8).

General formula (8)

In formula (8), R ¹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR. ⁴ represents, R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, R ² and, R ^3's each independently represent a methyl group, an ethyl group, or a phenyl group. "*" indicates a bond.

In the general formula (8), examples of the alkyl group having 1 to 18 carbon atoms of R ¹ and R ⁴ include linear, branched and cyclic alkyl groups. Specific examples thereof include a methyl group, ethyl group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group and hexadecyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ and R ⁴ in the general formula (8) include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

In the general formula (8), examples of the aralkyl group having 7 to 12 carbon atoms of R ¹ and R ⁴ include a group having an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 8 carbon atoms bonded to each other. To be Specific examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a 2-phenylpropan-2-yl group.

In the general formula (8), examples of the acyl group represented by R ¹ and R ⁴ include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group. Specific examples include an acetyl group and a benzoyl group.
In the present invention, R ¹ is preferably, for example, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an oxy radical group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

The dispersant (E2) has a piperidyl skeleton represented by the general formula (8) and thus has an antioxidant function.

The content of the monomer having a piperidyl skeleton represented by the general formula (8) in the dispersant (E2) is preferably 1 to 100% by mass, more preferably 25 to 100% by mass, and further preferably 40 to 100% by mass. preferable. By containing an appropriate amount, in addition to obtaining the desired antioxidant property, it is easy to suppress the decrease in brightness of the pixel.

The dispersant (E2) preferably has an amine value of 50 to 350 mgKOH/g. When it has an appropriate amine value, it is easy to adjust the viscosity of the photosensitive coloring composition, and the brightness is further improved.

The number average molecular weight of the dispersant (E2) is preferably 500 to 30,000. This makes it easy to adjust the viscosity of the photosensitive coloring composition and improves the viscosity stability.

Specific examples of the monomer having a piperidyl skeleton include compounds represented by the following general formula (8-1) and compounds represented by the following general formula (8-2).

In General Formula (8-1) and General Formula (8-2), R ⁵ and R ⁷ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a methylene group or a C 2-5 group. Represents an alkylene group, and X represents a group represented by the general formula (8). Y is _{-CONH - *, - SO 2 -} *, - SO 2 NH- * are shown (. However, the bond marked with "*" is bonded to X), n is an integer of 0-9. R ⁶ is preferably an ethylene group or a propylene group, more preferably an ethylene group. n is an integer of 0-8, and preferably an integer of 0-6.

Commercially available products of the monomer represented by the general formula (8-1) include, for example, compounds represented by the following general formulas (9-1) to (9-7).

In the general formula (9-1) ~ Formula (9-7), R ⁵ has the same meaning as R ⁵ in the general formula (8-1).

Specific examples of the monomer represented by the general formula (8-2) include compounds represented by the following general formulas (10-1) to (10-4).

In formula (10-1) to formula (10-4), R ⁷ has the same meaning as R ⁷ in the general formula (8-2).

Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R ⁵ is a methyl group in the general formula (10-1)), 1,2,2,6,6-pentamethyl Piperidyl methacrylate (a compound in which R ⁵ is a methyl group in the above general formula 10-2) is preferable, and 1,2,2,6,6-pentamethylpiperidyl methacrylate (the above general formula (10-2)) is more preferable. ..

The other monomer is not particularly limited as long as it is a monomer copolymerizable with the monomer having a piperidyl skeleton, and can be appropriately selected according to the application.
Examples of the copolymerizable monomer include (meth)acrylic acid alkyl ester, amino group-containing (meth)acrylate, nitrile, vinyl monomer, the above-mentioned (hydroxyl group-containing monomer), and (poly)alkylene glycol. Examples thereof include monomers, (meth)acrylates having an alkoxysilyl group, fluoroalkyl (meth)acrylates, silicone macromers, carboxyl group-containing monomers and amino group-containing monomers.

Examples of the (poly)alkylene glycol monomer include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate and diethylene glycol monoethyl. Ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, tri Propylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol mono (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as stearyl ether (meth)acrylate and octoxy polyethylene glycol-polypropylene glycol (meth)acrylate; phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, Phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (Poly)alkylene glycol having an aromatic ring such as (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polypropylene glycol (meth)acrylate, and nonylphenoxy poly(ethylene glycol-propylene glycol) (meth)acrylate (Meth)acrylates; and the like.
The (meth)acrylate having an alkoxysilyl group is, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl trimethoxysilane etc. are mentioned.
Examples of fluoroalkyl (meth)acrylates include trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate.
Examples of the silicone macromer include (meth)acryloxy-modified polydimethylsiloxane.

Carboxyl group-containing monomers include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acrylic acid. Loyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone (meth)acrylate, etc. Can be mentioned.

Examples of the amino group-containing monomer include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate and N,N-diethylamino. (Meth)acrylates having a tertiary amino group such as propyl(meth)acrylate; N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl( (Meth)acrylamide and (meth)acrylamides having a tertiary amino group such as N,N-diethylaminopropyl(meth)acrylamide; dimethylaminostyrene, diethylaminostyrene and the like.

As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. When the polymerization initiator is used, it is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the monomer.

In the step of producing the vinyl resin type dispersant (E2) having a piperidyl skeleton, a solvent-free or organic solvent can be used.

Further, it is desirable to use the acidic dispersant (E1) and the vinyl resin type dispersant (E2) having a piperidyl skeleton at the time of pigment dispersion.
By using it at the time of dispersing the pigment, the vinyl-based resin-type dispersant (E2) having a piperidyl skeleton is easily adsorbed on the surface of the pigment, and the interaction with the pigment is strengthened to improve the dispersibility.

The dispersant (E) can be used alone or in combination of two or more kinds.

<Dye derivative>
The photosensitive coloring composition may contain a dye derivative. When the pigment derivative is adsorbed on the surface of the pigment, the pigment surface has polarity and is easily compatible with the dispersant (E), whereby the dispersibility of the pigment is further improved. The dye derivative is a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue. For example, a compound having an acidic substituent such as a sulfo group, a carboxy group and a phosphoric acid group, an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group and a phthalimide. Examples thereof include compounds having a neutral substituent such as an alkyl group. Since the resin-type dispersant used in combination has an acidic group, a dye derivative having a basic group is preferable.
Examples of organic dyes include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzo. Indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo and the like. ..

Specifically, as the diketopyrrolopyrrole dye derivative, JP 2001-220520 A, WO 2009/081930 Pamphlet, WO 2011/052617 Pamphlet, WO 2012/102399 Pamphlet, JP 2017-156397 A, Phthalocyanine As the system dye derivative, JP 2007-226161 A, WO 2016/163351 pamphlet, JP 2017-165820 A, JP 575266 B, and as the anthraquinone dye derivative, JP 63-264674 A, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, and a quinacridone dye derivative are JP-A-48- 54128, JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 as a dioxazine-based dye derivative, and JP-A-2007-314785 as a thiazine-indigo-based dye derivative. The publications and triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 as benzoisoindole dye derivatives, JP-A-2003-167112 and JP-A-2006-291194 as quinophthalone dye derivatives. 2008-31281, JP 2012-226110 A, as naphthol dye derivatives, JP 2012-208329 A, JP 2014-5439 A, and as azo dye derivatives, JP 2001-172520 A. JP-A-2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, and JP-A-2005 as basic substituents. Known dye derivatives described in, for example, JP-A-181383 and JP-A-2005-213404. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. The compound having a substituent such as a functional group has the same meaning as a dye derivative.

The dye derivative can be used alone or in combination of two or more kinds.

The content of the dye derivative is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and further preferably 5 to 50 parts by mass, relative to 100 parts by mass of the colorant (A).

By adding a pigment derivative to the pigment and performing pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, and 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.

<Binder resin (B)>
The photosensitive coloring composition of the present invention contains a binder resin (B). As the binder resin (B), 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. Examples of the binder resin (B) include thermoplastic resins and thermosetting resins. Of these, thermoplastic resins are preferred. Further, the binder resin (B) is preferably an alkali-soluble resin capable of forming a pattern shape by a photolithography method.

<Thermoplastic resin>
The thermoplastic 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, Examples thereof include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
The alkali-soluble resin is preferably a thermoplastic resin having an acidic group. Examples of the acidic group include a carboxyl group and a sulfone group. Examples of the alkali-soluble resin include acrylic resin having an acid group, α-olefin/(anhydrous) maleic acid copolymer, styrene/styrene sulfonic acid copolymer, ethylene/(meth)acrylic acid copolymer, or isobutylene/ Examples thereof include (anhydrous) maleic acid copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer are preferable in terms of developability, heat resistance and transparency, and an acrylic resin having an acidic group is more preferable.

<Alkali-soluble resin>
The alkali-soluble resin imparts development solubility to the film formed from the photosensitive coloring composition when the color filter is produced by the photolithography method.

The mass average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The value of Mw/Mn is preferably 10 or less. Alkali development solubility is further improved by moderate Mw.
The acid value of the alkali-soluble resin is preferably 50 to 200 (KOHmg/g), more preferably 70 to 180, and even more preferably 90 to 170. When it has an appropriate acid value, the alkali developability is further improved.

The alkali-soluble resin includes an alkali-soluble resin (B1) having no ethylenically unsaturated double bond (hereinafter referred to as an alkali-soluble resin (B1)) and an alkali-soluble resin having an ethylenically unsaturated double bond (B2) ( Hereinafter, the alkali-soluble resin (B2) will be mentioned.

<Alkali-soluble resin (B1)>
The alkali-soluble resin (B1) is a resin that polymerizes a carboxyl group-containing monomer and a monomer other than the carboxyl group-containing monomer.

<Alkali-soluble resin (B2)>
The alkali-soluble resin (B2) is preferably, for example, a resin synthesized by the method (i) or (ii) below. As a result, the crosslink density of the coating film formed from the photosensitive coloring composition upon irradiation with light is further improved.

[Method (i)]
In the method (i), for example, first, an epoxy group-containing monomer and a polymer of the monomer are synthesized. Then, a method of adding a carboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble resin (B2) can be mentioned.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-. An epoxy cyclohexyl (meth)acrylate is mentioned. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxy, halogen, nitro and cyano substituents. And other monocarboxylic acids.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

The monomer and polybasic acid anhydride can be used alone or in combination of two or more kinds.

Further, as a method similar to the method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to prepare a polymer. Then, a method of adding an epoxy group-containing monomer to a part of the carboxyl group of the polymer to obtain the alkali-soluble resin (B2) can be mentioned.

[Method (ii)]
In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and another monomer are synthesized to prepare a polymer. Then, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

As the hydroxyl group-containing monomer, the monomers exemplified above can be used. Among them, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable from the viewpoint that foreign matter is unlikely to occur in the coating. Further, glycerol mono(meth)acrylate is preferable in terms of photosensitivity.

Examples of the monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

The binder resin (B) can be used alone or in combination of two or more kinds.

The content of the binder resin is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant (A). From the viewpoint of good film-forming properties and various resistances, the amount is preferably 20 parts by mass or more, and the concentration of the colorant is high, and the color properties can be expressed, and therefore, 400 parts by mass or less is preferable.

<Thermosetting compound>
The photosensitive coloring composition of the present invention can contain a thermosetting compound. Thus, when a color filter is produced, the crosslink density is improved in the heating step after the film is patterned by photolithography, so that the heat resistance is improved. Further, since the coloring agent (A) is less likely to aggregate in the heating step, the contrast ratio is further improved.

The thermosetting compound is a low molecular weight compound or a polymer (thermosetting resin) and is not limited in molecular weight.
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. Among these, epoxy compounds and oxetane compounds are preferable.

(Epoxy compound)
Examples of the epoxy compound include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted). Polycondensate of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol Of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones Polycondensates with (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, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) , Polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine-based epoxy resins, glycidyl ester-based resins Epoxy resin etc. are mentioned.

Commercial products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (these are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (the above are trade names. Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (product name; Mitsui Chemicals, Inc.), EPPN-501H, 502H (product name; Nippon Kayaku Co., Ltd.), JER 1032H60 (product name; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (these are trade names; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-. 103S, EOCN-104S, EOCN-1020 (these are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (these 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 (these are trade names; manufactured by Nagase Chemtex Corp.), TEPIC-L, TEPIC-H, TEPIC-. S (manufactured by Nissan Chemical Industries, Ltd.) and the like.

The content of the epoxy compound is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the colorant (A). Addition of an appropriate amount further improves the heat resistance of the coating and the pattern shape.

(Oxetane compound)
The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include a monofunctional oxetane compound, a bifunctional oxetane compound, and a trifunctional or higher functional oxetane compound.

Examples of the monofunctional oxetane compound include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-Ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy Silyl)propoxy]methyl}oxetane and the like.
Examples of commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry, and OXT-101 and OXT-212 manufactured by Toagosei.

The bifunctional oxetane compound is, for example, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 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-hydroxymethyl oxetane, 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-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycosebis (3-Ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(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 bisphenol 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-oxetanyl) Methyl) ether and the like.
Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

The oxetane group having three or more functional groups includes pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl). -3-Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3- Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane group (For example, an oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462) and a polymer obtained by radically polymerizing a (meth)acrylic monomer such as OXE-30 described above.

The content of the oxetane compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass. The solvent resistance of the coating is further improved by containing an appropriate amount.

(Melamine compound)
The melamine compound is a compound having a melamine ring structure. The melamine compound includes a low molecular weight compound and a high molecular weight compound. In this specification, the melamine compound is preferably a compound in which a methylol group or an ether group is bonded to the melamine ring. The number of methylol groups and/or ether groups bonded per melamine ring is preferably 5.0 or more on average. If it has an appropriate number of bonds, the solvent resistance of the coating film is further improved, and the contrast ratio is less likely to decrease.

Commercial products include, for example, Nicarac 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 ( Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries Co., Ltd.) and the like.

Among these, the number of methylol groups and/or ether groups per melamine ring is 5.0 or more on average, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30. , MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries, Inc.) Is preferable in that the crosslink density of the coating is further improved.

The content of the melamine compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass. The solvent resistance of the coating is further improved by containing an appropriate amount.

(Curing agent)
In the present specification, a curing agent can be contained in order to assist the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like.
Amine compounds include (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl). Amines, 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, etc.) and the like.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

<Photopolymerizable compound (C)>
The photosensitive coloring composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and contains a photopolymerizable compound [C1] having an isocyanurate skeleton and/or an alkylene chain. It is more preferable to include the photopolymerizable compound [C2]. The photopolymerizable compound (C) is, for example, a monomer or an oligomer that is cured by ultraviolet rays or heat as exemplified below to form a transparent resin.

(Photopolymerizable compound [C1] having isocyanurate skeleton)
The photopolymerizable compound [C1] having an isocyanurate skeleton is, for example, a photopolymerizable compound [C1] having an isocyanurate skeleton represented by the following general formula (11) (hereinafter referred to as photopolymerizable compound [C1]). ..

General formula (11)

In general formula (11), R ₁ , R ₂ , and R ₃ are each independently a group represented by general formulas (12-1) to (12-5) below, but at least one is It is any of the groups represented by formulas (12-1) to (12-4).

In formulas (12-1) to (12-5), R ₄ , R ₅ , and R ₆ each independently represent H or CH ₃ , and n and m each independently represent 1 to 20. It is an integer, and l is an integer of 1 to 5. * Is a bond that bonds to R ₁ , R ₂ , or R ₃ of the general formula (11).

Commercially available products of the photopolymerizable compound [C1] are ethoxylated isocyanuric acid triacrylate (A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)), tris(2-acryloyloxyethyl) isocyanurate (Funkryl FA-731A (Hitachi Chemical Co., Ltd.). Industrial Co., Ltd.)), ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate (A-9300-1CL (Shin Nakamura Chemical Co., Ltd.)), A9300-3CL (Shin Nakamura Chemical Co., Ltd.), CIC acrylate (Manufactured by Shikoku Kasei) and the like.

The content of the photopolymerizable compound [C1] is preferably 5 to 400 parts by mass and more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the colorant (A). When contained in an appropriate amount, photosensitivity is further improved.

(Alkylene chain-containing photopolymerizable compound [C2])
The alkylene chain-containing photopolymerizable compound [C2] (hereinafter referred to as the photopolymerizable compound [C2]) is a monomer having an alkylene chain in its molecule. When the photosensitive coloring composition contains the photopolymerizable compound [C2], the mobility of the ethylenically unsaturated group bonded to the alkylene chain is improved, and the curability of the coating is further improved. Examples of the alkylene chain include an ethylene chain, a propylene chain and a pentylene chain. Among these, a pentylene chain having high reactivity is preferable. The alkylene chain also includes a polyalkylene chain. The photopolymerizable compound [C2] does not include the alkylene chain-containing photopolymerizable compound [C1].

Examples of the photopolymerizable compound [C2] include compounds synthesized by reacting a polyhydric alcohol, (meth)acrylic acid and a cyclic ester.
Examples of the cyclic ester include α-acetolactone, β-propionlactone, γ-butyrolactone, σ-valerolactone, ε-caprolactone and the like.
Examples of the polyhydric alcohol include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and the like.

Specific examples of the photopolymerizable compound [C2] are shown in the following general formula (12).

General formula (12)

In general formula (12), 6 Rs are all groups represented by the following general formula (13), or 1 to 5 of 6 Rs are groups represented by the following general formula (13). The remainder is a group represented by the following general formula (14).

General formula (13)

In formula (13), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

General formula (14)

(In the general formula (14), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)

A commercially available product of the photopolymerizable compound [C2] is, for example, DPKA-20 (m=1 in the above formulas (12) to (14), represented by the general formula (13)) as KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. Number of groups=2, compound in which all R ¹ are hydrogen atoms, DPCA-30 (same formula, m=1, number of groups shown in general formula (13)=3, compound in which all R ¹ are hydrogen atoms) ), DPCA-60 (the same formula, m=1, the number of groups represented by the general formula (13)=6, compounds in which all R ¹ are hydrogen atoms), DPCA-120 (m=2 in the same formula, the general formula) The number of groups shown in (13)=6, compounds in which all R ¹ are hydrogen atoms) and the like.

The content of the photopolymerizable compound [C2] is preferably 5 to 400 parts by mass and more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the colorant (A). The reason for containing an appropriate amount is not clear, but this improves the pattern linearity.

In the present invention, it is preferable to use the photopolymerizable compound [C1] and the photopolymerizable compound [C2] together. By the combined use, solvent resistance and a good pattern shape can be more highly compatible.

The photopolymerizable compound (C) includes, in addition to the photopolymerizable compound [C1] and the photopolymerizable compound [C2], a photopolymerizable compound having an acid group, a photopolymerizable compound having a urethane bond, and other monomers. Can be included.

(Photopolymerizable compound having an acid group)
Examples of the acid group of the photopolymerizable compound having an acid group include a sulfonic acid group, a carboxyl group and a phosphoric acid group.

The photopolymerizable compound having an acid group is, for example, an esterification product of a poly(meth)acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; a polyvalent carboxylic acid and a monohydroxyalkyl. Examples thereof include esterified products with (meth)acrylates.
Examples of the photopolymerizable compound having an acid group include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentamethacrylate. Free carboxyl group-containing monoester products of acrylates or monohydroxyoligomethacrylates with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), Tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and 2 Examples include monohydroxy monoacrylates such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, and free carboxyl group-containing oligoester products with monohydroxy monomethacrylates.

Commercially available photopolymerizable compounds having an acid group include, for example, Viscoat #2500P manufactured by Osaka Organic Co., Ltd., and M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. Can be mentioned.

(Photopolymerizable compound having urethane bond)
The photopolymerizable compound can contain a photopolymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond (hereinafter referred to as a polymerizable compound having a urethane bond). The polymerizable compound having a urethane bond is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional isocyanate reacted with an alcohol to further have a hydroxyl group (meth). Examples thereof include polyfunctional urethane acrylates obtained by reacting acrylates.

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 Examples thereof include acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

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

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of crosslinking of the cured coating film is high and the solvent resistance is high. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

Commercial products of the polymerizable compound having a urethane bond are, for example, Kyoeisha Chemical Co., Ltd. AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167. , UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry, and the like.

Other monomers 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, phenoxy Tetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane 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, pentaerythritol 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, ester Acrylate, various acrylic and methacrylic esters such as (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol diester Examples thereof include vinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

Commercially available products of photopolymerizable compounds are, for example, KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAAR manufactured by Nippon Kayaku Co., Ltd. R712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYADPAKADAR, D-330. -30, KAYARAD DPCA-60, KAYARAD DPCA-120, and M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350 manufactured by Toagosei. , 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, viscoat #310HP, viscoat #335HP, viscoat #700, viscoat #295, viscoat #330, viscoat #360, viscoat #GPT, viscoat #400, viscoat #405, Shin-Nakamura manufactured by Osaka Organic Co., Ltd. Examples include A-9300 manufactured by Kagaku Co., Ltd.

A photopolymerizable compound (C) having an acid group, a photopolymerizable compound (C) having a urethane bond, a photopolymerizable compound [C1] having an isocyanurate skeleton, and an alkylene chain-containing photopolymerizable compound [C2] 5 to 400 parts by mass, and more preferably 10 to 300 parts by mass, based on 100 parts by mass of the colorant (A). This further improves the photosensitivity.

<Photopolymerizable initiator (D)>
The photosensitive coloring composition of the present invention is represented by the photopolymerization initiator [D1] represented by the following general formula (4) (hereinafter referred to as the photopolymerization initiator [D1]) and/or the general formula (5) below. A photopolymerization initiator [D2] (hereinafter, referred to as photopolymerization initiator [D2]) is included. As a result, the photosensitive coloring composition has high sensitivity and can form a film having a good pattern shape.

(Photopolymerization initiator (D1))
General formula (4)

In the general formula (4), X ¹ , X ³ and X ⁶ each independently represent R ¹³ , OR ¹³ , COR ¹³ , SR ¹³ , CONR ¹⁴ R ¹⁵ or CN, and X ² has a substituent. An alkyl group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may have a substituent, and 7 carbon atoms which may have a substituent. 30 arylalkyl group, or the number of carbon atoms which may have a substituent group represents a heterocyclic group of 2 to 20, X ⁴ and X ⁵ are each ^{independently, R 13, oR 13, SR} 13 , COR ¹³ , CONR ¹⁴ R ¹⁵ , NR ¹⁴ COR ¹³ , OCOR ¹³ , COOR ¹³ , SCOR ¹³ , COSR ¹³ , COSR ¹³ , CSOR ¹³ , CN, a halogen atom or a hydroxyl group. R<^13> , R<^14> and R< ¹⁵ > each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent; Represent a and b are each independently an integer of 0 to 3.

X ¹ in the general formula (4) is a methyl group, an ethyl group, an n-propyl group, an isopropyl group from the viewpoint of easiness of synthesis, sensitivity, solubility, and storage stability when contained in the photosensitive coloring composition. , N-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group, and other alkyl groups having 10 or less carbon atoms; cyclopentyl group, cyclohexyl A cyclic alkyl group which may have a side chain having 10 or less carbon atoms, such as a group; An alkyl group having 10 or less carbon atoms such as a group and having one ether bond in the methylene chain is preferable.

X ³ in the general formula (4) represents hydrogen, a methyl group, an ethyl group, or an n-propyl group from the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in the photosensitive coloring composition. , Isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and other alkyl groups having 6 or less carbon atoms; cyclopentyl group, cyclohexyl group, etc. A cyclic alkyl group having 6 or less carbon atoms; a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, a 2-(1-ethoxypropyl) group, or the like, which has 6 or less carbon atoms and is methylene. An alkyl group having one ether bond in the chain is preferable.

X ⁶ in the general formula (4) represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group from the viewpoints of easiness of synthesis, sensitivity, solubility, and storage stability when contained in the photosensitive coloring composition. , N-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and other alkyl groups having 6 or less carbon atoms; cyclopentyl group, cyclohexyl group and other carbon numbers A cyclic alkyl group having 6 or less; a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, a 2-(1-ethoxypropyl) group, or the like, having 6 or less carbon atoms and having a methylene chain. An alkyl group having one ether bond is preferable.

X ² in the general formula (4) is a methyl group, an ethyl group, an n-propyl group, an isopropyl group from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in the photosensitive coloring composition. , N-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and other alkyl groups having 6 or less carbon atoms, cyclopentyl group, cyclohexyl group and the like C6 or less cyclic alkyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc. An alkyl group having one ether bond is preferable.

X ⁴ and X ⁵ in the general formula (4) represent hydrogen, a methyl group, an ethyl group, or n, from the viewpoints of easiness of synthesis, sensitivity, solubility, and storage stability when contained in the photosensitive coloring composition. An alkyl group having 6 or less carbon atoms such as -propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, and n-hexyl group is preferable.

Examples of the heterocyclic group having 2 to 20 carbon atoms in X ^{1 to} X ⁶ in the general formula (4) include a 3 to 7-membered heterocyclic group, preferably pyridyl, pyrimidyl and furyl. A 5- to 7-membered heterocyclic ring such as, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl. Can be mentioned.

Examples of the photopolymerization initiator (D1) include the following compounds.

Examples of the method for synthesizing the photopolymerization initiator (D1) include the following methods.
<Step 1> Synthesis of Acyl Form: The nitrocarbazole compound 1 and the acid chloride 2 are reacted in the presence of aluminum chloride to obtain the desired acyl form 3.
<Step 2> Synthesis of Formula (1): An acyl compound 3, hydroxyamine hydrochloride, and dimethylformamide are charged and heated and stirred to obtain an oxime compound 4. The photopolymerization initiator (D1) is obtained by heating and stirring the oxime compound 4 and the acid anhydride 5 and neutralizing with an alkali after completion of the reaction.

When the photosensitive coloring composition contains the photopolymerization initiator (D1), it is possible to achieve both solvent resistance and good pattern shape (linearity, cross-sectional shape), and it is easy to obtain a color filter having excellent production stability.
The photopolymerization initiator (D1) cleaves the N—O bond of the oxime in the compound by absorbing ultraviolet light to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small exposure amount. Further, since the compound has an absorption wavelength in the range of 330 nm to 430 nm due to the nitrocarbazole group in the compound, the reaction efficiency by various UV-visible light sources is high. In general formula ^{_{(4) -C 6 H 3 (}} X 3) in OX ² site is considered to enhance the development resistance.

The content of the photopolymerization initiator (D1) is preferably 1 to 100 parts by mass and more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the colorant (A).

(Photopolymerization initiator (D2))
General formula (5)

R ₇ , R ₈ , R ₉ , and R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted An alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, It represents a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

The hydrogen atom of the substituent in R _{7 to} R ₁₀ described above may be further substituted with another substituent.

Examples of the other substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and aryloxy such as p-tolyloxy group. 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 Groups such as acyl groups, methylsulfanyl groups, tert-butylsulfanyl groups and other alkylsulfanyl groups, phenylsulfanyl groups, p-tolylsulfanyl groups and other arylsulfanyl groups, methylamino groups, cyclohexylamino groups and other alkylamino groups, dimethyl Dialkylamino groups such as amino group, diethylamino group, morpholino group and piperidino group, phenylamino group, arylamino groups such as p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group, phenyl Group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, aryl group such as phenanthryl group, benzofuranyl group, heterocyclic group such as furyl group and thienyl group, hydroxy group, carboxy group, formyl group Group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethyl group Examples thereof include a sulfoniumyl group and a triphenylphenacylphosphoniumyl group.

The most preferable structure of the photopolymerization initiator (D2) includes compounds represented by the following formulas (D2-1) and (D2-2).
Chemical formula (D2-1)

Formula (D2-2)

The content of the photopolymerization initiator (D2) is preferably 1 to 50 parts by mass and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the colorant (A).

The photopolymerization initiators (D1, D2) are oxime ester photopolymerization initiators. The oxime ester-based photopolymerization initiator decomposes an oxime ester portion by absorbing ultraviolet rays to generate an iminyl radical and an alkyloxy radical, and the radical of an active species generated by the decomposition causes a reaction. Since the photosensitive coloring composition of the present specification contains the photopolymerization initiator [D1, D2], the decomposition efficiency by light irradiation is very high, and a pattern can be formed with a small exposure amount (high sensitivity). ..
The inventor believes that the photopolymerization initiators (D1, D2) have higher sensitivity than other photopolymerization initiators as follows.
(1) By having the structure represented by the general formula (4) or the general formula (5), light energy can be efficiently absorbed. Furthermore, it is speculated that the obtained light energy is efficiently utilized for the decomposition of the oxime ester site, whereby the decomposition by light irradiation is fast and a large amount of radicals are instantly generated.
(2) The photopolymerization initiators (D1 and D2) are derived from the structure represented by the general formula (4) or the general formula (5) because the decomposition of iminyl radicals generated by light irradiation into radicals of active species I'm guessing it's very fast. If the generated iminyl radicals are metastable, the decomposition is slow and the amount of active radicals generated is small. The photopolymerization initiator (D1) has a structure represented by the general formula (4) or the general formula (5). It is speculated that the decomposition of the iminyl radical generated by the decomposition by light irradiation is very fast and a large amount of radical is generated. Further, the photopolymerization initiators (D1, D2) are considered to suppress the recombination of radicals because the decomposition of iminyl radicals is very fast. When the number of recombination of radicals is large, the number of active species generated by the decomposition is reduced, so that the function as a radical polymerization initiator is reduced.

The photopolymerizable initiator (D) can contain other photopolymerizable initiators other than the photopolymerization initiators (D1) and (D2).
Other photopolymerizable initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one. , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or acetophenone-based compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone compounds such as -4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone or 2,4-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 ,4-trichloromethyl-(4'-methoxystyryl)-6-triazine and other triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O- Benzoyl oxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), JP2011-209710A. , JP 2012-145721 A, JP 2012-177826 A, etc.; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide. And phosphine-based compounds; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; titanocene-based compounds. Among these, acetophenone-based initiators are preferable.

Other commercially available photopolymerizable initiators are "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) manufactured by BASF Japan Ltd., "IRGACURE 369". (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), "IRGACURE 379" 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butan-1-one and the like can be mentioned.

<Sensitizer (F)>
The photosensitive coloring composition of the present invention may further contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone. Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyllin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy Ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'. -Tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like can be mentioned. In addition, "Dye Handbook" edited by Shin Okawara et al. (1986, Kodansha), "Chemistry of Functional Dyes" edited by Shin Okawara (1981, CMC), edited by Chuzaburo Ikemori et al., and "Special Functional Materials" (1986). Year, CMC) sensitizers described in.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferable. 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 and the like are more preferable.

Commercially available sensitizers include "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone manufactured by Chemchemical Chemical). Can be mentioned.

The sensitizers can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerizable initiator (D). When contained in an appropriate amount, photocurability and developability are further improved.

<Thiol chain transfer agent>
The photosensitive coloring composition of the present invention may contain a chain transfer agent. The chain transfer agent is preferably a thiol chain transfer agent. When the thiol chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is less susceptible to polymerization inhibition by oxygen is generated during radical polymerization after irradiation with light, and the sensitivity of the photosensitive coloring composition is improved.

The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has 4 or more SH groups. As the number of functional groups increases, photo-curing becomes easier from the surface of the film to the deepest part.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , 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-dibutylamino)-4,6-dimercapto-s-triazine And the like, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and the like.

The thiol chain transfer agents can be used alone or in combination of two or more kinds.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, and more preferably 2.0 to 8.0% by mass in the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, photosensitivity and pattern shape are further improved.

<Polymerization inhibitor>
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor. This prevents exposure to light due to diffracted light from the mask during exposure and facilitates obtaining a good pattern shape.

The polymerization inhibitor is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl. Catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert -Butylcatechol, alkyl catechol compounds such as 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 , 5-di-tert-butylhydroquinone and other alkylhydroquinone compounds, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide and the like Examples thereof include phosphine oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in the nonvolatile content of the photosensitive coloring composition. If contained in an appropriate amount, it becomes easy to obtain a good pattern shape.

<Ultraviolet absorber>
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, salicylate compounds, and the like.

Examples of the benzotriazole compound include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 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% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1 -Dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and straight chain alkyl esters, 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 Reaction product of -(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 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-benzotriazol-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.

Commercially available products of benzotriazole compounds are TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF, and Adeka Stab LA-29, LA-31RG, LA manufactured by ADEKA. -32, LA-36, Kemipro Chemical Co., Ltd. KEMISORB71, 73, 74, 79, 279, Otsuka Chemical Co., Ltd. RUVA-93, etc. are mentioned.

The triazine-based compound is, for example, 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 Phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate reaction product, 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)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- Examples include tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products of triazine compounds are KEMISORB 102 manufactured by Chemipro Kasei Co., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, ADEKA ADEKA STAB LA-46, LA-F70, and CYASORB UV-1164 manufactured by Sun Chemical. Etc.

Examples of the benzophenone compound include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature and 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 Examples thereof include siloxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

Examples of commercially available benzophenone compounds include KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., SEESORB 101, 107 manufactured by Sipro Kasei Co., Adeka Stub 1413 manufactured by ADEKA, UV-12 manufactured by Sun Chemical Co., Ltd., and the like.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like.

The content of the ultraviolet absorber is preferably 5 to 70 mass% in the total 100 mass% of the photopolymerizable initiator (D) and the ultraviolet absorber. If contained in an appropriate amount, a good pattern shape can be easily obtained. When the photosensitive coloring composition contains the sensitizer (F), the content of the photopolymerizable initiator (D) includes the content of the sensitizer (F).

Further, the total content of the photopolymerizable initiator (D) and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion of the coating film to the substrate is further improved, and good sensitivity is easily obtained.

<Antioxidant>
The photosensitive coloring composition of the present invention can contain an antioxidant. As for the antioxidant, the photopolymerization initiator and the thermosetting compound contained in the photosensitive coloring composition can prevent yellowing due to oxidation due to a thermal process at the time of thermosetting or ITO annealing, and can suppress a decrease in transmittance of the coating film. .. In particular, when the colorant concentration of the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) decreases relatively. Therefore, it is necessary to increase the amount of the photopolymerization initiator or to mix the thermosetting compound to form a film. Easily turns yellow. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a decrease in the transmittance of the film can be suppressed.

The antioxidant is a compound having a radical scavenging function or a peroxide decomposition function. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds and hydroxyamine compounds. The antioxidant is preferably a compound containing no halogen atom.

The hindered phenol compound is, for example, 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), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy) Phenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10 -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-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,3) 5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-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 ,6-Dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol. Etc.

Commercially available products are ADEKA's ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, Kemipro's KEMINOX 101, 179, 76, 9425, BASF's. IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sianox CY-1790, CY-2777 and the like manufactured by Sun Chemical Co.

Examples of the hindered amine compound include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate and tetrakis(2,2,6,6-tetramethyl). -4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl -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, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-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-2,2,6,6-tetramethyl-1-piperidine ethanol and 3,5,5 -Ester of trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}- 1,3,5-Triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-decanedioate Piperidinyl) ester, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyrididyl)[[3,5-bis(1,1dimethylethyl )-4-Hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridyridyl 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-he Xamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. Can be mentioned.

Commercially available products are ADEKA's ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-. 402F, LA-502XP, KAMISTAB29, 62, 77, 94 made by Chemipro Kasei Co., Tinuvin249 made by BASF, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3529, UV-3853 made by Sun Chemical Co., etc. Can be mentioned.

Examples of phosphorus compounds include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and 2,2′-methylenebis(4,6-diphenylphosphite. -T-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropyi Redene 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'isopropyi Ridenediphenol alkyl phosphite, trisnonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl) pentaerythritol diphosphite, di(nonyl phenyl) ) Pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-Methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbisphosphite(2,4) -Ditert-butyl-6-methylphenyl) and the like.

Commercially available products include ADEKA's ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF's IRGAFOS 168, Clariant Chemicals' Hosta nox P-EPQ and the like.

Examples of sulfur compounds include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate] and 3,3′-thiobis. Ditridecyl propionate, 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 can be mentioned.

Commercially available products include ADEKA's ADEKA STAB AO-412S, AO-503, ChemiPro Chemical's KEMINOX PLS, and the like.

The antioxidants may be used alone or in admixture of two or more.

The content of the antioxidant is preferably 0.5 to 5.0% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition. This further improves the transmittance, the spectral characteristics, and the sensitivity.

<Leveling agent (K)>
The photosensitive coloring composition of the present invention may contain a leveling agent. This further improves the wettability of the transparent substrate and the drying property of the film when the film is formed. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants and anionic surfactants.

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

Commercial products of silicone-based surfactants are BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370 manufactured by BYK Chemie. 377, 378, 3455, UV3510, 3570, Toray Dow Corning 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, KP-341 and the like.

The fluorosurfactant is a compound having a fluorocarbon chain.

Commercially available products of the fluorine-based surfactant are Surfon S-242, S-243, S-420, S-611, S-651, S-386, and DIC Megafac F-253, F manufactured by AGC Seimi Chemical Co., Ltd. -477, 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, Sumitomo 3M FC-4430, FC-4432, Mitsubishi Materials Electronics Co., Ltd. EF-PP31N09, EF-PP33G1, EF-PP32C1, and Neos Futgent 602A.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene mysteryl ether, polyoxyethylene octyl. Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene tetraoleate Sorbit, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples thereof include alkanolamide and alkyl imidazoline.

Commercial products of nonionic surfactants are Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV manufactured by Kao Corporation. 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, Rheodor 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), Amate 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA manufactured by ADEKA Pluronic L-23, 31, 44, 61, 62,. 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based copolymer Polyflow No. 75, No. 90, No. 95 and the like.

Examples of the cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Examples of commercially available cationic surfactants include Acetamine 24, Coatamine 24P, 60W, and 86P Conk manufactured by Kao Corporation.

Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanol lauryl sulfate. Examples thereof include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester.

Examples of commercially available anionic surfactants include Fusegent 100 and 150 manufactured by Neos, ADEKA HOPE YES-25 manufactured by ADEKA, ADEKA COL TS-230E, PS-440E, and EC-8600.

Examples of the amphoteric surfactant include lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkyl betaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Commercially available amphoteric surfactants include Amohthol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B and 20N manufactured by Kao Corporation.

The surfactants may be used alone or in admixture of two or more.

The content of the surfactant is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass% in the nonvolatile content of the photosensitive coloring composition. Within this range, the balance between the coating property of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

<Storage stabilizer>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include organic acids such as benzyl trimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, oxalic acid and its methyl ether, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples include phosphine and phosphite.

The content of the storage stabilizer is preferably 0.1 to 10 mass% with respect to 100 mass parts of the colorant (A).

<Adhesion improver>
The photosensitive coloring composition of the present invention may contain an adhesion improver. This further improves the adhesion between the coating and the substrate. Further, it becomes easy to form a pattern having a narrow width by the photolithography method. Examples of the adhesion improver include silane coupling agents and the like.

Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- Aminosilanes such as dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, and bis(triethoxysilylpropyl)tetrasulfide. Isocyanates such as sulfides and 3-isocyanatopropyltriethoxysilane may be mentioned.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the coating film is further improved, and the resolution of the pattern is further improved.

<Solvent>
The photosensitive coloring composition of the present invention can contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, and thus it is easy to form a film having a smooth surface. The solvent may be appropriately selected according to the purpose of use and may contain an appropriate amount.

The solvent is, for example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), an 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 (containing OH in the molecule, -O -, -CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, 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, butyric acid. Examples include butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

The ether solvent is, for example, 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, propylene glycol monoethyl ether. 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, diethylene glycol methyl Examples thereof include ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetole, and methylanisole.

The ether ester solvent includes, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxypropionate. Ethyl ethoxypropionate, 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 Examples thereof include monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and dipropylene glycol diacetate.

The ketone solvent is, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, Examples include isophorone.

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.

Among these, a solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm is preferable in terms of coating properties and drying properties. For example, 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 more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are further preferable.

The solvent may be used alone or in combination of two or more.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition of the present invention is subjected to dispersion treatment using, for example, the colorant (A) and the dispersant (E) to prepare a colorant (A) dispersion. Then, the colorant (A) dispersion, the binder resin (B), the photopolymerizable compound (C), and the photopolymerizable initiator (D) can be mixed to prepare.

For the dispersion treatment, a dispersion device 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 can be used.

<Removal of coarse particles>
In the present invention, it is preferable to remove coarse particles contained in the dispersion of the colorant (A) or after preparing the photosensitive coloring composition. As a result, foreign matter can be removed from the coating, which facilitates formation of a fine pattern.
The removal is preferably performed by a method such as centrifugation, a sintering filter, a membrane filter, or the like. This makes it possible to remove foreign matter such as coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more. Thus, the photosensitive coloring composition preferably contains substantially no particles of 0.5 μm or more, and preferably contains no particles of 0.3 μm or less.

<Color filter>
The color filter in the present invention includes a base material (also referred to as a transparent substrate) and a filter segment formed from the photosensitive coloring composition of the present invention. The color filter segment (hereinafter, also referred to as a filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (A) to be used. Further, the color filter can further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment as the color filter segment. A reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include those using an aluminum electrode or a metal thin film as reflective noodles.

<Method of manufacturing color filter>
In the color filter, it is preferable to first form the black matrix on the substrate and then form the filter segment. The black matrix can be formed after forming a thin film transistor (TFT) on the substrate in advance.
Examples of the black matrix include chromium, a chromium/chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light shielding agent is dispersed.

The filter segment can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
In the printing method, a pattern can be formed simply by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, and therefore, as a method for producing a color filter, it is low in cost and excellent in mass productivity. Furthermore, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. In addition, it is important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

In the electrodeposition method, a transparent conductive film formed on a transparent substrate is used, and a filter segment of each color is electrodeposited on the transparent conductive film by electrophoresis of colloidal particles to form a color filter. In the transfer method, a filter segment is formed on the release-treated surface of the release sheet. Next, this filter segment is transferred and produced on a transparent substrate.

In the photolithography method, for example, a photosensitive coloring composition containing a colorant having a certain color tone is applied on a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained coating (hereinafter referred to as the first coating) is exposed (light irradiation) through a mask having a predetermined pattern. Then, the resultant is dipped in a solvent or an alkaline developing solution or sprayed with a developing solution to perform development, and the uncured portion is removed to obtain a desired pattern. By performing this step in the same manner using a photosensitive coloring composition having a colorant of another color tone, a color filter having filter segments of each color can be manufactured. Further, a second coating (oxygen blocking film) can be formed on the first coating before exposure by using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first coating does not come into contact with oxygen, so that the exposure sensitivity is further improved. The color filter may also be heated to cure the uncured photopolymerizable compound in the filter segment. Note that the photolithography method is preferable because it can manufacture a color filter with higher accuracy than the printing method.

Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying step can be performed during the coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkali developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; organic alkalis such as dimethylbenzylamine and triethanolamine. Further, a defoaming agent or a surfactant can be added to the developer.

In the present specification, the color filter is formed by, after forming the filter segment, adhering it to the counter substrate with a sealant, injecting liquid crystal from the injection port provided in the sealing portion, and then sealing the injection port, and if necessary, a polarizing film. A liquid crystal display device can be manufactured by laminating a retardation film or a retardation film on the outside of the substrate. This liquid crystal display device is, for example, Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Alignment (VA), Optically Convenient Bend ( OCB) and the like.

In this specification, the color filter can be used for applications such as a solid-state imaging device, an organic EL display device, a quantum dot display device, and electronic paper, in addition to a liquid crystal display device.

<Liquid crystal display>
The liquid crystal display device of the present specification includes a color filter.
A liquid crystal display device includes the color filter of the present invention and a light source. The light source may be, for example, a cold cathode fluorescent lamp (CCFL) or a white LED, but in the present invention, it is preferable to use the white LED because the red reproduction area is widened. FIG. 1 is a schematic cross-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 facing each other with a space therebetween, and a liquid crystal LC is sealed between them.

The liquid crystal LC is oriented 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). A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on the TFT array 12. An alignment layer 14 is provided on the transparent electrode layer 13. 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 forming the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed so as to cover the color filter 22, a transparent electrode layer 23 made of, for example, ITO is further formed thereon, and an alignment layer 24 is formed so as to cover the transparent electrode layer 23. Is provided.

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

The white LED light source includes, for example, one in which a fluorescent filter is formed on the surface of a blue LED, and one in which a phosphor is contained in a resin package of the blue LED, and a wavelength at which the emission intensity becomes maximum in the range of 430 nm to 485 nm. (Λ3), a wavelength (λ4) having a maximum emission intensity in the range of 530 nm to 580 nm, a wavelength (λ5) having a maximum emission intensity in the range of 600 nm to 650 nm, and The ratio (I4/I3) of the emission intensity I3 at the wavelength λ3 and 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 and the emission intensity I5 at the wavelength λ5 (I5/ I3) is a white LED light source (LED1) having a spectral characteristic of 0.1 or more and 1.3 or less, or a wavelength (λ1) that maximizes the emission intensity within a range of 430 nm to 485 nm, and a wavelength of 530 nm to 580 nm. A spectrum having a peak wavelength (λ2) of the second emission intensity within the range and a ratio (I2/I1) of the emission intensity I1 at the wavelength λ1 and the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less. A characteristic white LED light source (LED2) is preferred.

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 Corporation) and NSSW304D (manufactured by Nichia Corporation).

The present invention will be described below with reference to examples. In addition, "part" and "%" in an Example represent a "mass part" and "mass %", respectively.

Weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), amine value (mgKOH/g), ammonium salt relating to resins such as binder resins, resin-type dispersants, and resins for forming dye salts The values (mgKOH/g) are as follows.

<Weight average molecular weight (Mw), number average molecular weight (Mn)>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as a device, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used in a double connection for both packing materials, with an oven temperature of 40. The temperature was measured at a temperature of 0.35 ml/min using a THF solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in an amount of 20 microliters. All molecular weights are polystyrene equivalent values.

<Acid value (mgKOH/g)>
To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to be uniformly dissolved, and a 0.1 mol/L KOH aqueous solution was used as a titration liquid to prepare an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.). ) Was used to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Amine value (mgKOH/g)>
The amine value is a value obtained by converting the measured total amine value (mgKOH/g) into solid content according to the method of ASTM D 2074.

<Ammonium salt value (mgKOH/g)>
The ammonium salt value is a value obtained by titrating with an aqueous solution of 0.1N silver nitrate using a 5% potassium chromate aqueous solution as an indicator, and then converted into the equivalent of potassium hydroxide, and represents the ammonium salt value of the nonvolatile content.

<Preparation of micronized pigment>
<Method for producing organic pigment (A1)>
(Base compound)
The base compounds ([B-1] to [B-5]) used this time are shown in Table 1.

(Production of coupler compound [C-1])

After mixing 167 parts of 3-hydroxy-2-naphthoic acid, 1500 parts of tetrahydrofuran and 1 part of N,N-dimethylformamide, 221 parts of thionyl chloride was added, and the mixture was stirred at room temperature for 1 hour to give a carboxylic acid chloride solution. Obtained. Separately, a solution prepared by mixing 1000 parts of N-methylpyrrolidone and 48 parts of 1,3-phenylenediamine was prepared, and the carboxylic acid chloride solution was added dropwise to this solution over 30 minutes. At this time, dropping was performed while maintaining the temperature of the reaction solution at 10° C. or lower. After completion of dropping, the mixture was stirred at room temperature for 2 hours, and the precipitated reaction product was collected by filtration to obtain the target product. Further, by washing with 1000 parts of methanol and drying under reduced pressure, 196 parts of coupler compound [C-1] (yield 98.5%) was obtained.

(Production of coupler compounds [C-2] to [C-17])
In place of 48 parts of 1,3-phenylenediamine used in the production of the coupler compound [C-1], diamines described in Table 2 were used, except that the mass parts were changed. The same operation was performed to produce coupler compounds [C-2] to [C-17].

(Production of Azo Pigment 1)
After adding 169 parts of the base compound [B-1] to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added, and the mixture was cooled to −2 to 0° C. After adding 208 parts of 25% sodium nitrite aqueous solution to this solution, it was stirred for 30 minutes while maintaining it at 0 to 5°C to prepare a diazonium solution. Separately, a coupler solution consisting of 167 parts of the coupler compound [C-1], 316 parts of a 25% sodium hydroxide solution, and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise to 1000 parts of an acetate buffer solution having a pH of 5.4 for 10 minutes. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes and further stirred at 80° C., the precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 337 parts of azo pigment 1 (yield: 98.1%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 1.

Azo pigment 1

(Production of Azo Pigment 2)
Azo pigment 1 was prepared in the same manner as in Azo pigment 1 except that 181 parts of base compound [B-2] was used instead of 169 parts of base compound [B-1] used in manufacture of azo pigment 1. 340 parts (yield: 95.6%) of 2 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 2.

Azo pigment 2

(Production of Azo Pigment 3)
Azo pigment 1 was prepared in the same manner as in Azo pigment 1 except that 128 parts of base compound [B-3] was used instead of 169 parts of base compound [B-1] used in manufacture of azo pigment 1. 296 parts (yield: 97.9%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 3.

Azo pigment 3

(Production of Azo Pigment 4)
Azo pigment 1 was prepared in the same manner as in Azo pigment 1 except that 187 parts of base compound [B-4] was used instead of 169 parts of base compound [B-1] used in manufacture of azo pigment 1. 4 was obtained (357 parts, yield: 98.9%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 4.

Azo pigment 4

(Production of Azo Pigment 5)
Azo pigment 2 was produced in the same manner as in Azo pigment 2 except that 172 parts of coupler compound [C-3] was used instead of 167 parts of coupler compound [C-1] used in the manufacture of azo pigment 2. 352 parts of 5 was obtained (yield: 97.6%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 5.

Azo pigment 5

(Production of Azo Pigment 6)
Azo pigment 2 was prepared in the same manner as in Azo pigment 2 except that 167 parts of coupler compound [C-4] was used instead of 167 parts of coupler compound [C-1] used in the manufacture of azo pigment 2. 6 was obtained (353 parts, yield: 95.0%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 6.

Azo pigment 6

(Production of Azo Pigment 7)
The same operation as in the production of Azo Pigment 2 was carried out except that 197 parts of the coupler compound [C-5] was used instead of 167 parts of the coupler compound [C-1] used in the production of azo pigment 2. 379 parts of 7 (yield: 98.4%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 7.

Azo pigment 7

(Production of Azo Pigment 8)
An azo pigment was prepared in the same manner as the azo pigment 2 except that 190 parts of the coupler compound [C-6] was used instead of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 2. 368 parts (yield: 97.3%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 8.

Azo pigment 8

(Production of Azo Pigment 9)
The same operation as in the production of Azo Pigment 2 was performed, except that 189 parts of the coupler compound [C-7] was used instead of 167 parts of the coupler compound [C-1] used in the production of azo pigment 2. 373 parts (yield: 98.8%) of 9 was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 9.

Azo pigment 9

(Production of Azo Pigment 10)
Azo pigment 1 was prepared in the same manner as in Azo pigment 1 except that 197 parts of coupler compound [C-2] was used instead of 167 parts of coupler compound [C-1] used in manufacture of azo pigment 1. 390 parts (yield: 98.7%) of 10 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 10.

Azo pigment 10

(Production of Azo Pigment 11)
An azo pigment was prepared in the same manner as in the production of the azo pigment 10 except that 181 parts of the base compound [B-2] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 10. 397 parts (yield: 97.4%) of 11 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 11 was identified.

Azo pigment 11

(Production of Azo Pigment 12)
The azo pigment was prepared in the same manner as in the production of the azo pigment 10 except that 128 parts of the base compound [B-3] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 10. 337 parts (yield: 95.2%) of 12 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 12.

Azo pigment 12

(Production of Azo Pigment 13)
The azo pigment was prepared in the same manner as in the production of the azo pigment 10 except that 190 parts of the base compound [B-5] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 10. 405 parts (yield: 97.4%) of 13 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 13 was identified.

Azo pigment 13

(Production of Azo Pigment 14)
The same operation as in the production of Azo Pigment 2 was carried out except that 195 parts of the coupler compound [C-8] was used instead of 167 parts of the coupler compound [C-1] used in the production of azo pigment 2. 14 was obtained in an amount of 375 parts (yield: 97.7%). As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 14 was identified.

Azo pigment 14

(Production of Azo Pigment 15)
The same operation as in the production of Azo Pigment 2 was carried out except that 263 parts of the coupler compound [C-9] was used instead of 167 parts of the coupler compound [C-1] used in the production of azo pigment 2. 437 parts of 15 (yield: 96.9%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 15.

Azo pigment 15

(Production of Azo Pigment 16)
The same operation as in the production of Azo Pigment 2 was performed, except that 201 parts of the coupler compound [C-10] was used instead of 167 parts of the coupler compound [C-1] used in the production of Azo Pigment 2, thereby producing an azo pigment. 382 parts (yield: 98.1%) of 16 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 16.

Azo pigment 16

(Production of Azo Pigment 17)
Azo pigment 2 was prepared in the same manner as in Azo pigment 2 except that 207 parts of coupler compound [C-11] was used instead of 167 parts of coupler compound [C-1] used in manufacture of azo pigment 2. 383 parts (Yield: 96.9%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 17.

Azo pigment 17

(Production of Azo Pigment 18)
The same operation as in the production of Azo Pigment 2 was carried out except that 206 parts of the coupler compound [C-12] was used instead of 167 parts of the coupler compound [C-1] used in the production of Azo Pigment 2, thereby producing an azo pigment. 183 parts (yield: 97.3%) of 18 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 18 was identified.

Azo pigment 18

(Production of Azo Pigment 19)
An azo pigment was prepared in the same manner as the azo pigment 2 except that 212 parts of the coupler compound [C-15] was used instead of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 2. 195 parts (yield: 98.7%) of 19 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as Azo Pigment 19.

Azo pigment 19

(Production of Azo Pigment 20)
Azo pigment 2 was prepared in the same manner as in Azo pigment 2 except that 211 parts of coupler compound [C-16] was used instead of 167 parts of coupler compound [C-1] used in the manufacture of azo pigment 2. 390 parts (yield: 97.7%) of 20 were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 20 was identified.

Azo pigment 20

(Production of Azo Pigment 21)
The same operation as in the production of Azo Pigment 2 was carried out except that 237 parts of the coupler compound [C-17] was used instead of 167 parts of the coupler compound [C-1] used in the production of azo pigment 2. 21 was obtained in 409 parts (yield: 96.0%). As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 21 was identified.

Azo pigment 21

(Production of Azo Pigment 22)
The same operation as in the production of Azo Pigment 2 was performed, except that 229 parts of the coupler compound [C-13] was used instead of 167 parts of the coupler compound [C-1] used in the production of Azo pigment 2. 22 was obtained in 400 parts (yield: 95.8%). As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 22 was identified.

Azo pigment 22

(Production of Azo Pigment 23)
Azo pigment 2 was prepared in the same manner as in Azo pigment 2 except that 241 parts of coupler compound [C-14] was used instead of 167 parts of coupler compound [C-1] used in manufacture of azo pigment 2. 423 parts (yield: 98.4%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 23 was identified.

Azo pigment 23

(Production of A1-1) Micronization of azo pigment 80 parts of azo pigment 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 6 hours. , Salt milled. The resulting kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. , 78 parts of finely divided pigment (A1-1) was obtained.

(Production of A1-2 to 23) Micronization of azo pigment Finely divided pigments A1-2 to A1-2 in the same manner as in the production of A1-1 except that the azo pigments shown in Table 3 are used instead of the azo pigment 1. I got 23.

(Production of A1-24 to 39)
Azo compounds 1 to 16 shown in Table 4 were obtained based on the description of JP-A-2013-161026. Furthermore, the salt milling treatment of the same publication was performed to obtain finely divided pigments (A1-24 to 39) of azo compounds 1 to 16.

(Production of micronized pigment (A2-1))
100 parts of the brominated diketopyrrolopyrrole pigment of the following formula (101), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 80° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80° C. for one day and pulverized. As a result, 96.9 parts of finely divided pigment (A2-1) having a diketopyrrolopyrrole pigment was obtained. The average primary particle diameter was 33.1 nm.

Chemical formula (101)

(Production of finely divided pigment (A2-2))
The brominated diketopyrrolopyrrole pigment of formula (101) was prepared using commercially available C.I. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals), and the same diketopyrrolopyrrole micronized pigment (A2-) as in the production of micronized pigment (A2-1). 2) 97.3 parts were obtained. The average primary particle diameter was 34.2 nm.

(Production of finely divided pigment (A2-3))
C. I. Pigment Red 242 (“Novopalm Scarlet 4RF” manufactured by Clariant Co., Ltd.) 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and the solvent, and then 80 It was dried at ℃ for 1 day to obtain a finely divided pigment (A2-3). The average primary particle diameter was 35.2 nm.

(Production of finely divided pigment (A2-4))
Anthraquinone red pigment C.I. I. Pigment Red 177 (“Chlomophthal Red A2B” manufactured by Ciba Specialty Chemicals): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and at 120° C. for 8 hours. Kneaded Next, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating at 70°C to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. Then, a finely divided pigment (A2-4) was obtained. The average primary particle diameter was 34.5 nm.

(Production of finely divided pigment (A2-5))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (“Pariotor Yellow K0961HD” manufactured by BASF), 800 parts of crushed salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 4 hours. This mixture was poured into 3000 parts of warm water and stirred at a high speed mixer for about 1 hour while heating to about 80°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then at 80°C for 24 hours. After drying, 98 parts of finely divided pigment (A2-5) was obtained.
The average primary particle diameter was 34.3 nm.

(Production of finely divided pigment (A2-6))
Isoindoline yellow pigment C.I. I. Pigment yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Specialty Chemicals), 1600 parts of sodium chloride, and 190 parts of diethylene glycol are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and the temperature is 60° C. It was kneaded for 10 hours. Next, this mixture was poured into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and the solvent, and then 80 It was dried at ℃ for 1 day to obtain a finely divided pigment (A2-6). The average primary particle diameter was 34.6 nm.

(Production of micronized pigment (A2-7))
100 parts of a metal complex yellow pigment (CI pigment yellow 150, “Yellow Pigment E4GN” manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), Kneading was performed at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and the solvent, and then 80 The mixture was dried at ℃ for 1 day to obtain a finely divided pigment (A2-7). The average primary particle size was 36.6 nm.

(Production of finely divided pigment (A2-8))
Yellow pigment C.I. I. Pigment Yellow 185 (“” manufactured by Ciba Japan) (“Pariotor Yellow D1155” manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) The mixture was charged and kneaded at 120° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. 490 parts of micronized pigment (A2-8) was obtained. The average primary particle diameter was 35.9 nm.

<Production of finely divided pigments (A2-9 to 11)>
The following quinophthalone compounds (a) to (c) were obtained according to the synthetic method described in JP 2012-226110 A.

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60° C. for 6 hours, and subjected to salt milling treatment. The resulting kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight. , 98 parts of a finely divided pigment (A2-9) was obtained. The average primary particle diameter was 31.3 nm.

100 parts of quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for one day. 98 parts of finely divided pigment (A2-10) was obtained. The average primary particle diameter was 31.1 nm.

100 parts of the quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product was poured into warm water, stirred for 1 hour while heating to about 70° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for one day. 97 parts of finely divided pigment (A2-11) was obtained. The average primary particle diameter was 34.1 nm.

Table 5 shows the relationship between the finely divided pigment number and its type.

<Method for producing dye (a)>
Resin 1 having a cationic group in the following side chain and each dye were used to produce a resin salt-forming product of the dye.
(Resin 1 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile). (6) and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more based on the nonvolatile content, and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. Methyl chloride (3.2 parts) and ethanol (22.0 parts) were added thereto, reacted at 50°C for 2 hours, heated to 80°C over 1 hour, and further reacted for 2 hours. In this manner, Resin 1 having a cationic group in the side chain of which the resin component has 47% by mass of ammonium group was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Other colorants (dye 1: AS-1))
The resin 1 having a cationic group in the side chain of 30 parts in terms of nonvolatile content was added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise to the resin solution. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution onto a filter paper and deciding the end point when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and C.I. I. A colorant (dye 1: AS-1), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in its side chain, was obtained. At this time, C.I. in the colorant (dye 1) was used. I. The content of the effective pigment component derived from Acid Red 52 was 25% by mass.

(Other colorants (dye 2: AS-2))
C. I. Acid Red 52 to C.I. I. Acid Red 289, except that the colorant (dye 1) was prepared in the same manner as in C.I. I. A colorant (dye 2: AS-2), which is a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in its side chain, was obtained. At this time, C.I. in the colorant (dye 2) was used. I. The content of the effective pigment component derived from Acid Red 289 was 27% by mass.

(Other colorants (dye 3: AS-3))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, C.I. I. Basic Violet 10 (BV10: Tadamine Chemical Co., Ltd.: Rodamine B) 5.0 parts and hydroxyethyl methacrylate (HEMA) 1.6 parts were dissolved in 40 ml of dichloromethane to prepare 1-(3-dimethylaminopropyl)-3-ethyl. 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added, and the mixture was stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and then purified with a silica gel column to obtain a colorant (dye 3: AS-3).

<Dye derivative>
The following dye derivatives were used.

Dye derivative (1)

Dye derivative (2)

Dye derivative (3)

Dye derivative (4)

<Acidic dispersant: E1>
(Acidic dispersant: Synthesis of E1-1)
A reaction vessel equipped with a gas inlet tube, temperature, condenser, and 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, 50 parts of propylene glycol monomethyl ether acetate, and nitrogen gas. Replaced with.
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 reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2′-azobisisobutyronitrile in 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by the non-volatile matter measurement that 95% had reacted.
19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was heated at 100°C. The reaction was carried out 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 so that the nonvolatile content would be 30%. A resin type dispersant (E1-1) having a valence of 70 mgKOH/g and a mass average molecular weight of 8500 was obtained.

(Acidic dispersant: Synthesis of E1-2)
In a reaction vessel equipped with a gas introduction 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 KK), ETERACOLLL OXMA ( 20 parts of Ube Industries, Ltd.) 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 of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol was added. And reacted for 10 hours. It was confirmed by the non-volatile matter measurement that 95% had reacted. Next, BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (manufactured by JFE Chemical Co.) 39 parts, C-1015N (bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N( Hydroxyl value 112 mg KOH/g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, and 1,8-diazabicyclo-[5.4.0]-7-undecene 0.40 part as a catalyst. It was added and reacted at 100° C. for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The non-volatile content was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain a resin type dispersant (E1-2) liquid having an acid value of 94 mgKOH/g and a mass average molecular weight of 25,000.

(Acidic dispersant: Synthesis of E1-3)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone, 0.01 parts of mono-n-butyltin(IV) oxide was charged and 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 reacted for 10 hours. It was confirmed by the solid content measurement that the polymerization proceeded 95%, and the reaction was terminated. After the reaction was completed, the non-volatile content was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain a resin type dispersant (E1-3) liquid having a mass average molecular weight of 9,500.

(Acidic dispersant: Synthesis of E1-4)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc (methoxypropylacetate), and 0.2 parts of monobutyltin oxide as a catalyst. Was charged, the atmosphere was replaced with nitrogen gas, and the mixture was reacted at 120° C. for 5 hours (first step). It was confirmed by acid value measurement 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 nonvolatile 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 acrylate. Parts, methacrylic acid 50 parts, and PGMAc 663 parts were charged, the inside of the reaction vessel was heated to 80° C., and 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added and reacted for 12 hours. (Second step). It was confirmed by the non-volatile matter measurement that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate and 0.1 part of hydroquinone were charged, and IR of 2270 cm −1 based on the isocyanate group was used. The reaction was carried out until the disappearance of the peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the nonvolatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (E1-3) solution having a nonvolatile content of 30%. The obtained dispersant had an acid value of 68, an unsaturated double bond equivalent of 1593 and a mass average molecular weight of 13,000.

[Production of Vinyl-Based Resin Dispersant (E2) Having Piperidyl Skeleton]
(Production of Vinyl Resin Dispersant (E2-1) Having Piperidyl Skeleton)
A reaction tank equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of propylene glycol monomethyl ether acetate, and the temperature was raised to 110° C. while substituting with nitrogen. In a dropping tank, 120 parts of tetramethylpiperidyl methacrylate (Fancrylic FA-712HM manufactured by Hitachi Chemical Co., Ltd.), 70 parts of methyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 61 parts of propylene glycol monomethyl ether acetate, and 2,2'- 6 parts of azobis(2,4-dimethylvaleronitrile) was charged, and the mixture was stirred until it became uniform, then added dropwise to the reaction tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. A non-volatile content of 30% was adjusted with propylene glycol monomethyl ether acetate, and a vinyl-based resin dispersant (E2-1) having a piperidyl skeleton with an amine value per non-volatile content of 145 mgKOH/g and a number average molecular weight of 3,500 (Mn). A liquid was obtained.

(Production of Vinyl Resin Dispersant (E2-2) Having Piperidyl Skeleton)
A reaction tank equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of propylene glycol monomethyl ether acetate, and the temperature was raised to 110° C. while substituting with nitrogen. 80 parts of pentamethylpiperidyl methacrylate (Fancryl FA-711MM manufactured by Hitachi Chemical Co., Ltd.), 100 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of propylene glycol monomethyl ether acetate, and 2,2'- in a dropping tank. 6 parts of azobis(2,4-dimethylvaleronitrile) was charged, and the mixture was stirred until it became uniform, then added dropwise to the reaction tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. A non-volatile content of 30% is adjusted with propylene glycol monomethyl ether acetate, and a vinyl-based resin dispersant (E2-2) having a piperidyl skeleton having an amine value per non-volatile content of 91 mgKOH/g and a number average molecular weight of 3,800 (Mn). A liquid was obtained.

(Production of Vinyl Resin Dispersant (E2-3) Having Piperidyl Skeleton)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and flushed with nitrogen. While stirring at 50° C. for 1 hour, the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride and 133 parts of methoxypropyl acetate were charged and heated to 110° C. under a nitrogen stream to polymerize the first block (B block). Started. After the polymerization for 4 hours, the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the nonvolatile content.
Next, 61 parts of methoxypropylacetate and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate as a second block (A block) monomer (Fancryl manufactured by Hitachi Chemical Co., Ltd.) were added to the reactor. (FA-711MM) was added, and the mixture was stirred while maintaining a nitrogen atmosphere at 110° C. to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled to measure the nonvolatile content, and the polymerization conversion rate of the second block (A block) was 98 when calculated from the nonvolatile content. %, and the reaction solution was cooled to room temperature to terminate the polymerization.
In this way, a vinyl-based resin-type dispersant having a piperidyl skeleton having an amine value per nonvolatile component of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn) was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180° C. for 20 minutes to measure the nonvolatile content, and the propylene content was adjusted to 30% by mass in the previously synthesized block copolymer solution. Glycol monomethyl ether acetate was added to prepare a vinyl resin dispersant (E2-3) liquid having a piperidyl skeleton.

(Production of vinyl resin type dispersant (E3-1))
A reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of propylene glycol monomethyl ether acetate, and the temperature was raised to 100° C. while substituting with nitrogen. In a dropping tank, 200 parts of N,N-dimethylaminoethyl methacrylate, 61 parts of propylene glycol monomethyl ether acetate, and 6 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) were charged, and after stirring until uniform, Then, the solution was dropped into the reaction tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Then, the non-volatile content was adjusted to 30% with propylene glycol monomethyl ether acetate, and the vinyl-based resin having a tertiary amino group having an amine value per non-volatile content of 345 mgKOH/g and a number average molecular weight of 2,500 (Mn) (E3-1. ) Obtained liquid.

<Production Example of Binder Resin (B) Liquid>
<Production of Binder Resin (B1: Non-Photosensitive Resin)>
(Preparation of Binder Resin (B1-1) Solution)
Charge 196 parts of propylene glycol monomethyl ether acetate 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 4-neck flask, raise the temperature to 80° C., and replace the inside of the reaction vessel with nitrogen. After that, from a dropping pipe, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) A mixture of 20.7 parts and 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was 20% in the resin solution synthesized above. A binder resin (B1-1) solution was prepared by adding acetate. The mass average molecular weight (Mw) was 26000.

(Preparation of Binder Resin (B1-2) Solution)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was filled with a nitrogen atmosphere, 210 parts of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100° C. with stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and 2,2′-azobisisobutyrate was further dissolved. A solution prepared by dissolving 3.6 parts of ronitrile was added dropwise to the flask, and stirring was continued at 100° C. for 5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was 20% in the resin solution synthesized above. A binder resin was prepared by adding acetate to obtain a resin (B1-2) solution having a mass average molecular weight (Mw) of 10,000.

(Preparation of Binder Resin (B1-M) Liquid)
The binder resin (B1-1) liquid and the binder resin (B1-2) liquid were mixed and stirred in the same amount to prepare a binder resin (B1-M) liquid.

<Production Example of Binder Resin (B2: Photosensitive Resin)>
(Preparation of Binder Resin (B2-1) Solution)
A separable 4-neck flask was charged with 207 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, heated to 80° C., and the inside of the reaction vessel was replaced with nitrogen. Then, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2 from a dropping pipe. A mixture of 1.33 parts of'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and after stirring while injecting dry air for 1 hour, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenzu manufactured by Showa Denko KK) A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate, and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70° C. over 3 hours. After the dropping was completed, the reaction was continued for another hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was 20% in the resin solution synthesized above. Binder resin (B2-1) was prepared by adding acetate. The mass average molecular weight (Mw) was 18,000.

(Preparation of Binder Resin (B2-2) Solution)
In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 333 g of propylene glycol monomethyl ether acetate was introduced, the atmosphere in the flask was changed from air to nitrogen, and the temperature was raised to 100° C., 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution of 164 g of propylene glycol monomethyl ether acetate and 3.6 g of azobisisobutyronitrile was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol% based on the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol. 9 g and 0.145 g of hydroquinone were put into the flask, the reaction was continued at 110° C. for 6 hours, and the reaction was terminated when the nonvolatile acid content value reached 1 mgKOH/g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a photosensitive transparent resin solution having an acid value of 80 mgKOH/g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and the nonvolatile content of the photosensitive transparent resin solution synthesized above was 20% by mass. Thus, propylene glycol monomethyl ether acetate was added to prepare a binder resin (B2-2) solution. The mass average molecular weight (Mw) was 12,000.

(Adjustment of binder resin (B2-3) liquid)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 182 g of propylene glycol monomethyl ether acetate, the atmosphere in the flask was changed from air to nitrogen, and the temperature was raised 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 A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture of 136 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was 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)], trisdimethylaminomethylphenol. 9 g and 0.145 g of hydroquinone were put into the flask and the reaction was continued at 110° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 mgKOH/g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and the nonvolatile content of the photosensitive transparent resin solution synthesized above was 20% by mass. Thus, propylene glycol monomethyl ether acetate was added to prepare a binder resin (B2-3) solution. The mass average molecular weight (Mw) was 13,000.

(Preparation of Binder Resin (B2-4) Solution)
A separable flask equipped with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate and 40 parts of methacrylic acid were used as a monomer dropping tank. A chain transfer agent was prepared by thoroughly stirring and mixing 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF CORPORATION), and 40 parts of propylene glycol monomethyl ether acetate. As a dropping tank, a well-mixed mixture of 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate was prepared.
After 395 parts of propylene glycol monomethyl ether acetate was charged into the reaction tank and the atmosphere was replaced with nitrogen, the temperature of the reaction tank was raised to 90° C. by heating in an oil bath while stirring. After the temperature of the reaction tank became stable at 90° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed for 135 minutes while maintaining the temperature at 90°C. 60 minutes after the dropping was completed, the temperature was raised to 110° C. in the reaction tank. After maintaining at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen/nitrogen=5/95 (volume ratio) mixed gas was started. Then, 70 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis(4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were charged into a reaction tank and allowed to react for 12 hours at 110°C. It was Then, 150 parts of propylene glycol monomethyl ether acetate was added and cooled to room temperature, and about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to 20% by mass to obtain a binder resin (B2-4) solution. The weight average molecular weight (Mw) of the resin was 18,000, and the acid value per nonvolatile matter was 2 mgKOH/g.

(Preparation of Binder Resin (B2-M) Solution)
Binder resin (B2-M) liquid was prepared by mixing and stirring the same amount of four kinds of binder resin (B2-1) to (B2-4) liquid.

<Solvent (N)>
(N-1) Cyclohexanone 20 parts (N-2) Ethyl 3-ethoxypropionate 20 parts (N-3) Propylene glycol monomethyl ether 20 parts (N-4) Cyclohexanol acetate 20 parts (N-5) Diproprene glycol 20 parts (N-1) to (N-5) of methyl ether acetate were mixed in the respective parts by mass to give a solvent (N).

<Preparation of colored composition>
(Production of Colored Composition (Dispersant Treatment: R-1))
[Production Example 1]
After the following mixture was stirred and mixed so as to be uniform, it was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then the pore size was 5. It filtered with a 0-micrometer filter and produced the coloring composition (R-1) whose nonvolatile component is 20 mass %.
Colorant (A1-1) 14.0 parts Dispersant (E1-1: 30% non-volatile content liquid) 4.0 parts Binder resin (B1-M: 20.0% non-volatile content liquid) 24.0 parts Solvent (N ) 58.0 copies

[Production Examples 2 to 72]
(Production of Coloring Compositions (R-2 to 72))
Coloring compositions (R-2 to 72) were prepared in the same manner as the coloring composition (R-1) except that the composition shown in Table 6 was changed.

(Production of Colored Composition (Adding Mixed Color Resin Solution or Resin Solution: S-1))
[Production Example 101]
(Preparation of colored composition (S-1))
The following raw materials were mixed, stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a colored composition (S-1).
Coloring composition 1 (R-1: 20.0% nonvolatile content liquid) 95.0 parts Binder resin (B1-M: 20.0% nonvolatile content liquid) 5.0 parts

[Production Examples 102 to 183]
(Preparation of colored composition (S-2 to 83))
Coloring compositions (S-2 to 83) were prepared in the same manner as in Production Example 101, except that the material types and masses were changed as described in Table 7.

[Synthesis of Photopolymerization Initiators D1-1 to D1-4]
The above photopolymerization initiators D1-1 to D1-4 were synthesized by the following method.

<Synthesis of photopolymerization initiator (D1-1)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane and 53 mmol of N-ethyl-3-nitro-carbazole were placed in an ice-cooled reaction vessel. While maintaining the reaction temperature at 5° C. or lower, 64-mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixed solution. After the dropping was completed, this mixed solution was stirred at 20° C. for 4 hours. Then, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the solution constituting this oily phase was dried using magnesium sulfate. Next, the desiccant was removed from this liquid by filtration, and the solvent was removed by distillation. An acyl derivative was obtained as described above.

(Step 2)
In a stream of nitrogen, 20 mmol of the above acyl derivative, 2.1 g (30 mmol) of hydroxyamine hydrochloride and 16.9 g of dimethylformamide were placed in a reaction vessel. The mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90° C. for 1 hour, cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. As described above, the photopolymerization initiator (D1-1) was obtained.

<Synthesis of photopolymerization initiator (D1-2)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane and 53 mmol of N-(2-ethyl-hexyl)-3-nitrocarbazole compound were placed in an ice-cooled reaction vessel. did. While maintaining the reaction temperature at 5° C. or lower, 64-mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixed solution. After the dropping was completed, this mixed solution was stirred at 20° C. for 4 hours. Then, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the solution constituting this oily phase was dried using magnesium sulfate. From this liquid, the desiccant was removed by filtration, and the solvent was removed by distillation. An acyl derivative was obtained as described above.

(Step 2)
In a stream of nitrogen, 20 mmol of the above acyl derivative, 2.1 g (30 mmol) of hydroxyamine hydrochloride and 16.9 g of dimethylformamide were placed in a reaction vessel. The mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90° C. for 1 hour, cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. As described above, a photopolymerization initiator (D1-2) was obtained.

<Synthesis of photopolymerization initiator (D1-3)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane and 53 mmol of N-ethyl-3-nitrocarbazole compound were placed in an ice-cooled reaction vessel. While maintaining the reaction temperature at 5° C. or lower, 64 mmol of 4-(ethoxymethyl)-2-methyl-benzoyl chloride was gradually added dropwise to this mixed solution. After the dropping was completed, this mixed solution was stirred at 20° C. for 4 hours. Then, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the solution constituting this oily phase was dried using magnesium sulfate. From this liquid, the desiccant was removed by filtration, and the solvent was removed by distillation. An acyl derivative was obtained as described above.

(Step 2)
In a stream of nitrogen, 20 mmol of the above acyl derivative, 2.1 g (30 mmol) of hydroxyamine hydrochloride and 16.9 g of dimethylformamide were placed in a reaction vessel. The mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90° C. for 1 hour, cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. As described above, the photopolymerization initiator (D1-3) was obtained.

<Synthesis of photopolymerization initiator (D1-4)>
(Step 1)
In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane and 53 mmol of N-(2-ethyl-hexyl)-3-nitrocarbazole compound were placed in an ice-cooled reaction vessel. did. While maintaining the reaction temperature at 5° C. or lower, 64-mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixed solution. After the dropping was completed, this mixed solution was stirred at 20° C. for 4 hours. Then, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the solution constituting this oily phase was dried using magnesium sulfate. From this liquid, the desiccant was removed by filtration, and the solvent was removed by distillation. An acyl derivative was obtained as described above.
(Step 2)
In a stream of nitrogen, 20 mmol of the above acyl derivative, 2.1 g (30 mmol) of hydroxyamine hydrochloride and 16.9 g of dimethylformamide were placed in a reaction vessel. The mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 3.12 g (24 mmol) of propionic anhydride were added to the distillation residue. The mixture was stirred at 90° C. for 1 hour, cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. As described above, a photopolymerization initiator (D1-4) was obtained.

Formula (7):

Formula (8):

Formula (9)

Formula (10):

<Method for producing photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (X-1))
The following raw materials were mixed, stirred, and filtered with a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (S-1: Nonvolatile content 20.0%): 50.0 parts Binder resin (B2-M: Nonvolatile content 20.0%): 15.0 parts Thermosetting compound (CE-1): 1 0.0 part Thermosetting compound (CE-2): 1.0 part Photopolymerizable compound (C1-1/C2-2): 3.0 parts Photopolymerization initiator (D11-1): 1.8 parts Increase Sensitizer (F): 0.2 part Thiol chain transfer agent (G): 0.4 part Polymerization inhibitor (H): 0.1 part Ultraviolet absorber (I): 0.1 part Antioxidant (J ): 0.1 part Leveling agent (K: non-volatile content 3%): 1.0 part Storage stabilizer: 0.1 part Silane coupling agent (M): 0.2 part Solvent (N): 26.0 parts

[Examples 2 to 111, Comparative Examples 1 and 2]
(Preparation of Photosensitive Coloring Composition (X-2 to 113))
Photosensitive coloring compositions (X-2 to 113) were prepared in the same manner as in Example 1 except that the types of the coloring composition and the binder resin solution in Example 1 were changed as described in Table 8.
The respective raw materials are as follows.

<Thermosetting compound (CE)>
・Epoxy compound (CE-1)
1,2-Epoxy-4-(2-oxiranyl)cyclohexane adduct of (CE-1-1)2,2'-bis(hydroxymethyl)-1-butanol
[EHPE-3150 (manufactured by Daicel)],
(CE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase Chemtex)],
(CE-1-3) Triglycidyl isocyanurate (CE-1-1) to (CE-1-3) were mixed in the same amount to obtain an epoxy compound (CE-1).
-Oxetane compound (CE-2):
3-Ethyl-3-[(3-ethyloxetane-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Photopolymerizable compound (C)>
(C1-1) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(C1-2) Pentylene chain-containing tris-(2-acryloxyethyl) isocyanurate [A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(C2) Pentylene chain-containing polyfunctional (meth)acrylate
[KAYARAD DPCA60 (manufactured by Nippon Kayaku Co., Ltd.)]
(C1-1/C2): The above (C1-1) and (C2) were mixed at a ratio of 80:20.
(C3-M): The following (C3-1) to (C3-5) were mixed in the same amount to give a polymerizable compound (C3-M).
(C3-1) trimethylolpropane triacrylate
[Aronix M309 (Toagosei Co., Ltd.)]
(C3-2) Dipentaerythritol penta and hexaacrylate
[Aronix M402 (Toagosei Co., Ltd.)]
(C3-3) Polybasic acidic acrylic oligomer
[Aronix M520 (Toagosei Co., Ltd.)]

(C3-4) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a 5-neck reaction vessel having a polyfunctional urethane acrylate content of 1 liter synthesized by the following method, and the mixture was reacted at 60° C. for 8 hours. ) A product containing a polyfunctional urethane acrylate (C3-4) having an acryloyl group was obtained, in which the proportion of the polyfunctional urethane acrylate (C3-4) was 70% by mass, and the balance was other. It is occupied by photopolymerizable compounds, and it was confirmed by IR analysis that there were no isocyanate groups in the reaction product.

(C3-5) Bifunctional bisphenol A type (meth)acrylate
[ABE-300 (Shin Nakamura Chemical Co., Ltd.)]

<Photopolymerizable initiator (D)>
(D1-1 to D1-4) As described above.
(D11-1) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one [IRGACURE 369 (manufactured by BASF Japan)] and (D1-1 to D1-4). The above five photopolymerization initiators are mixed in equal amounts.
(D2-1) Represented by the chemical formula (D2-1) (D2-2) Represented by the chemical formula (D2-2) (D21-1) 2-benzyl-2-dimethylamino-1-(4 -Morpholinophenyl)-butan-1-one [Irgacure 369 (manufactured by BASF Japan Ltd.)] and three photopolymerization initiators (D2-1, D2-2) mixed in equal amounts.
(D1-1/D2-1) A mixture of two types of (D1-1) and (D2-1) photopolymerization initiators in equal amounts.
(D3-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(D3-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(D3-3) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide
[Lucirin TPO (Ciba Japan)]
(D3-4)2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei)]
(D3-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(D3-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(D3-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(D3-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
As described above, (D3-1) to (D3-8) were mixed in the same amount to obtain a photopolymerization initiator (D3-M).

<Sensitizer (F)>
(F-1) 2,4-diethylthioxanthone
[Kayakyu DETX-S (Nippon Kayaku Co., Ltd.)]
(F-2) 4,4'-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemmark Chemical)]
As described above, (F-1) and (F-2) were mixed in the same amount to obtain a sensitizer (F).

<Thiol chain transfer agent (G)>
(G-1) trimethylolethane tris (3-mercaptobutyrate)
[TEMB (Showa Denko)]
(G-2) Trimethylolpropane tris(3-mercaptobutyrate)
[TPMB (Showa Denko)]
(G-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (made by Sakai Chemical Industry)]
(G-4) Trimethylolpropane tris(3-mercaptopropionate)
[TMMP (made by Sakai Chemical Industry)]
(G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (made by Sakai Chemical Industry)]
As described above, (G-1) to (G-5) were mixed in the same amount to obtain a thiol chain transfer agent (G).

<Polymerization inhibitor (H)>
(H-1) 3-methylcatechol (H-2) methylhydroquinone (H-3) tert-butylhydroquinone or higher, and (H-1) to (H-3) are mixed in the same amount, and a polymerization inhibitor is added. (H).

<Ultraviolet absorber (I)>
(I-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine
[TINUVIN 400 (manufactured by BASF Japan)]
(I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described above, (I-1) and (I-2) were mixed in the same amount to obtain an ultraviolet absorber (I).

<Antioxidant (J)>
(J-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (J-2)3,3′-Dioctadecyl thiodipropanoate (J-3) Tris[2 , 4-di-(tert)-butylphenyl]phosphine (J-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate or higher, (J -1) to (J-5) were mixed in the same amount to obtain an antioxidant (J).

<Leveling agent (K)>
1 part of BYK-330: Polyether-modified polydimethylsiloxane manufactured by BYK Chemie,
1 part of "Megafuck F-551: Fluorine-containing/lipophilic group-containing oligomer" manufactured by DIC,
A mixed solution prepared by dissolving 1 part of "Emulgen 103: polyoxyethylene lauryl ether" manufactured by Kao Corporation in 97 parts of propylene glycol monomethyl ether acetate.

<Storage stabilizer>
(L-1)2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine ("TPP" manufactured by Kitako Chemical Co., Ltd.)
As described above, (L-1) and (L-2) were mixed in the same amount to obtain a storage stabilizer.

<Adhesion improver>
(M-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (Shin-Etsu Chemical Co., Ltd.)]
(M-3)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (Shin-Etsu Chemical Co., Ltd.)]
As described above, (M-1) to (M-4) were mixed in the same amount to obtain an adhesion improver.

<Evaluation of photosensitive coloring composition>
The photosensitive coloring composition was evaluated as follows. The results are shown in Table 9.

[Filter segment formation]
The obtained photosensitive coloring composition was applied to a glass substrate measuring 10 cm in length and 10 cm in width by a spin coating method, and then heated in a clean oven at 70° C. for 15 minutes to remove the solvent to obtain a film of about 2 μm. It was Next, this glass substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed with an aqueous sodium carbonate solution at 23° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230° C. for 30 minutes to prepare a filter segment. The spray development was carried out for the coating film of each photosensitive coloring composition in the shortest possible time for pattern formation in which no development remained, and this was taken as the proper development time. The film thickness of the coating film was measured using Dektak3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Sensitivity evaluation]
The thickness of the pattern in the 100 μm photomask portion of the obtained filter segment was measured, and the minimum exposure amount which was 90% or more of the thickness immediately after coating was evaluated. The smaller the minimum exposure amount, the higher the sensitivity and the better the evaluation of the photosensitive coloring composition. The evaluation criteria are as follows.
◯: less than 50 mJ/cm ² (good)
Δ: 50 mJ/cm ² or more and less than 100 mJ/cm ² (practical range)
×: 100 mJ/cm ² or more (not practical)

<Regarding pattern shape>
[Linearity evaluation]
The linearity of the pattern in the 100 μm photomask portion of the obtained filter segment was evaluated by observing it with an optical microscope. The evaluation criteria are as follows.
○: Good linearity (good)
Δ: Partial linearity defect (slight chipping) (practical range)
×: Poor linearity (impractical)

[Cross-sectional shape evaluation]
The cross section of the pattern in the 100 μm photomask portion of the obtained filter segment was observed and evaluated using an electron microscope. The evaluation criteria are as follows. The turn cross section has a good forward taper.
◯: Forward tapered shape with a gentle cross section (good)
Δ: Cross-section has a forward taper shape (practical range)
X: Cross-section is reverse taper shape (not practical)

<About coating resistance>
[Solvent resistance evaluation]
The obtained filter segment was immersed in an N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and evaluated by observing the pattern at the 100 μm photomask portion using an optical microscope. The evaluation criteria are as follows.
◯: Good (good) with no change in appearance or color
Δ: Wrinkles, etc. partially occur, but the color does not change and is good (practical range)
×: Fading occurred (not practical)

From the results in Table 9, Examples 1 to 111 contain a specific azo pigment, and the photopolymerizable initiator (D) contained at least one of the photopolymerization initiator [D1] and the photopolymerization initiator [D2]. By including it, good sensitivity, pattern linearity, cross-sectional shape, and solvent resistance can be obtained.

10 Liquid Crystal Display Device 11 Transparent Substrate 12 TFT Array 13 Transparent Electrode Layer 14 Alignment Layer 15 Polarizing Plate 21 Transparent Substrate 22 Color Filter 23 Transparent Electrode Layer 24 Alignment Layer 25 Polarizing Plate 30 Backlight Unit 31 White LED Light Source LC Liquid Crystal

Claims (8)

A color filter coloring composition containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerizable initiator (D), wherein the colorant (A) is: The photopolymerizable initiator (D) contains at least one organic pigment (A1) selected from the group consisting of pigments represented by the general formulas (1) to (3), and the photopolymerizable initiator (D) is represented by the following general formula (4). )) and/or a photopolymerization initiator [D2] represented by the following general formula (5).
General formula (1)

[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. .. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{1 to} X ₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfo group. Represents a halogen atom. ]
General formula (2)

[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. .. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X _{5 to} X ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group or a halogen atom. A represents a direct bond or a divalent linking group. Examples of the divalent linking group include an alkylene group which may have a substituent, —O—, —S—, —CO—, —SO ₂ —, —COO—, —CONH—, and —SO ₂ NH—. Represent ]
General formula (3)

[In the general formula (3), A′ represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , Alternatively, it represents —SO ₂ NHR ^12, and at least one of R ^{2 to} R ⁶ represents a trifluoromethyl group. R ^{7 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

General formula (4)

[In the general formula (4), X ¹ , X ³ and X ⁶ each independently represent R ¹³ , OR ¹³ , COR ¹³ , SR ¹³ , CONR ¹⁴ R ¹⁵ or CN, and X ² represents a substituent. An alkyl group having 1 to 20 carbon atoms which may have, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon atom which may have a substituent 7 to 30 arylalkyl group or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and X ⁴ and X ⁵ each independently represent R ¹³ , OR ¹³ , SR. ¹³ , COR ¹³ , CONR ¹⁴ R ¹⁵ , NR ¹⁴ COR ¹³ , OCOR ¹³ , COOR ¹³ , SCOR ¹³ , COSR ¹³ , COSR ¹³ , CSOR ¹³ , CN, a halogen atom or a hydroxyl group. R<^13> , R<^14> and R< ¹⁵ > each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent; Represent a and b are each independently an integer of 0 to 3. ]
General formula (5)

[In the general formula (5), R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted Alternatively, it represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ] The colorant (A) further comprises C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, and the photosensitive coloring composition according to claim 1, containing at least one selected from the group consisting of yellow pigments represented by the following general formula (6).
General formula (6)

[In general formula (6), Z _{1 to} Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H, —COOH, and a monovalent to trivalent metal salt of these acidic groups, an alkylammonium salt, a phthalimidomethyl group which may have a substituent, or a substituent Represents a sulfamoyl group which may have,
The adjacent groups of Z _{1 to} Z ₄ and/or Z _{10 to} Z ₁₃ may be combined together to form an aromatic ring which may have a substituent. ] The photosensitive coloring composition according to claim 1 or 2, wherein the photopolymerizable initiator (D) further contains an acetophenone-based initiator. 4. The photopolymerizable compound (C) contains a photopolymerizable compound [C1] having an isocyanurate skeleton and/or an alkylene chain-containing photopolymerizable compound [C2]. The photosensitive coloring composition according to the item. Further, the photosensitive coloring composition according to claim 1, further comprising an antioxidant. Content of the coloring agent (A) with respect to the total solid content in a photosensitive coloring composition is 30-70 mass %, The photosensitive coloring composition in any one of Claims 1-5 characterized by the above-mentioned. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to claim 1. A liquid crystal display device comprising the color filter according to claim 7.