JP2021031652A - Phthalocyanine pigment, coloring composition, and color filter - Google Patents

Abstract

To provide a phthalocyanine pigment and a coloring composition using the same, having a low viscosity and excellent filterability, to provide a phthalocyanine pigment and a coloring composition using the same, having excellent color characteristics (luminance) and coloring power when used for color filters and the like and having good electrical characteristics even when a high luminance backlight is used, and also to provide a high quality color filter using the coloring composition.SOLUTION: Provided is a phthalocyanine pigment represented by general formula (1). Also provided is a phthalocyanine pigment represented by general formula (1), where an average value n of the number of substitution of a halogen atom represented by X is 1 to 8, and an average value m of the substituent represented by Y is 1 to 4.SELECTED DRAWING: None

Description

Embodiments of the present invention relate to a novel phthalocyanine pigment and a method for producing the same. Another embodiment relates to a coloring composition containing the phthalocyanine pigment and a color filter formed from the coloring composition. The color filter can be suitably used for a color liquid crystal display device, an organic EL display device, a color image pickup tube element, and the like.

In recent years, as an image recording material, a material for forming a color image has become the mainstream. Specifically, as a color image recording material, an inkjet recording material, a heat-sensitive transfer recording material, an electrophotographic recording material, a transfer silver halide photosensitive material, a printing ink, a recording pen and the like are actively used. ing. Further, a color filter is used for recording and reproducing a color image in an imaging element such as a CCD in a photographing device and in an LCD, PDP, organic electroluminescence, or electronic paper (electronic paper) in a display. In these color image recording materials and color filters, three primary color dyes (dye and pigment) of so-called additive color mixing method and subtractive color mixing method are used for displaying or recording a full-color image. However, the fact is that there is no dye that has absorption characteristics and color characteristics that can realize a preferable color reproduction range and is suitable for various usage conditions, and improvement is strongly desired.

The pigments used in each of the above applications differ in the color characteristics required for each application and the required quality for each application, but from the viewpoint of light resistance and heat resistance of recorded materials, pigments are mainly used as pigments. ing.

In the production of green filters in color filters, it is common to use various phthalocyanine compounds as colorants, and many color filter compositions containing these compounds have been proposed. Among them, C.I. I. Copper phthalocyanine compounds represented by Pigment Green 36 and C.I. I. Many colorants for color filters using zinc phthalocyanine compounds represented by Pigment Green 58 have been proposed.

As a colorant for a color filter, it has been required to achieve high transmittance (high brightness) and high contrast of a color filter. In recent years, in addition to these, there has been an increasing demand for colorants having high coloring power from the viewpoints of thinning color filters and high color reproducibility.

Patent Document 1 discloses a composition for a color filter using an aluminum phthalocyanine pigment as a green dye.
Further, Patent Document 2 discloses a composition for a color filter using a halogenated aluminum phthalocyanine pigment as a green dye.

However, although all of these phthalocyanine pigments have been materials for providing color filters that give high brightness, in recent years, in the industrial world, there is a demand for higher brightness and higher coloring power for color filters. There is a problem that the desired performance cannot be obtained with the composition using these phthalocyanine pigments.

Further, in recent years, with the spread of 4KTV and the like in color liquid crystal display devices, the miniaturization of pixels is progressing as the image quality is further improved. As the pixel miniaturization, the aperture ratio of the display decreases, and the brightness of the conventional backlight is insufficient. Therefore, in recent color liquid crystal display devices, a colored film is formed directly on a driving substrate on which a thin film transistor (TFT) is arranged or through a passivation film such as a silicon nitride film, and the substrate on which the colored film is formed is used. The aperture ratio is reduced by developing a COA method (see Patent Document 2) in which a transparent electrode for driving a liquid crystal is bonded to a substrate formed by vapor deposition or sputtering, and by increasing the brightness of the backlight. Even so, it is possible to maintain high brightness. On the other hand, when a high-brightness backlight is used, the pigment in the color filter is photoexcited by the emitted light energy, and as a result, the insulation between the TFT and the transparent electrode cannot be maintained, and a voltage can be applied to the transparent electrode. At that time, the voltage cannot be maintained, causing poor alignment of the liquid crystal, and the number of cases where display color unevenness on the panel occurs is increasing. These phenomena also occur in the green color filter, which is a problem.

Japanese Unexamined Patent Publication No. 2012-155231 Japanese Unexamined Patent Publication No. 2016-153481

The problem to be solved by the present invention is to provide a phthalocyanine pigment having low viscosity and excellent filterability and a coloring composition using the same, and to provide color characteristics (brightness) and coloring power when used in a color filter or the like. It is an object of the present invention to provide a phthalocyanine pigment and a coloring composition using the same, which are excellent in quality and have good electrical characteristics even when a high-intensity backlight is used. Another object of the present invention is to provide a high quality color filter using the coloring composition.

As a result of intensive studies to solve the above problems, the present inventors have conducted an alkyl group which may have a substituent, an aryl group which may have a substituent, and an aryl group which may have a substituent. It may have a good cycloalkyl group, a heterocyclic group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. By using a phthalocyanine pigment having any one of the arylthio groups and having a halogen as a substituent, a coloring composition having low viscosity and excellent filterability can be obtained, and further, a photosensitive coloring composition can be obtained. It has been found that a product has excellent color characteristics (brightness), high brightness and high coloring power, and good electrical characteristics can be obtained, and the present invention has been made based on this finding.

That is, the present invention
The present invention relates to a phthalocyanine pigment represented by the following general formula (1).

General formula (1)

[In the formula, X represents a halogen atom. n is 1 to 15 representing the average value of the number of substitutions of the halogen atom.
Y is an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a heterocycle which may have a substituent, respectively. Represents a group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. m is 1 to 15 representing the average value of the substituents represented by Y.
Z represents −OP (= O) R ₁ R ₂ , where R ₁ and R ₂ independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents a good aryl group, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring.

The average value n of the number of substitutions of the halogen atom represented by X of the phthalocyanine pigment represented by the general formula (1) is 1 to 8, and the average value m of the substituents represented by Y is 1 to 4. The present invention relates to the phthalocyanine pigment described above.

Y of the phthalocyanine pigment represented by the general formula (1) is an alkyl group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. It relates to a phthalocyanine pigment according to the above description.

The present invention relates to a coloring composition for a color filter comprising a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains the phthalocyanine pigment described above.

Further, the present invention relates to the above-mentioned coloring composition for a color filter, which comprises a resin-type dispersant.

The present invention relates to the above-mentioned coloring composition for a color filter, which further contains a yellow pigment.

The yellow pigment is C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. The coloring composition for a color filter according to the above, which is at least one selected from the group consisting of Pigment Yellow 185 and a quinophthalone pigment represented by the following general formula (2).
General formula (2)

[In the general formula (2), R ^{1 to} R ¹³ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxy group or a substituent which may have a substituent. Represents an aryl group that may have. However, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. ]

The present invention relates to the above-mentioned coloring composition for a color filter, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

In a color filter having at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one green filter segment is formed by the coloring composition for a color filter described above. Regarding.

According to the present invention, by using the phthalocyanine pigment represented by the above general formula (1), a coloring composition having a low viscosity and excellent filterability, and a color characteristic (luminance) when used in a color filter or the like. ) And excellent coloring power, and a coloring composition having good electrical characteristics can be obtained even when a high-luminance backlight is used. Another object of the present invention is to provide a high quality color filter using the coloring composition.

Hereinafter, the present invention will be described in detail.
In the present specification, the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" is particularly described. "Acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid", respectively, unless Represent. Further, in the present specification, "CI" means a color index (CI).

The present invention is a phthalocyanine pigment represented by the above general formula (1). Further, the present invention is a coloring composition for a color filter composed of a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine pigment represented by the above general formula (1). It is a coloring composition for a color filter.

<Parthalocyanine pigment>
The phthalocyanine pigment of the present invention is represented by the following general formula (1), and can be suitably used as a colorant used in a coloring composition, particularly a green colorant.

General formula (1)

In the formula, X represents a halogen atom. n is 1 to 15 representing the average value of the number of substitutions of the halogen atom.
Y is an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a heterocycle which may have a substituent, respectively. Represents a group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. m is 1 to 15 representing the average value of the substituents represented by Y.
Z represents −OP (= O) R ₁ R ₂ , where R ₁ and R ₂ independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents a good aryl group, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring.

The halogen atom of X is chlorine, bromine, and iodine.

Examples of the "alkyl group" of the alkyl group which may have a substituent in Y 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. Examples thereof include a linear or branched alkyl group such as a group, an n-octyl group, a stearyl group and a 2-ethylhexyl group, and examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group and 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-putylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

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

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent in Y include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the "cycloalkyl group having a substituent" include 2. , 5-Dimethylcyclopentyl group, 4-tert-Ptylcyclohexyl group and the like.

Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent in Y include a pyridyl group, a pyrazil group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group and the like, and "complex having a substituent". Examples of the "ring group" include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrrolyl group and the like.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent in Y include a phenoxy group, a naphthoxy group, an anthryloxy group and the like, and examples of the "aryloxy group having a substituent" include p. Examples thereof include a-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group and the like.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent in Y include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group and an octadecylthio group. Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

Examples of the "arylthio group" of the arylthio group which may have a substituent in Y include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like, and "an arylthio group having a substituent". Examples thereof include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group and the like.

Y of the phthalocyanine pigment represented by the general formula (1) is an alkyl group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. It is more preferable to have it because it has excellent coloring power.

The average value n of the number of substitutions of the halogen atom represented by X of the phthalocyanine pigment represented by the general formula (1) is 1 to 8, and the average value m of the substituents represented by Y is 1 to 4. It is preferable to have. When n and m are in this range, the coloring power, the brightness, the viscosity stability, and the filterability are all excellent.

Alkyl groups in R ₁ and R ₂ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group and stearyl group. , 2-Ethylhexyl group and other linear or branched alkyl groups, preferably alkyl groups having 1 to 6 carbon atoms.

Examples of the substituent of the alkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxy group such as a methoxy group, an aryl group such as a phenyl group and a trill group, and a nitro group. Moreover, there may be a plurality of substituents. Therefore, examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group and a 2-butoxy. Ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl The group etc. can be mentioned.

Examples of the aryl group in R ₁ and R ₂ include a monocyclic aromatic hydrocarbon group such as a phenyl group and a p-tolyl group, and a condensed aromatic hydrocarbon group such as a naphthyl group and an anthryl group. A hydrocarbon group is preferred. Further, an aryl group having 6 to 12 carbon atoms is preferable.

Examples of the substituent of the aryl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxy group, an amino group and a nitro group. Moreover, there may be a plurality of substituents. Therefore, examples of the aryl group having a substituent include a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group and a 2-dimethylaminophenyl group. Examples thereof include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Alkoxy groups in R ₁ and R ₂ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3-. Examples thereof include a linear or branched alkoxy group such as a pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group and a 2-ethylhexyloxy group, and an alkoxy group having 1 to 6 carbon atoms is preferable.

Examples of the substituent of the alkoxy group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an aryl group such as an alkoxy group, a phenyl group and a trill group, and a nitro group. Moreover, there may be a plurality of substituents. Therefore, examples of the alkoxy group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group and a 2,2-. Examples thereof include a ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, a benzyloxy group and the like.

Examples of the aryloxy group in R ₁ and R ₂ include an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group, and a condensed aromatic hydrocarbon such as a naphthaloxy group and an anthryloxy group. Examples thereof include an aryloxy group composed of a group, and an aryloxy group composed of a monocyclic aromatic hydrocarbon group is preferable. Further, an aryloxy group having 6 to 12 carbon atoms is preferable.
Examples of the substituent of the aryloxy group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxy group, an amino group and a nitro group. Moreover, there may be a plurality of substituents. Therefore, examples of the aryloxy group having a substituent include a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group and the like. Can be mentioned.

As the phthalocyanine pigment represented by the general formula (1) used in the present invention, _{at least one of R 1} and R ₂ may have an aryl group from the viewpoint of dispersibility and color characteristics. Alternatively, it is preferably an aryloxy group that may have a substituent. More preferably, both R ₁ and R ₂ are aryl groups or aryloxy groups. Further, preferably, _{both R 1} and R ₂ are phenyl groups or phenoxy groups.

Typical examples of Z in the general formula (1) include the structures shown below (* represents the bonding position of the substituent with Al in the general formula (1)). It is not limited to. The cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

In a preferred embodiment of the phthalocyanine pigment of the present invention, X in the general formula (1) is a bromine atom, Y is a methyl group, and Z is −OP (= O) (OC ₆ H ₅ ) ₂ . Things can be mentioned. This phthalocyanine pigment has properties as a pigment and can be suitably used as a colorant, particularly a green colorant.

<Manufacturing method of phthalocyanine pigment>
A method for producing a phthalocyanine pigment represented by the general formula (1) of the present invention will be described. The phthalocyanine compound represented by the following general formula (2) is halogenated and then hydrolyzed to obtain the compound of the general formula (3). Subsequently, the phthalocyanine pigment represented by the general formula (3) _{is reacted with the acidic compound represented by HOP (= O) R 1} R ₂ to obtain a phthalocyanine pigment having a desired substituent. Can be done. _R 1, _{R 2} in the acidic compounds are respectively synonymous with _R 1, _{R 2} in the general formula (1).

General formula (2)

General formula (3)

In the formula, X represents a halogen atom. n is 1 to 15 representing the average value of the number of substitutions of the halogen atom.
Y is an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a heterocycle which may have a substituent, respectively. Represents a group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. m is 1 to 15 representing the average value of the substituents represented by Y.

The halogenation of the phthalocyanine compound represented by the general formula (2) is described in, for example, "The Phthalocyanines Volume II Manufacture and Applications" (CRC Press, Inc., 1983) and the like, a chlorosulfonic acid method, a melting method and the like. It can be manufactured by the method of.

Examples of the chlorosulfonic acid method include a method in which a phthalocyanine compound represented by the general formula (2) is dissolved in a sulfur oxide-based solvent such as chlorosulfonic acid and sulfuric acid, and a halogenating agent is added thereto to halogenate the compound. Be done. The reaction at this time is preferably carried out at a temperature of 20 to 120 ° C., preferably in the range of 1 to 10 hours.

As a melting method, for example, as described in JP-A-51-64534 (US Pat. No. 4,077,974), halogenation such as aluminum chloride, aluminum bromide, and titanium tetrachloride. One or two types of various halogenating agents such as alkali metal halides such as titanium, sodium chloride and sodium bromide or alkaline earth metal halides (hereinafter referred to as alkali (earth) metal halides] and thionyl chloride. A method of halogenating phthalocyanine represented by the general formula (2) in a melt of the above mixture at about 10 to 170 ° C. can be mentioned.

The halogenating agent used for halogenation means a fluorinating agent, a chlorinating agent, a brominating agent and an iodizing agent. For example, examples of the fluorinating agent include fluoroxitrifluoromethane, cesium sulfate, acetylhypofluorite, N-fluorosulfonamide, diethylaminosulfatrifluoride, N-fluoropyridinium salt and the like.
Examples of the chlorinating agent include chlorine (Cl2), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone, Examples thereof include 2,3,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethylammonium chloride and benzeneselenenyl chloride.

Examples of the brominating agent include bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexy. Sa-2,5-dieneon, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethylhydantoin, etc. Can be mentioned.

Examples of the iodinating agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, N-iodosuccinimide and the like. ..

Further, since the phthalocyanine represented by the general formula (3) has properties as a pigment, it may be used in combination with the phthalocyanine pigment represented by the general formula (1). The phthalocyanine represented by the general formula (3), which is the starting material of the phthalocyanine pigment represented by the general formula (1), is subjected to an acid pacing method prior to the reaction in order to improve the reaction efficiency with the acidic compound. It is desirable to refine the phthalocyanine represented by the general formula (3) by a method such as the solvent salt milling method or the like. By refining the phthalocyanine represented by the general formula (3) in advance, it becomes easy to obtain a phthalocyanine pigment produced by using the phthalocyanine in a fine state. When such a finely divided phthalocyanine pigment is used as a coloring composition, it becomes easy to obtain high brightness and high contrast.

Further, the reaction between the phthalocyanine represented by the general formula (3) and the acidic compound can be allowed to proceed by, for example, mixing and stirring in an organic solvent. Then, by removing the organic solvent, a desired phthalocyanine pigment can be obtained.

Examples of the organic solvent used in the production of the phthalocyanine pigment include the following.
Monohydric alcohol solvents such as methanol, ethanol, isopropanol, and t-butanol,
Ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin, trimethylolpropane, etc. Polyhydric alcohol solvent represented by
1-Methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea, or amide-based solvents such as tetramethylurea,
In addition, lower monoalkyl ether solvents of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether,
Polyester-based solvents such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether (triglyme),
Sulfur-containing solvent such as sulfolane, dimethyl sulfoxide, or 3-sulfolene,
Polyfunctional solvents such as diacetone alcohol and diethanolamine,
Carboxylic acid solvents such as acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, or trifluoroacetic acid,
Sulfonic acid-based solvents such as methanesulfonic acid or trifluorosulfonic acid,
Aromatic hydrocarbon solvents such as benzene, toluene and xylene.
In one embodiment, since the dissolution of diphenyl phosphate is good, monovalent alcohol solvents such as methanol, ethanol and isopropyl alcohol, dimethyl sulfoxide, N, N-dimethylformamide and 1-methyl-2-pyrrolidinone are used. It is preferable to use an aprotic polar solvent such as. These organic solvents can be used alone or in combination of two or more.

As a method for removing the organic solvent after completion of the reaction, a method known in the industry can be used. In one embodiment, it is desirable to perform suction filtration or pressure filtration, wash with an organic solvent compatible with the organic solvent used, and have a low boiling point, and then remove by drying. In the case of a water-soluble organic solvent, it is desirable to mix it with water and then remove it by washing with water.

<Miniaturization of phthalocyanine pigment>
Examples of the miniaturization method include industry-known methods used for miniaturization of general colorants and pigments such as an acid pacing method and a solvent salt milling method.

The acid pacing method is a method in which a pigment is added to sulfuric acid to dissolve it, and then a sulfuric acid solution is added dropwise to a large amount of water and precipitated to obtain a fine colorant. By optimizing the amount of water used for precipitation, temperature, etc., it is possible to obtain pigment particles having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution. it can.

The solvent salt milling method is a method of heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment particles are 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 width, and a sharp particle size distribution.
As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate and the like can be used. From the viewpoint of price, it is preferable to use sodium chloride (salt). 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 weight, most preferably 300 to 1000% by weight, based on the total weight of the phthalocyanine pigment (100% by weight).

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. Examples of such water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, and 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 Polyethylene glycol or the like is used. These water-soluble organic solvents are preferably used in the range of 5 to 1000% by weight, more preferably 50 to 500% by weight, based on the total weight of the phthalocyanine pigment (100% by weight).

When the solvent salt milling treatment is performed, a resin may be added if necessary. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. The amount of the resin used is preferably in the range of 2 to 200% by weight based on the total weight of the phthalocyanine pigment (100% by weight).

The phthalocyanine pigment of the present invention may be used in combination with two or more types of phthalocyanine pigments, depending on the intended use. In this case, separately produced phthalocyanine pigments may be mixed and used. Alternatively, those produced by synthesizing or refining two or more types of phthalocyanine pigments at the same time may be used.

<Coloring composition>
The coloring composition of the present invention contains a colorant, a binder resin and an organic solvent, and the colorant contains a phthalocyanine pigment represented by the general formula (1). In one embodiment, the coloring composition has a green tint derived from the phthalocyanine pigment represented by the general formula (1) used as a coloring agent. The coloring composition of the present invention may contain an additional dye as a colorant for the purpose of adjusting the chromaticity, etc., as long as the effect of the phthalocyanine pigment represented by the general formula (1) is not impaired.

<Colorant>
(Green pigment)
In one embodiment of the present invention, the coloring composition contains a green pigment other than the phthalocyanine pigment represented by the general formula (1) in order to further adjust the chromaticity, as long as the effect of the present invention is not impaired. May be good. The green pigment is not particularly limited, but generally includes a green pigment or a green dye.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 62, 63, Examples thereof include zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342, etc., and aluminum phthalocyanine pigments described in Japanese Patent No. 4893859. , Especially not limited to these. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36, 58, 62, 63.

As a green dye, C.I. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. Acid dye, C.I. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye, C.I. I. Modant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Examples include modern dyes. Examples of the green pigment include C.I. I. It is preferably at least one selected from the group consisting of Pigment Greens 7, 36 and 58.

(Yellow pigment)
In order to further adjust the chromaticity, the coloring composition of the present invention preferably contains a yellow dye within a range that does not impair the effects of the present invention. The yellow pigment is not particularly limited, but generally includes a yellow pigment or a yellow dye.

As the yellow pigment, an organic or inorganic pigment can be used alone or in combination of two or more, and a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and usually Organic pigments are used. As the organic pigment, a commercially available pigment can be used, and a natural pigment or an inorganic pigment can be used in combination depending on the desired hue of the filter segment.

Specific examples of the yellow organic pigment that can be used in the above coloring composition are shown below. Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as quinophthalone pigments represented by the general formula (5) described in 192, 193, 194, 196, 198, 199, 213, 214 and JP-A-2012-226110 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, 185 and at least one selected from the group consisting of quinophthalone pigments represented by the general formula (4) are preferable.

General formula (4)

[In the general formula (4), R ^{1 to} R ¹³ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxy group or a substituent which may have a substituent. Represents an aryl group that may have. However, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. ]

In the general formula (4), examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a petit group, an isoptyl group, a tert-ptyl group, a neopentyl group, an n-hexyl group and an n-octyl group. In addition to linear or branched alkyl groups such as groups, stearyl groups and 2-ethylhexyl groups, trichloromethyl groups, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, 2,2-dibromoethyl groups, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, penzyl group, 4-methylpentyl group, 4-tert-ptylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a penzyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group.

Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-ptyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples thereof include an alkoxy group having a substituent such as a propoxy group and a benzyloxy group.

The aryl group which may have a substituent includes an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and a 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-naphthyl group, 4 , 5,8-Trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having substituents can be mentioned.

Yellow dyes include azo dyes, azo metal complex salt dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, and quinoline dyes. , Naftquinone dyes, oxazine dyes and the like.

Therefore, specific examples of the yellow dye include C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191 and 192, 199 and the like can be mentioned.

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like can also be mentioned.

In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, Examples include 105 and 106.

In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like can also be mentioned.

In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 , 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 , 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

When a green pigment is used in combination with the phthalocyanine pigment represented by the general formula (1), the mass ratio of the green pigment / the phthalocyanine pigment represented by the general formula (1) is 10/90 from the viewpoint of brightness and hue. The range of ~ 70/30 is preferable. It is more preferably in the range of 20/80 to 40/60, and even more preferably in the range of 20/80 to 35/65.

When a yellow pigment is used in combination with the phthalocyanine pigment represented by the general formula (1), the mass ratio of the yellow pigment / the phthalocyanine pigment represented by the general formula (1) is 70/30 to 70/30 from the viewpoint of brightness and hue. The range of 10/90 is preferable. It is more preferably in the range of 70/30 to 20/80, and even more preferably in the range of 40/60 to 20/80.

(Miniaturization of colorants)
The colorant used in the coloring composition of the present invention is suitable as a colorant for a color filter by finening the colorant particles by, if necessary, salt milling treatment or the like in order to obtain high brightness and high contrast. Can be used for. The volume average primary particle size of the colorant is preferably 10 nm or more in order to enhance the dispersibility in the colorant carrier. Further, in order to obtain a filter segment having high contrast, it is preferably 80 nm or less. In one embodiment, it is more preferably in the range of 20 to 60 nm, and even more preferably in the range of 30 to 50 nm.

The salt milling treatment is synonymous with the solvent salt milling method described above in the section “Miniaturization of phthalocyanine pigment”.

<Binder resin>
The binder resin may be any one that disperses a colorant such as a pigment or a pigment, particularly a phthalocyanine pigment represented by the general formula (1). Specific examples of the binder resin include thermoplastic resins and thermosetting resins.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, cardo resin, and phenol resin.

The thermosetting resin may be a low molecular weight compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts when the filter segment is fired, the crosslink density of the coating film is increased, the heat resistance is improved, and the pigment aggregation during the firing of the filter segment is suppressed. Be done. Among these, epoxy resin, cardo resin, or melamine resin is preferable.

When a color filter is produced using the coloring composition, the binder resin is a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is preferable.
The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

Since the binder resin has good film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 30 parts by mass or more in terms of resin solid content with respect to 100 parts by mass of the total mass of the colorant, and the colorant concentration is high. Since good color characteristics can be exhibited, it is preferable to use the resin solid content in an amount of 500 parts by mass or less. In one embodiment, the binder resin is preferably used in an amount of 50 to 500 parts by mass, more preferably 100 to 400 parts by mass, based on 100 parts by mass of the total mass of the colorant.

In one embodiment, when the coloring composition is used in the form of an alkali-developing colored resist material, an alkali-soluble vinyl-based resin prepared by using an acidic group-containing ethylenically unsaturated monomer from the viewpoint of developability. Is preferably used as the binder resin. Further, in another embodiment, a photosensitive coloring composition may be formed for the purpose of improving the light sensitivity and the solvent resistance. In this case, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used as the binder resin. Hereinafter, these embodiments will be described in more detail.

As the vinyl-based alkali-soluble resin that can be suitably used as a binder, for example, a homopolymer or a copolymer prepared by using an ethylenically unsaturated monomer having an acidic group such as a carboxy group, a hydroxyl group, or a sulfone group. Can be mentioned. Specific examples of the vinyl-based alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, and an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (anhydrous) maleic acid copolymer and the like. Of these, at least one resin selected from a (meth) acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer is preferable. In particular, a (meth) acrylic resin having an acidic group is preferably used because it has high heat resistance and transparency.

As the acidic group in the acidic group-containing ethylenically unsaturated monomer used for preparing the resin, those having a carboxylic acid or a hydroxyl group are preferable. Examples of ethylenically unsaturated monomers having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. Examples of ethylenically unsaturated monomers having a hydroxy group include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4 Examples thereof include −hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (preferably 1 to 5 addition moles).

In one embodiment, when a photosensitive coloring composition for a color filter is formed, the binder resin is a colorant adsorbing group and an alkali during development from the viewpoints of pigment dispersibility, permeability, developability, and heat resistance. The balance between the carboxy group acting as a soluble group and the aliphatic group and the aromatic group acting as an affinity group for the colorant carrier and the solvent is the weight. In one embodiment, from the viewpoint of pigment dispersibility, permeability, developability, and durability, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g as the binder resin. By using a resin having an acid value within the above range, appropriate solubility in a developing solution can be obtained, and it becomes easy to form a fine pattern.

From the above viewpoint, the vinyl-based alkali-soluble resin obtained by polymerizing the acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mgKOH / g and a weight average molecular weight (Mw) of 10,000 to 80. It is preferably 000. In one embodiment, the resin may be a copolymer of methacrylic acid, 2-hydroxyethyl (meth) acrylate, and other monomers such as n-butyl methacrylate.

As another embodiment, when a photosensitive coloring composition is formed as an alkali-developable coloring resist for a color filter, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin. In particular, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. When the above resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, foreign matter in the coating film is not generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When the linear resin having no ethylenically unsaturated double bond in the side chain is used, the colorant is less likely to be trapped by the resin in a liquid in which the resin and the colorant are mixed, and has a degree of freedom. As a result, the colorant component is likely to aggregate and precipitate. On the other hand, when an active energy ray-curable resin having an ethylenically unsaturated double bond is used in the side chain, the colorant is likely to be trapped in the resin in a liquid in which the resin and the colorant are mixed. Therefore, in the solvent resistance test, the dye is less likely to elute, and the colorant component is less likely to aggregate and precipitate. Further, when the resin is three-dimensionally crosslinked to form a film by exposure with active energy rays, the colorant molecules are fixed, and even if the solvent is removed in the subsequent developing step, the colorant components are aggregated and precipitated. It is estimated that it will be difficult to do.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (a) and (b) shown below.

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other monomers is used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. , And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. It remained by using a tricarboxylic acid anhydride such as trimellitic dianhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride as needed, such as by increasing the number of carboxyl groups. It is also possible to hydrolyze the anhydride group. Further, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further increased.

As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group with one or more other monomers. There is a method of introducing an unsaturated ethylenically double bond and a carboxyl group by adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxy group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and by copolymerizing with another unsaturated monobasic acid monomer having a carboxy group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

<Organic solvent>
In the coloring composition of the present invention, the filter segment is formed by sufficiently dissolving the coloring agent in a monomer, a resin, or the like, and further applying the colorant on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, and 1,4-dioxane. , 2-Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, o-xylene, o-chlorotoluene, o-diethylbenzene , O-Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, and isophorone.
Furthermore, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene. Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Vryx acetate, dibasic acid ester and the like.
These organic solvents may be used alone or in admixture of two or more.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl are good because of the good dispersibility and permeability of the colorant and the applicability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, the amount is 500 to 4000 parts by mass with respect to 100 parts by mass of the total mass of the colorant. It is preferable to use in. In one embodiment, the organic solvent is used in an amount of more preferably 500 to 2000 parts by mass, still more preferably 500 to 1000 parts by mass, based on 100 parts by mass of the total mass of the colorant.

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a coloring agent containing a phthalocyanine pigment represented by the general formula (1) is contained in a coloring agent carrier composed of the binder resin and, if necessary, a solvent, preferably a dye derivative or the like. Together with the dispersion aid, it can be finely dispersed and produced by using various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Further, if the phthalocyanine pigment represented by the general formula (1) is highly soluble, specifically, if it is highly soluble in the organic solvent used, is dissolved by stirring, and no foreign matter is confirmed. It is not necessary to disperse and manufacture as described above.

Further, the coloring composition of the present invention is produced by separately mixing a pigment, a phthalocyanine pigment represented by the general formula (1), another coloring agent, etc., dispersed in a coloring agent carrier such as a binder resin. You can also do it.

[Dispersion aid]
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the colorant and has a great effect of preventing the reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid is used. When used, a color filter having high spectral transmittance can be obtained.

<Dye derivative>
Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acrydone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent. For example, those described in JP-A-63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Patent Publication No. 5-1469, etc. They can be used alone or in admixture of two or more.

The blending amount of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. From the viewpoint of heat resistance and light resistance, the blending amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant.

<Resin type dispersant>
In the present invention, it is preferable to include a resin-type dispersant from the viewpoint of viscosity stability.
The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the colorant and a moiety compatible with the colorant carrier, and adsorbs to the colorant to stabilize the dispersion on the colorant carrier. It works. Specifically, as the resin type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, and modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone. Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Examples of commercially available resin-type dispersants include the following.
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, manufactured by Big Chemie Japan. 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, Or Lactimon, Lactimon-WS or Bykumen and the like.
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Japan Lubrizol. 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.
BASF's EFKA-46, 47, 48, 452, 4008, 4060, 4406, 4408, 450, 451, 453, 4540, 4800, 5070, 7500, 7554, 1101, 120, 150, 1502, Efka PU 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4061, 4063, 4080, Efka PA 4400, 4401, 4402, 4403, 4414, 4450, Efka PX 4300, 4310, 4320, 4330, 4340, 4350, 4700, 4701, 4731, 4732, Efka FA4610, 4665, 4666, Dispex Ultra PA 4501, 4503, 4550, 4560, 4580, 4590 and the like.
Ajinomoto Fine Techno Co., Ltd. Ajispar PA111, PB711, PB821, PB822, PB824, etc.

Examples of the surfactant include the following.
Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate , Anionic surfactants such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
An amphoteric surfactant such as alkyl betaine such as alkyldimethylaminoacetic acid betaine and alkyl imidazoline.
These can be used alone or in admixture of two or more, but are not necessarily limited to these.

When a resin-type dispersant and / or a surfactant is added, the blending amount thereof is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 55 parts by mass with respect to 100 parts by mass of the colorant, respectively, from the viewpoint of the effect on dispersion. Is 0.1 to 45 parts by mass.
As one embodiment, the colorant may be independently dispersed before the dispersion treatment on the colorant carrier such as the binder resin. That is, after preparing a pigment dispersion by a pigment dispersion treatment, it may be used as a colorant.

In one embodiment, the coloring composition of the present invention may further contain at least one of a photopolymerizable monomer and a photopolymerization initiator in the colorant, the binder resin, and the organic solvent. The coloring composition of such an embodiment can be suitably used as a photosensitive coloring composition for a color filter. Further, the coloring composition of the present invention may contain a sensitizer, a polyfunctional thiol, an amine compound, a leveling agent, a curing agent, a curing accelerator, and other additive components in addition to the above-mentioned components. .. Hereinafter, each component will be described.

<Photopolymerization initiator>
The coloring composition of the present invention can contain a photopolymerization initiator. When the photopolymerization initiator is used, the blending amount is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the phthalocyanine pigment represented by the general formula (1), and 10 to 150 parts by mass from the viewpoint of photocurability. More preferably, it is by mass.

As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specifically, the following can be mentioned.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo [2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2 Acetphenones such as -methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Others such as phenylglycolic methyl ester.
More specifically, Irga Cure 651, Irga Cure 184, Daro Cure 1173, Irga Cure 500, Irga Cure 1000, Irga Cure 2959, Irga Cure 907, Irga Cure 369, Irga Cure 379, Irga Cure 1700, Irga Cure 149, Irga. Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01, Irgacure OXE-02 (BASF), ADEKA OPTMER N1717, ADEKA OPTMER N1919, ADEKA ARCULS 831 (ADEKA) and Esacure1001M (Lamberti) can be mentioned.

In addition, the triazine derivatives described in JP-A-59-1281, JP-A-61-9621 and JP-A-60-60104, and JP-A-59-1504 and JP-A-61-243807. Organic peroxides, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and Diazonium Compound Publication No. USP No. 3567453, USP No. 2848328, USP No. 2852379 and USP 2940853 organic azide compounds, JP-A-36-22062, JP-A-37-13109, JP-A-38-18015 and JP-A-45-9610. Ortho-quinone diazodes, JP-A-55-39162, JP-A-59-140203, and the iodonium compounds described in "MACROMOLECULES", Vol. 10, p. 1307 (1977). Examples thereof include various onium compounds and azo compounds described in JP-A-59-142205.
Further, Japanese Patent Application Laid-Open No. 1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J.IMAG.SCI)", Vol. 30, No. 174. Metal Allen Complex described on page (1986), Titanosens described in JP-A-61-151197, "COORDINATION CHEMISTRY REVIEW", Vol. 84, pp. 85-277 (1988). ) And the transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, the aluminate complex described in JP-A-3-209477, and the borate compound described in JP-A-2-157760. 2,4,5-Triarylimidazole dimer described in JP-A-55-127550 and JP-A-60-202437, carbon tetrabromide, and organic halogen compounds described in JP-A-59-107344. , JP-A-5-255347, sulfonium complex or oxosulfonium complex, JP-A-54-99185, JP-A-63-264560, and JP-A-10-299777, aminoketone compounds, JP-A-2001-264530. Japanese Patent Application Laid-Open No. 2001-261716, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2001-233842, Japanese Patent Application Laid-Open No. 2004-534977, Japanese Patent Application Laid-Open No. 2006-342166, Japanese Patent Application Laid-Open No. 2008-094770, Japanese Patent Application Laid-Open No. 2009 -40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010-189280, Japanese Patent Application Laid-Open No. 2010-526846, Japanese Patent Application Laid-Open No. 2010-527338, Japanese Patent Application Laid-Open No. 2010-527339, USP3558309 (1971), USP4202697 No. 6 (1980) and the oxime ester compound described in JP-A-61-24558 can be mentioned.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary. In one embodiment, it is preferable to use an α-aminoalkylphenone-based compound or an oxime ester-based compound from the viewpoint of patterning sensitivity. For example, select from the group consisting of the above-exemplified Irgacure 907, Irgacure 369, Irgacure 379, Irgacure OXE-01, Irgacure OXE-02 (manufactured by BASF), and ADEKA Optomer N1919 (manufactured by ADEKA). At least one of the above can be used.

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin, and these can be used alone or in combination of two or more. More specifically, the photopolymer monomer is a compound having one or more photopolymerizable groups in the molecule, and its molecular weight is typically 1000 or less.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and epoxy (meth). Acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, Polyester (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Tris (Acryloxyethyl) Isocyanurate, Tris (Methyloxyethyl) Isocyanurate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) ) Acrylate, various acrylic acid esters such as caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate, and methacrylic acid ester, (meth) acrylic acid, styrene, acetic acid. Vinyl, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned, but the effects of the present invention are limited thereto. It is not something that is done.

Further, the photopolymerizable monomer may contain an acid group. For example, esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acid and monohydroxyalkyl (meth) acrylates, etc. Can be mentioned. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates, but the effects of the present invention are limited thereto. It is not something that is done.

In one embodiment, it is preferable to use a polyfunctional monomer having a plurality of photopolymerizable groups in one molecule from the viewpoint of patterning sensitivity and adhesion to a glass substrate. The polyfunctional monomer preferably has 3 to 6 photopolymerizable groups per molecule. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used. For example, the trade name "Aronix M-402" manufactured by Toagosei Co., Ltd. and "A-DPH" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. can be used.

The content of the photopolymerizable monomer is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the colorant from the viewpoint of photocurability and developability. , More preferably in an amount of 20 to 100 parts by mass.

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo Examples thereof include porphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropirane derivatives, spiroxazine derivatives, thiospiropirane derivatives, metal arene complexes, and organic ruthenium complexes. , Not limited to these.

More specific examples include Nobu Ogawara et al., "Dye Handbook" (1986, Kodansha), Nobu Ogawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "Special". Examples include dyes and sensitizers described in "Functional Materials" (1986, CMC). However, the present invention is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near infrared region may be used. Two or more of these may be used in any ratio as required.
Among the sensitizers exemplified above, the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4. -Propoxythioxanthone and the like can be mentioned. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-bis (diethylamino) benzophenone. be able to. Examples of coumarins include coumarin 1, coumarin 338, coumarin 102 and the like. Examples of ketocoumarins include 3,3'-carbonylbis (7-diethylaminocoumarin) and the like. However, it is not limited to these.

Two or more sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the total mass of the photopolymerization initiator (E) contained in the colored photosensitive composition, and is photocured. From the viewpoint of sex, it is more preferably 5 to 50 parts by mass. In one embodiment, it is preferable to use a benzophenone derivative from the viewpoint of patterning sensitivity. For example, the trade name "EAB-F" manufactured by Hodogaya Chemical Co., Ltd. can be used.

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that acts as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanthithioglycolate, trimethylolpropanetristhiopropionate, trimethylolpropanthris (5-mercaptobutyrate), pentaerythritol tetraxthioglycolate Pentaerythritol tetraxthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-) Dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned.
These polyfunctional thiols can be used alone or in admixture of two or more at any ratio as required.

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the mass of the total solid content of the coloring composition (100% by mass). If the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-333 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably used in a ratio of 0.003 to 0.5% by mass based on 100% by mass of the total coloring composition.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. More specifically, it preferably has the characteristics that it has a hydrophilic group but has low solubility in water, and when added to a coloring composition, its surface tension lowering ability is low. In addition, those having good wettability to the glass plate despite having low surface tension lowering ability are useful, and those capable of sufficiently suppressing chargeability at an addition amount that does not cause defects in the coating film due to foaming. It can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyoxyalkylene alkyl ether such as polyethylene glycol monolaurate; alkyl betaine such as alkyldimethylaminoacetic acid betaine, amphoteric surfactant such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg, dimethylamine). 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.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-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 can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (5, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (5,4-epoxycyclohexyl) methyltrimethoxysilane, β- (5,4-epoxycyclohexyl) ethyltriethoxysilane, β- (5,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total amount of the colorant in the coloring composition.

Although not particularly limited, in one embodiment, the coloring composition includes a coloring agent containing a phthalocyanine pigment represented by the general formula (1), a binder resin, and an organic solvent. Here, as the binder resin, it is preferable to use a vinyl-based alkali-soluble resin prepared by using an acidic group-containing ethylenically unsaturated monomer. In another embodiment, the coloring composition further comprises a photopolymerization initiator and a photopolymerizable monomer in addition to the above components. In another embodiment, the coloring composition further comprises a sensitizer in addition to the above components. In these embodiments, in particular, a vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer is used as the binder resin, and a plurality of photopolymerizable groups are contained in one molecule as the photopolymerizable monomer. It is preferable to use a polyfunctional monomer having. Here, it is more preferable to use a copolymer of a (meth) acrylic polymerizable monomer having an acidic group and another polymerizable monomer as the binder resin. According to such an embodiment, it becomes easy to obtain a coloring composition having excellent developability, pattern sensitivity, and glass adhesion.

<Removal of coarse particles>
As described above, the coloring composition of the present invention can be produced by finely dispersing each component using various dispersion means. In one embodiment, by using means such as centrifugation, sintering filter, membrane filter, etc., coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more in the coloring composition. It is preferable to remove particles and mixed dust. Here, the coarse particles mean a secondary particle state in which primary particles are aggregated. Therefore, it is preferable that the coloring composition does not contain secondary particles having a size of 0.5 μm or more. In one embodiment, the particle size of the particles in the coloring composition is preferably less than 0.5 μm, more preferably 0.3 μm or less.

<Color filter>
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment.

As the base material such as the transparent substrate constituting the color filter, glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate are used. Used. Further, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the paneling.

<Manufacturing method of color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method using the above coloring composition.

The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as the printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. There is. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, the developing solution is immersed in a solvent or an alkaline developing solution, or the developing solution is sprayed by a spray or the like to remove the uncured portion to form a desired pattern. A color filter can be manufactured by repeating the same operation for other colors. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above methods, and the coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

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

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optical convencend bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by mass" unless otherwise specified.

The phthalocyanine of the present invention is identified by the molecular ion peak of the mass spectrum obtained by using a time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by Bruker Daltonics) and the mass number obtained by calculation. The results were based on the agreement with the theoretical values and the ratios of carbon, hydrogen and nitrogen obtained by using an elemental analyzer (2400CHN elemental analyzer, manufactured by PerkinElmer).

The average number of halogen atom substitutions in the pigment is determined by burning the pigment by the oxygen combustion flask method and absorbing the burned material in water by using an ion chromatograph (ICS-2000 ion chromatography, manufactured by DIONEX). ) Was used to quantify the amount of halogen, which was then converted to the average number of halogen atom substitutions.

<Manufacturing of phthalocyanine pigment>
[Manufacturing Example 1]
(Manufacturing of phthalocyanine pigment (CP-1))
In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine.
Then, in the reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 205 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was injected into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, dried, and dried, and the following chemical formula (5). ) Was obtained.
When the number of bromine substitutions was calculated for the obtained hydroxyaluminum phthalocyanine, the average number was 8, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum.

Chemical formula (5)

Next, 120 parts of hydroxyaluminum phthalocyanine and 50 parts of p-toluenethiol were placed in 2400 parts of 1-methyl-2-pyrrolidinone in a reaction vessel. After reacting at 95 ° C. for 3 hours, the solution was injected into 12000 parts of water. The reaction product was filtered, washed with 16000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 117 parts of a blue product.
The resulting blue product was then slowly added to 1800 parts of concentrated sulfuric acid at room temperature. The sulfuric acid solution was injected into 24,000 parts of cold water at 3 ° C. with stirring at 40 ° C. for 3 hours. The blue precipitate was filtered, washed with water and dried to obtain 112 parts of a phthalocyanine pigment (CP-1). When the number of thiol substitutions and the number of bromine substitutions were calculated for the obtained phthalocyanine pigment (CP-1), the average number was 4 each, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum.

[Manufacturing Example 2]
(Manufacturing of phthalocyanine pigment (CP-2))
In the production of the phthalocyanine pigment (CP-1), hydroxyaluminum phthalocyanine was produced in the same manner as in Production Example 1 except that 205 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 129 parts.
When the number of bromine substitutions was calculated for the obtained hydroxyaluminum phthalocyanine, the average number was 5, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum.
Next, 120 parts of hydroxyaluminum phthalocyanine and 50 parts of p-toluenethiol were placed in 2400 parts of 1-methyl-2-pyrrolidinone in a reaction vessel. After reacting at 95 ° C. for 3 hours, the solution was injected into 12000 parts of water. The reaction product was filtered, washed with 16000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 105 parts of a blue product.
The resulting blue product was then slowly added to 1800 parts of concentrated sulfuric acid at room temperature. The sulfuric acid solution was injected into 24,000 parts of cold water at 3 ° C. with stirring at 40 ° C. for 3 hours. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of a phthalocyanine pigment (CP-2). When the number of thiol substitutions and the number of bromine substitutions were calculated for the obtained phthalocyanine pigment (CP-2), the average number was 1 thiol and 4 bromine, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum. ..

[Manufacturing Example 3]
(Manufacturing of phthalocyanine pigment (CP-3))
In the production of the phthalocyanine pigment (CP-1), hydroxyaluminum phthalocyanine was produced in the same manner as in Production Example 1 except that 205 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 555 parts.
When the number of bromine substitutions was calculated for the obtained hydroxyaluminum phthalocyanine, the average number was 16, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum.
Next, 120 parts of hydroxyaluminum phthalocyanine and 131 parts of p-toluenethiol were placed in 2400 parts of 1-methyl-2-pyrrolidinone in a reaction vessel. After reacting at 95 ° C. for 3 hours, the solution was injected into 12000 parts of water. The reaction product was filtered, washed with 16000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 125 parts of a blue product.
The resulting blue product was then slowly added to 1800 parts of concentrated sulfuric acid at room temperature. The sulfuric acid solution was injected into 24,000 parts of cold water at 3 ° C. with stirring at 40 ° C. for 3 hours. The blue precipitate was filtered, washed with water and dried to obtain 122 parts of a phthalocyanine pigment (CP-3). When the number of thiol substitutions and the number of bromine substitutions were calculated for the obtained phthalocyanine pigment (CP-3), the average number was 15 thiols and 1 bromine, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum. ..

[Manufacturing Example 4]
(Manufacturing of phthalocyanine pigment (CP-4))
In the reaction vessel, 225 parts of 4-methylphthalodinitrile and 53 parts of aluminum chloride anhydride were mixed and stirred with 1350 parts of octanol. To this, 265 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 120 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 16200 parts of methanol and 10800 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 150 parts of chloroaluminum phthalocyanine represented by the following chemical formula (6). Elemental analysis of the obtained chloroaluminum phthalocyanine revealed that the measured values (C) 66.85%, (H) 2.80%, and (N) 19.49% were measured. It was 7%, (H) 3.0%, and (N) 19.2%, and it was identified as the target compound.

Chemical formula (6)

Then, in the reaction vessel, 120 parts of the chloroaluminum phthalocyanine was added to 2400 parts of concentrated sulfuric acid under an ice bath. Then, 140 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was injected into 12,000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, and dried to 144 parts of phthalocyanine. A pigment (CP-4) was obtained. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-4), the average number was 4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound.

[Manufacturing Example 5]
(Manufacturing of phthalocyanine pigment (CP-5))
In the production of the phthalocyanine pigment (CP-1), 102 parts of the phthalocyanine pigment (CP-5) was obtained in the same manner as in Production Example 1 except that 50 parts of p-toluenethiol was changed to 77 parts of 2-ethylhexyl thioglycolic acid. Manufactured. When the number of thiol substitutions and the number of bromine substitutions were calculated for the obtained phthalocyanine pigment (CP-5), the average number was 4 each, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum.

[Manufacturing Example 6]
(Manufacturing of phthalocyanine pigment (CP-6))
In the production of the phthalocyanine pigment (CP-1), 101 parts of the phthalocyanine pigment (CP-6) was produced in the same manner as in Production Example 1 except that 50 parts of p-toluenethiol was changed to 48 parts of 4-methylbenzyl alcohol. Manufactured. When the number of oxy substitutions and the number of bromine substitutions were calculated for the obtained phthalocyanine pigment (CP-6), the average number was 4 each, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum.

[Manufacturing Example 7]
(Manufacturing of phthalocyanine pigment (CP-7))
In the production of the phthalocyanine pigment (CP-4), 107 parts of the phthalocyanine pigment (CP-) was obtained in the same manner as in Production Example 4, except that 140 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 42 parts. 7) was manufactured. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-7), the average number was 1, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[Manufacturing Example 8]
(Manufacturing of phthalocyanine pigment (CP-8))
In the production of the phthalocyanine pigment (CP-4), 193 parts of the phthalocyanine pigment (CP-) were obtained in the same manner as in Production Example 4, except that 140 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 252 parts. 8) was manufactured. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-8), the average number was 8, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound.

[Manufacturing Example 9]
(Manufacturing of phthalocyanine pigment (CP-9))
In the production of the phthalocyanine pigment (CP-4), 205 parts of the phthalocyanine pigment (CP-) were obtained in the same manner as in Production Example 4, except that 140 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 378 parts. 9) was manufactured. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-9), the average number was 12, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound.

[Manufacturing Example 10]
(Manufacturing of phthalocyanine pigment (CP-10))
In the production of the above-mentioned phthalocyanine pigment (CP-4), 102 parts of the phthalocyanine pigment (12 parts) were obtained in the same manner as in Production Example 4, except that 140 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 76 parts of trichloroisocyanuric acid. CP-10) was manufactured. When the number of chlorine substitutions was calculated for the obtained phthalocyanine pigment (CP-10), the average number was 4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound.

[Manufacturing Example 11]
(Manufacturing of phthalocyanine pigment (CP-11))
Production Example 4 in the production of the above phthalocyanine pigment (CP-4), except that 140 parts of 1,3-dibromo-5,5-dimethylhydranthin was changed to 186 parts of 1,3-diiodo-5,5-dimethylhydranthin. In the same manner as above, 130 parts of a phthalocyanine pigment (CP-11) was produced. When the number of iodine substitutions was calculated for the obtained phthalocyanine pigment (CP-11), the average number was 4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound.

[Example 12]
(Manufacture of phthalocyanine pigment (P-1))
To the reaction vessel, 2000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the phthalocyanine pigment (CP-1) obtained in Example 1, and 27.6 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, the solution was injected into 16000 parts of water. The reaction product was filtered, washed with 16000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 125 parts of a blue product. Then, the obtained blue product was added to 600 parts of propylene glycol monomethyl ether acetate, and the mixture was heated at 120 ° C. for 2 hours. The product was filtered and dried under reduced pressure at 60 ° C. for 24 hours to obtain 121 parts of a phthalocyanine pigment (P-1). When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-1), the average number was 4, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound.

[Examples 13 to 26]
(Manufacture of phthalocyanine pigments (P-2 to 15))
In the production of the phthalocyanine pigment (P-1), the same operations as in Example 12 were carried out except that the raw material phthalocyanine pigment and the acidic compound were changed to the compositions and blending ratios shown in Table 1, respectively. (P-2 to 15) were obtained. Table 2 shows the average values of the substituent species and the number of substitutions, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound.

<Manufacturing of comparative phthalocyanine pigments>
[Comparative Example 1] (Production of Phthalocyanine Pigment (P-16))
In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was injected under stirring into a mixed solvent of 5000 parts of methanol and 10000 parts of water to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine.
Then, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. The sulfuric acid solution was injected into 24,000 parts of cold water at 3 ° C. with stirring at 40 ° C. for 3 hours. The blue precipitate was filtered, washed with water and dried to obtain 101 parts of hydroxyaluminum phthalocyanine (CP-12).
Next, 100 parts of the obtained phthalocyanine pigment (CP-12) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol and dried to obtain 114 parts of a phthalocyanine pigment (P-16).

[Comparative Example 2] (Production of Phthalocyanine Pigment (P-17))
In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine.
Then, in the reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 185 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was injected into 9000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, dried, and 160 parts of phthalocyanine. A pigment (CP-13) was obtained. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-13), the average number was 8, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum.
Next, 100 parts of the obtained phthalocyanine pigment (CP-13) and 31.6 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to obtain 115 parts of a phthalocyanine pigment (P-17).

[Comparative Example 3] (Production of Phthalocyanine Pigment (P-18))
In the production of the phthalocyanine pigment (CP-4), after the chloroaluminum phthalocyanine represented by the chemical formula (6) was obtained, the same operation as in Example 12 was carried out to obtain a phthalocyanine pigment (P-18).

[Comparative Example 4] (Production of Phthalocyanine Pigment (P-19))
In the production of the phthalocyanine pigment (P-1), the same operations as in Example 12 were carried out except that the raw material phthalocyanine pigment and the acidic compound were changed to the compositions and blending ratios shown in Table 1, respectively, and the phthalocyanine pigment (P-1) was produced. P-19) was obtained. Table 2 shows the average values of the substituent species and the number of substitutions, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound.

<Coloring composition>
The following examples relate to a coloring composition (pigment dispersion) using the phthalocyanine pigment produced earlier. The dispersant and binder resin used were produced as follows.

<Manufacturing method of binder resin>
(Preparation of acrylic resin solution 1)
70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000.
After cooling the resin solution to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Next, in consideration of the measured values, propylene glycol monoethyl ether acetate was added so that the non-volatile content was 20% by mass to prepare an acrylic resin solution 1.

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

(Acid value of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 part of the resin solution and stirred to uniformly dissolve the solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator (“COM-555”” The acid value of the resin solution was measured by titration using (manufactured by Hiranuma Sangyo). 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.

<Preparation of resin type dispersant solution>
A commercially available resin-type dispersant, Efka PX4300 manufactured by BASF, and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a non-volatile content of 40% by mass to obtain a resin-type dispersant solution 1.

<Manufacturing of pigment dispersion>
[Example 27]
(Pigment dispersion (GP-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 4 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.1 mm. Then, the obtained mixture was filtered through a filter having a pore size of 5.0 μm to prepare a pigment dispersion (GP-1) having a non-volatile component of 20% by mass.
Phthalocyanine pigment (P-1): 11.0 parts Acrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate (PGMAc): 66.5 parts Resin type dispersant solution 1: 5.0 parts

[Examples 28 to 41, Comparative Examples 6 to 10]
(Pigment dispersions (GP-2) to (GP-20))
Pigment dispersions (GP-2) to (GP-20) were prepared in the same manner as in Example 27, except that the phthalocyanine pigment (P-1) was changed to the phthalocyanine pigment shown in Table 3.

<Evaluation of pigment dispersion>
The pigment dispersions (GP-1) to (GP-20) obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 3.

<Initial viscosity evaluation>
The viscosity of the coloring composition was measured at 25 ° C. on the day of adjustment using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm (initial viscosity). In the evaluation results below, ⊚ is very good, ◯ is good, Δ is a level with high viscosity but no problem in use, and × is a level with problem in use.
⊚: Less than 10.0 [mPa · s]
◯: 10.0 or more and less than 15.0 [mPa · s]
Δ: 15.0 or more and less than 20.0 [mPa · s]
X: 20.0 or more [mPa · s]

(Evaluation of filterability)
10 g of the obtained coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) at nitrogen pressure (0.3 MPa), and the amount obtained through the filter was measured and evaluated according to the following criteria. did.
⊚: Filtration amount is 9.0 g or more
〇: Filtration amount is 5.0 g or more and less than 9.0 g
Δ: Filtration amount is 3.0 g or more and less than 5.0 g
X: Filtration amount is 3.0 g or less

When there was no substituent as in Comparative Example 6, the result was poor filterability. Further, in Comparative Examples 7 and 8 in which only the halogen group or only the methyl group was substituted, the filterability was also poor. Further, in Comparative Example 9 in which Z of the general formula (1) did not have the structure specific to the present application, the storage stability was deteriorated. In Comparative Example 10 to which no acidic compound was added, both the initial viscosity and the filterability were poor.
On the other hand, in Examples 27 to 41 of the present invention, the initial viscosity was low and the filterability was excellent.

<Manufacturing of other refined pigments>
(Manufacturing of refined green pigment (PG58-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a fine green pigment (PG58-1).

(Manufacturing of refined green pigment (PG7-1))
Phthalocyanine-based green pigment C.I. I. 200 parts of Pigment Green 7 (“GreenGNX” manufactured by CLARIANT), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a fine green pigment (PG7-1).

(Manufacturing of refined green pigment (PG36-1))
Phthalocyanine-based green pigment C.I. I. 200 parts of Pigment Green 36 (“Green8G” manufactured by CLARIANT), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a fine green pigment (PG36-1).

(Manufacturing of refined green pigment (PG62-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 62 (“OPTLION GREEN 8880” manufactured by TOYOCOLOR), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a fine green pigment (PG62-1).

(Manufacturing of refined yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a finely divided yellow pigment (PY150-1).

(Manufacturing of refined yellow pigment (PY138-1))
Kinoftalone yellow pigment C.I. I. Pigment Yellow 138 (BASF's "Pariotor Yellow L 0960HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a finely divided yellow pigment (PY138-1).

(Manufacturing of refined yellow pigment (PY139-1))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (BASF's "Pariotor Yellow L 2146HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a finely divided yellow pigment (PY139-1).

(Manufacturing of refined yellow pigment (PY185-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 185 (BASF "Pariotor Yellow L 1155"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a finely divided yellow pigment (PY185-1).

(Manufacturing of refined yellow pigments (BY-1, BY-2))
Kinophthalone compounds (5-1) and (5-2) were obtained according to the synthesis method described in JP-A-2012-226110.

Kinoftalone compound (5-1)

Chemical formula (5-2)

(Manufacturing of refined red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. Pigment Red 254 (BASF's "IRGAPHOR RED S3610 CF"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain 190 parts of a finely divided diketopyrrolopyrrole pigment (PR254-1).

(Manufacturing of refined red pigment (PR177-1))
Anthraquinone red pigment C.I. I. Pigment Red 177 (BASF's "Paliongen Red L4039"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain an anthraquinone-based finely divided red pigment (PR177-1).

(Manufacturing of refined blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyo Color "LIONOL BLUE ES", specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). , 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a fine blue pigment (PB15: 6-1).

(Manufacturing of refined purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a purple finely divided purple pigment (PV23-1).

<Manufacturing of other fine pigment dispersions>
(Miniaturized Pigment Dispersion (GP-21) to (GP-24), (YP-1) to (YP-6), (RP-1), (RP-2), (BP-1), (VP -1) Manufacture)
The pigment dispersions (GP-21) to (GP-24), ( YP-1) to (YP-6), (RP-1), (RP-2), (BP-1), and (VP-1) were prepared.

<Manufacturing of photosensitive coloring composition>
[Example 42]
(Green Photosensitive Coloring Composition (GR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
Pigment Dispersion (GP-1) (Green Pigment Dispersion): 42.3 Parts PY185 / Pigment Dispersion (YP-4) (Yellow Pigment Dispersion): 7.7 Parts Acrylic Resin Solution 1: 7.5 Parts Light Polymerizable monomer ("Aronix M-402" manufactured by Toa Synthetic Co., Ltd.): 2.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer (Hodogaya Chemical Industry Co., Ltd.) Manufactured by "EAB-F"): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 43 to 65, Comparative Examples 11 to 15]
In the green photosensitive coloring composition (GR-1), the green pigment dispersant and the yellow pigment dispersion so that the hue of the colored pixel layer described later becomes x = 0.210 and y = 0.685 in the C light source. The green photosensitive coloring compositions (GR-2) to (GR-29) were obtained in the same manner as in Example 42, except that the components and parts by mass were changed to those shown in Table 5.

<Evaluation of photosensitive coloring composition>
The photosensitive coloring compositions obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 5.

(Evaluation of brightness)
The photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and dried in a clean oven at 70 ° C. for 20 minutes. Then, after cooling this substrate to room temperature, ultraviolet light was exposed through a photomask using an ultra-high pressure mercury lamp.
Then, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped green colored pixel layer on the substrate. The hue of the colored pixel layer was adjusted so that x = 0.210 and y = 0.685 in the C light source. The brightness (Y) of the obtained colored pixels was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.
◎: 40.0 or more: Extremely good ○: 38.0 or more and less than 40.0: Good Δ: 36.0 or more and less than 38.0: Practical use ×: Less than 36.0: Practical use (evaluation of coloring power)
The film thickness when the chromaticity of y (C) = 0.685 was measured using the same coating film as that for which the brightness was evaluated was measured, and the determination was made according to the following four-step criteria. The smaller the film thickness that gives the chromaticity of x (C) = 0.210 and y (C) = 0.685, the greater the coloring power, and it can be said that it is superior.
⊚: Film thickness less than 2.0 μm (extremely good)
◯: Film thickness of 2.0 μm or more and less than 2.3 μm (good)
Δ: Film thickness of 2.3 μm or more and less than 2.6 μm (practical)
X: Film thickness 2.6 μm or more (not practical)

[ΔVHR (voltage retention rate change rate) evaluation]
The green photosensitive coloring composition (GR-1 to GR-28) is applied to a glass substrate having an ITO transparent electrode having an effective electrode size of 10 mm × 10 mm, and a spin coater is used to obtain a dry film thickness of 3.2 μm. After the coating film on the electrode portion was wiped off with a solvent, ^{ultraviolet exposure was performed at an integrated light amount of 50 mJ / cm 2} and developed with an alkaline developer at 23 ° C. to obtain a coating film substrate. Then, after heating at 230 ° C. for 20 minutes and allowing to cool, two sample-coated substrates for measurement were prepared.

The two sample-coated glass substrates were placed facing each other so that the ITO transparent electrode surfaces faced each other, and a small cell was prepared using a sealant so that the cell gap was 9 μm. A liquid crystal liquid is injected into this small cell between the cell gaps, a voltage is applied at a voltage of 5 V for 60 μsec at 50 ° C., and the cell voltage [V1] after 16.67 msec after the voltage is released is set to VHR manufactured by Toyo Corporation. Measured at -1S. The measured cell voltage was averaged, and the obtained cell voltage was used to obtain the initial VHR (%) from the following formula.
VHR (voltage retention rate) (%) = ([V1] / 5) x 100
The initial VHR measured cell sample was irradiated with LED illumination of 150,000 nits for 3 hours, and the VHR (%) after irradiation was measured again, and ΔVHR (voltage retention rate change rate) was calculated from the following formula.
ΔVHR = | Initial VHR-VHR after exposure |
It was evaluated on the following four stages.
⊚: 2% or less
◯: 2% or more and less than 5%
Δ: 5% or more and less than 10% Practical use
×: 10% or more not practical

When the substituent was only halogen as in Comparative Example 12, the result was that the coloring power was low. Further, even in Comparative Example 14 in which the acidic compound was other than the phosphoric acid compound, the coloring power was poor. Further, in Comparative Example 15 to which no acidic compound was added, the coloring power was good, but the brightness was low.
On the other hand, in Examples 42 to 65 of the present invention, the results were high in brightness and excellent in coloring power and ΔVHR. In addition, the phthalocyanine pigment of the present invention showed good results even when other green pigments and yellow pigments were used in combination.

<Making color filters>
A color filter was prepared using the green photosensitive coloring composition containing the phthalocyanine pigment of the present invention. The red photosensitive coloring composition and the blue photosensitive coloring composition used were prepared as follows.

(Red Photosensitive Coloring Composition (RR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).
PR254 / Pigment dispersion (RP-1): 30.0 parts PR177 / Pigment dispersion (RP-2): 20.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toa Synthetic Co., Ltd.) "Aronix M-402"): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer (Hodogaya Chemical Industry Co., Ltd. "EAB-F"): 0. 3 parts cyclohexanone: 39.0 parts

(Blue Photosensitive Coloring Composition (BR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a blue photosensitive coloring composition (BR-1).
PB15: 6 / Pigment dispersion (BP-1): 45.0 parts PV23 / Pigment dispersion (VP-1): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Toa Synthetic) "Aronix M-402" manufactured by Aronix M-402): 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.): 0.3 part cyclohexanone: 39.0 parts

[Example 66]
The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix was formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, after cooling this substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultra-high pressure mercury lamp.
Then, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (GR-4) of the present invention was used to form a green colored pixel layer in the same manner as the red colored pixel layer. Further, in the same manner, the blue photosensitive coloring composition (BR-1) was used to form a blue colored pixel layer to obtain a color filter (CF-1). The film thickness of each colored pixel layer was 2.0 μm.

The brightness and coloring power of the obtained color filter were evaluated. The measuring method is the same as in the case of evaluation of the pigment dispersion. All of the color filters using the green coloring composition of the present invention had high brightness and excellent coloring power. From the above, the effect of the phthalocyanine pigment of the present invention was proved.

Claims (9)

A phthalocyanine pigment represented by the following general formula (1).

General formula (1)

[In the formula, X represents a halogen atom. n is 1 to 15 representing the average value of the number of substitutions of the halogen atom.
Y is an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a heterocycle which may have a substituent, respectively. Represents a group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. m is 1 to 15 representing the average value of the substituents represented by Y.
Z represents −OP (= O) R ₁ R ₂ , where R ₁ and R ₂ independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents a good aryl group, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring. The average value n of the number of substitutions of the halogen atom represented by X of the phthalocyanine pigment represented by the general formula (1) is 1 to 8, and the average value m of the substituents represented by Y is 1 to 4. The phthalocyanine pigment according to claim 1. Y of the phthalocyanine pigment represented by the general formula (1) is an alkyl group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent. The phthalocyanine pigment according to claim 1 or 2. A coloring composition for a color filter comprising a colorant, a binder resin, and an organic solvent, wherein the colorant contains the phthalocyanine pigment according to any one of claims 1 to 3. Coloring composition. The coloring composition for a color filter according to claim 4, further comprising a resin-type dispersant. The coloring composition for a color filter according to claim 4 or 5, further containing a yellow pigment. The yellow pigment is C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. The coloring composition for a color filter according to claim 6, which is at least one selected from the group consisting of Pigment Yellow 185 and a quinophthalone pigment represented by the following general formula (2).
General formula (2)

[In the general formula (2), R ^{1 to} R ¹³ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxy group or a substituent which may have a substituent. Represents an aryl group that may have. However, ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ together have a substituent. Form an aromatic ring which may be used. ] The coloring composition for a color filter according to any one of claims 4 to 7, further containing a photopolymerizable monomer and / or a photopolymerization initiator. In a color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, at least one green filter segment is the coloring composition for a color filter according to any one of claims 4 to 8. A color filter formed by.