JP2018154792A - Coloring agent and method for producing coloring composition - Google Patents

Abstract

[Problem] To provide a coloring composition which is excellent in fastness (heat resistance, light resistance, solvent resistance), excellent in contrast ratio and dispersibility when used in a color filter, and does not generate foreign matters.
A coloring composition comprising a colorant obtained by reacting a phthalocyanine compound represented by the formula (1) with two kinds of phosphoric acid compounds represented by diphenyl phosphate and diphenylphosphinic acid.

[X is a halogen atom; n is 4 to 16; provided that the average value of the number of substitutions of X is 6 to 15, the distribution width is 4 or more; Y is —OH or —Cl]
[Selection figure] None

Description

  The present invention relates to a coloring composition and a color filter used for producing a color filter used for a color liquid crystal display device, an organic EL display device, a color image pickup tube element and the like.

  In the production of a green filter, it is common to use various phthalocyanine compounds as colorants, and among them, many color filter colorants using copper phthalocyanine compounds and zinc phthalocyanine compounds have been proposed. In order to achieve high brightness with the phthalocyanine compound, it is necessary to precisely control the absorption wavelength of the phthalocyanine compound itself and the absorption wavelength / absorbance derived from the aggregate formed at the time of coating. , A method of changing the central metal species, and a method of introducing a functional group into the phthalocyanine ring.

  Patent Document 1 proposes a composition for a color filter using an aluminum phthalocyanine compound using aluminum phthalocyanine and two kinds of reaction reagents.

  Patent Document 2 proposes a color filter composition using an aluminum halide phthalocyanine compound.

  However, the pigment compositions containing these aluminum phthalocyanine compounds are not sufficiently improved in problems such as high viscosity of the colored composition, insufficient contrast ratio, and generation of foreign matter on the resist coating film. It is.

Japanese Patent Laying-Open No. 2015-183126 JP, 2006-153481, A

  The problem to be solved by the present invention is a coloring composition and color excellent in fastness (heat resistance, light resistance, solvent resistance), excellent in contrast ratio and dispersibility when used in a color filter, and free from foreign matter. To provide a filter.

  That is, the present invention is a method for producing a colorant obtained by reacting a phthalocyanine compound represented by the following general formula (1) with a phosphoric acid compound, wherein at least the following general formula (2) and The present invention relates to a method for producing a colorant characterized by using two types of phosphoric acid compounds (3).

General formula (1)

[In General Formula (1), X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X is 6 to 15, and the halogen distribution width is 4 or more. Y is —OH or —Cl. ]

[In General Formulas (2) and (3), R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, An alkoxyl group which may have a substituent or an aryloxy group which may have a substituent is represented. However, general formula (2) and general formula (3) are different compounds. ]

  Moreover, this invention is a manufacturing method of the coloring composition containing a coloring agent, binder resin, and an organic solvent at least, Comprising: A coloring agent reacts the phthalocyanine compound and phosphoric acid compound which are represented by following General formula (1). It is related with the manufacturing method of the coloring composition characterized by using at least 2 types of phosphoric acid compounds of following General formula (2) and (3) as a phosphoric acid compound.

General formula (1)

[In General Formula (1), X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X is 6 to 15, and the halogen distribution width is 4 or more. Y is —OH or —Cl. ]

[In General Formulas (2) and (3), R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, An alkoxyl group which may have a substituent or an aryloxy group which may have a substituent is represented. However, general formula (2) and general formula (3) are different compounds. ]

  Moreover, this invention relates to the manufacturing method of the said coloring composition in which a coloring agent contains a green pigment | dye and / or a yellow pigment | dye further.

  In the present invention, the green pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. Pigment Green 58 is at least one selected from the group consisting of C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. The present invention relates to a method for producing the colored composition, which is at least one selected from the group consisting of CI Pigment Yellow 185.

  Furthermore, this invention relates to the manufacturing method of the said coloring composition containing a photopolymerizable monomer and / or a photoinitiator further.

  The colored composition of the present invention can provide a color filter that is excellent in fastness (heat resistance, light resistance, solvent resistance), has high brightness and high contrast ratio, and does not generate foreign matter.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ". Further, “CI” mentioned in the present specification means a color index (CI).

<Colorant>
A method for producing a colorant obtained by reacting a phthalocyanine compound represented by the following general formula (1) and a reaction reagent, wherein at least two kinds of the following general formulas (2) and (3) are used as reaction reagents: It is a manufacturing method of the coloring agent characterized by using a phosphoric acid compound.

[Phthalocyanine compound represented by general formula (1)]
General formula (1)

[In General Formula (1), X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X is 6 to 15, and the halogen distribution width is 4 or more. Y is —OH or —Cl. ]

  Here, “halogen” includes fluorine, bromine, chlorine, and iodine, and two or more kinds may be used in combination. As the halogen, bromine, chlorine and iodine are preferable, and bromine is particularly preferable.

  In the phthalocyanine pigment represented by the general formula (1), the average value of the number of substitutions of the halogen atom represented by X is 6 to 15, and 8 to 15 is preferable from the viewpoint of hue and fastness. The halogen distribution width is 4 or more, and preferably 4-9. It is clear that when the halogen distribution width is 4 or more, the association between phthalocyanine molecules is remarkably suppressed, which greatly contributes to the increase in particle size due to the association between molecules, and further to the reduction in contrast. became. Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigment represented by the general formula (1). In the mass spectrum obtained by mass spectrometry, the halogen distribution width calculates the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value (total peak value) obtained by integrating each peak value, The number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width.

[Two types of phosphate compounds of general formulas (2) and (3)]
The reaction reagent which is a phosphoric acid compound to be reacted with the phthalocyanine compound represented by the general formula (1) means a reaction reagent capable of reacting with a hydroxyl group bonded to Al in the general formula (1). In this production method, as the phosphate compound, a reaction reagent that is at least two kinds of phosphate compounds is used, but three or more kinds of reaction reagents may be used. The phosphoric acid compound may be mixed in advance and reacted with the phthalocyanine compound represented by the general formula (1), or may be added sequentially while changing the order of addition during the reaction. In order to obtain, it is preferable to mix beforehand and make it react with the phthalocyanine compound represented by General formula (1).

  As the phosphoric acid compound, it is preferable to use two types of phosphoric acid compounds represented by the general formula (2) and the general formula (3). Here, each substituent in General formula (2) and General formula (3) is demonstrated.

[In General Formulas (2) and (3), R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, An alkoxyl group which may have a substituent or an aryloxy group which may have a substituent is represented. However, general formula (2) and general formula (3) are different compounds. ]

Examples of the alkyl group in R _{1 to} R ₄ 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, an n-hexyl group, an n-octyl group, and a stearyl group. , A straight-chain or branched alkyl group such as 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and 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 Groups and the like.

Examples of the aryl group in R _{1 to} R ₄ include monocyclic aromatic hydrocarbon groups such as a phenyl group and a p-tolyl group, and condensed aromatic hydrocarbon groups such as a naphthyl group and an anthryl group. A hydrocarbon group is preferred. Moreover, a C6-C12 aryl group is preferable. Examples of the substituent of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryl group having a substituent, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, Examples 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.

Examples of the alkoxyl group in R _{1 to} R ₄ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, and 2,3-dimethyl-3- Examples thereof include linear or branched alkoxyl groups such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, and an alkoxyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkoxyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Therefore, examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples include ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the aryloxy group in R _{1 to} R ₄ 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. An aryloxy group comprising a group, and an aryloxy group comprising a monocyclic aromatic hydrocarbon group is preferred. Moreover, a C6-C12 aryloxy group is preferable. Examples of the substituent of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryloxy group having a substituent, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. Can be mentioned.

As the phosphoric acid compounds represented by the general formulas (2) and (3), R _{1 to} R ₄ have an aryl group or a substituent which may have a substituent from the viewpoint of dispersibility and contrast ratio characteristics. Are preferably aryloxy groups, R ₁ and R ₂ are aryl groups, R ₃ and R ₄ are more preferably aryloxy groups, and R ₁ and R ₂ are phenyl groups. More preferably, R ₃ and R ₄ are phenoxy groups.

  The ratio of the phthalocyanine compound and the phosphate compound represented by the general formula (1) is within the range of the phthalocyanine compound represented by the general formula (1): reaction reagent = 1.0 to 1.2 (molar ratio). Is preferred.

  In the present invention, the phthalocyanine compound represented by the general formula (1) is represented by [AlPc (Y)] Xn (4 ≦ n ≦ 16) (where Pc is a phthalocyanine ring, X is a halogen atom, and n is 4 to 16). Are represented by [AlPc (Y)] Brn (4 ≦ n ≦ 16), [AlPc (Y)] Cln (4 ≦ n) as representative examples of the general formula (1). ≦ 16), [AlPc (Y)] In (4 ≦ n ≦ 16), [AlPc (Y)] Fn (4 ≦ n ≦ 16), and the like, but the present invention is not limited to these. Absent. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

  As typical examples of the phosphoric acid compound in the general formulas (2) and (3), the following structures may be mentioned, but the present invention is not limited thereto. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

  When two types of phosphoric acid compounds represented by the general formula (2) and the general formula (3) are used as the phosphoric acid compound, the phosphoric acid compound is represented by the following general formula (4) and the general formula (5). A colorant containing a phthalocyanine compound can be obtained.

  The contents of the phthalocyanine compound represented by the general formula (4) and the phthalocyanine compound represented by the general formula (5) contained in the obtained colorant are represented by the general formula (2) and the general formula (3). It is possible to adjust by the ratio of the phosphoric acid compound made.

[In General Formulas (4) and (5), R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, An alkoxyl group which may have a substituent or an aryloxy group which may have a substituent is represented. However, general formula (4) and general formula (5) are different compounds. ]

Further, the molar ratio of the phthalocyanine compound represented by the general formula (4) and the phthalocyanine compound represented by the general formula (5) in which R ₁ and R ₂ are phenoxy groups and R ₂ and R ₃ are phenyl groups is 55: 45-97: 3 is preferred, 75: 25-97: 3 is more preferred, and 85: 15-97: 3 is most preferred.

(Solvent used during reaction)
An organic solvent used for reacting the phthalocyanine compound represented by the general formula (1) with at least two types of phosphoric acid compounds (referred to as a “reaction solvent” in order to distinguish it from an “organic solvent” used in a colored composition) May be, for example, methanol, ethanol, isopropanol, monohydric alcohol solvents represented by t-butanol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl -1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, polyhydric alcohol solvents represented by trimethylolpropane, 1-methyl-2-pyrrolidinone, 1,3- Dimethyl-2-imidazolidino 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, Amide solvents such as urea or tetramethylurea, and other polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether Lower monoalkyl ether solvent, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether Polyether solvents such as ter (triglyme), sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, or 3-sulfolene, polyfunctional solvents such as diacetone alcohol and diethanolamine, acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, Or a carboxylic acid solvent such as trifluoroacetic acid, a sulfonic acid solvent such as methanesulfonic acid or trifluorosulfonic acid, and an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc. Therefore, it is preferable to use a monovalent alcohol solvent such as methanol, ethanol or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide or 1-methyl-2-pyrrolidinone. Among them, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-2, which has good solubility of the colorant produced by reacting with the phthalocyanine compound represented by the general formula (1) and two kinds of reaction reagents. More preferred are aprotic polar solvents such as pyrrolidinone. These reaction solvents can be used alone or in admixture of two or more.

  As a method for removing the reaction solvent after completion of the reaction, a method known in the art can be used. For example, after performing suction filtration or pressure filtration, there is a method in which the reaction solvent is compatible with the reaction solvent used, washed with another organic solvent having a low boiling point, and then dried and removed. When the reaction solvent is a water-soluble organic solvent, it is desirable that the reaction solution is mixed with water and then removed by filtration and washing with water.

  In order to obtain fine particles of the colorant, the colorant obtained by the above method is dissolved in a soluble solvent and then precipitated with a solvent insoluble in the colorant, or the reaction solution and the colorant Examples thereof include a method of mixing with an insoluble solvent.

(Green pigment)
The coloring composition of the present invention may further contain a green pigment within a range not impairing the effects of the present invention, for example, in order to adjust the chromaticity. Although there is no restriction | limiting in particular as a green pigment | dye, Generally, a green pigment or a green dye is mentioned.

  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, JP2008- The zinc phthalocyanine pigment described in JP 19383, JP 2007-320986 A, JP 2004-70342 A, and the like, and the aluminum phthalocyanine pigment described in JP 4893859 A, and the like can be mentioned. It is not limited. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36, and 58.

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

(Yellow pigment)
The colored composition of the present invention may further contain a yellow pigment within a range not impairing the effects of the present invention, for example, in order to adjust the chromaticity. Although there is no restriction | limiting in particular as a yellow pigment | dye, Generally, a yellow pigment or a yellow dye is mentioned.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

  Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments 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, 82,185,187,188,192,193,194,196,198,199,213,214, may be used yellow pigment quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, examples of the yellow pigment include C.I. I. It is preferably at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and 185.

  As yellow dye, azo dye, azo metal complex dye, anthraquinone dye, indigo dye, thioindigo dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline dye , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes 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, 192, 199 And the like.

  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 etc. are also 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, 105, 106 and the like.

  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 are also included.

  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 the phthalocyanine compound represented by the general formulas (4) and (5) and the green pigment are used in combination, the mass ratio of the green pigment / the phthalocyanine pigment represented by the general formula (1) from the viewpoint of brightness and hue. Is preferably in the range of 10/90 to 70/30.

  When a yellow pigment is used in combination with the phthalocyanine compounds represented by the general formulas (4) and (5), from the viewpoint of brightness and hue, the mass ratio of the yellow pigment / the phthalocyanine pigment represented by the general formula (1) is A range of 70/30 to 10/90 is preferred.

(Miniaturization of colorant)
The colorant used in the coloring composition of the present invention is suitable as a color filter colorant by obtaining finer colorant particles by a salt milling process or the like as necessary in order to obtain high brightness and high contrast. Can be used for The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to enhance dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 80 nm or less. A particularly preferred range is 20 to 60 nm.

  Salt milling is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or 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 serves as a crushing aid, and the colorant is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the colorant, it is possible to obtain a colorant having a sharp particle size distribution in which the volume average primary particle diameter is very fine and the distribution width is wide. .

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass) in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the colorant and 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 to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

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

<Binder resin>
The binder resin disperses colorants such as pigments and pigments, particularly phthalocyanine compounds represented by the general formulas (4) and (5), and examples thereof include thermoplastic resins and thermosetting resins.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Furthermore, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of further improving photosensitivity and improving solvent resistance.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating film foreign matter is generated after the colorant is applied. The stability of the colorant is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped in the resin and the colorant mixture, and has a degree of freedom. The colorant component easily aggregates and precipitates, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the colorant is converted into a resin in a mixture of resin and colorant. Because it is easily trapped, it is difficult for the dye to elute in the solvent resistance test, the colorant component does not easily aggregate and precipitate, and the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film. It is estimated that the colorant component is less likely to aggregate and precipitate even if the colorant molecules are fixed and the solvent is removed in the subsequent development step.

  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 disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, it acts as a colorant-adsorbing group and an alkali-soluble group during development from the viewpoint of dispersibility, penetrability, developability and heat resistance of the pigment. The balance of aliphatic groups and aromatic groups acting as affinity groups for the carboxyl group, colorant carrier and solvent is important for the dispersibility, penetrability, developability, and durability of the pigment, with an acid value of 20-300 mg KOH / G of resin is preferably used. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the binder resin has good film formability and various resistances, it is preferable to use it in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by mass or less.

(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, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[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 and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be 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 carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

  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 or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

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

The thermosetting resin may be, for example, a low-molecular 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 at the time of firing the filter segment, the cross-linking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. It is done.
Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.
<Organic solvent>
In the coloring composition of the present invention, a colorant is sufficiently dissolved in a monomer, a resin, and the like, and applied to a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. In order to facilitate this, an organic solvent is included.

  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, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 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-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary 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, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Moreover, since the organic solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the amount of 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.

<Method for producing colored composition>
The coloring composition of the present invention preferably contains a coloring agent containing a phthalocyanine compound represented by the general formulas (4) and (5) in a coloring agent carrier composed of the resin and, if necessary, a solvent. In addition to a dispersion aid such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor can be used to finely disperse and produce. In addition, when the solubility of the phthalocyanine pigment represented by the general formula (1) is high, specifically, the solubility in an organic solvent to be used is high, and if it is in a state where dissolution and foreign matter are not confirmed by stirring, There is no need to produce such finely dispersed products.

  The colored composition of the present invention is produced by mixing pigments, phthalocyanine compounds represented by the general formulas (4) and (5), and other colorants separately dispersed in a colorant carrier. You can also.

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment 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. Further, from the viewpoint of heat resistance and light resistance, the 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.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include 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, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  In the case of adding a resin-type dispersant and a surfactant, from the viewpoint of the effect on dispersion, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. It is.

  The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator. Furthermore, the coloring composition of the present invention can contain a sensitizer, a polyfunctional thiol, an amine compound, a leveling agent, a curing agent, a curing accelerator, and other additive components.

<Photopolymerization initiator>
The coloring composition of the present invention can contain a photopolymerization initiator. The amount of the photopolymerization initiator used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant containing the phthalocyanine compound represented by the general formulas (4) and (5). From a viewpoint of property, it is more preferable that it is 10-150 mass parts.

  As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specifically, 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 Acetophenones such as phenyl] -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Examples include glyoxylic methyl ester. More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01, IRGACURE OXE-02 (BASF), Adekaoptomer N1717, Adekaoptomer N1919, Adeka Arcles NCI- 831 (ADEKA), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621, and Triazine derivatives described in JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, Japanese Patent Publication No. 47-1604 and diazonium compound publications described in US Pat. No. 3,567,453, USP No. 2,848,328, USP No. 2,852,379, and USP No. 2,940,853, organic azide compounds described in Japanese Patent Publication No. Sho 36- Ortho-quinonediazides described in JP-A-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-39162, JP-A-59-140203 And `` MACROMOLECULES '', No. Vol. 0, various onium compounds including iodonium compounds described on page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851 EP-A-126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986), metal allene complexes described in JP-A-61-151197. Transition metals such as ruthenium described in JP-A-2-182701, as well as the titanocenes described in Japanese Patent Publication No. 1993, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) Transition metal complexes, aluminate complexes described in JP-A-3-209477, JP-A-2-1577 No. 60, borate compounds, JP-A Nos. 55-127550 and 60-202437, 2,4,5-triarylimidazole dimers, carbon tetrabromide and JP-A No. Nos. 59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977. Aminoketone compounds described in JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, JP-T-2004-534797, JP-A-2006-342166 , JP2008-094770, JP2009-40762, 2010-15025, JP 2010-189279, JP 2010-189280, JP 2010-526946, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP 4202697 (1980) And oxime ester compounds described in JP-A No. 61-24558.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins 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 (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di Various acrylic esters such as enterythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile The effects of the present invention are not limited to these.

  Moreover, the photopolymerizable monomer may contain an acid group. For example, esterified product of poly (meth) acrylates containing free hydroxyl group of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; esterified product of polycarboxylic acid and monohydroxyalkyl (meth) acrylates, etc. Can be mentioned. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

  The content of the photopolymerizable monomer is preferably 10 to 300 parts by mass and 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. It is preferable.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers 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. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, teto Benzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran Examples thereof include, but are not limited to, derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, the dyes and sensitizers described in “Functional Materials” (1986, CMC), and other dyes and sensitizers that absorb light from the ultraviolet to the near infrared region. There may be mentioned sensitizers, and these may be used in an arbitrary ratio as required. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). Raised Although it is Rukoto, but is not limited thereto.

  Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass parts with respect to 100 mass parts of total mass of the photoinitiator (E) contained in a coloring photosensitive composition, and photocuring. It is more preferable that it is 5-50 mass parts from a viewpoint of property.

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (5-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  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 (100% by mass) of the total solid content of the colored composition. When the polyfunctional thiol content is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, 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 end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane 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 thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. 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 amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. A storage stabilizer can be used in the quantity of 0.1-10 mass parts with respect to 100 mass parts of whole quantity of a coloring agent.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and 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 with respect to 100 parts by mass of the total amount of the colorant in the coloring composition.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

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

  As a base material such as a transparent substrate constituting the color filter, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Used. In addition, 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 in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method. The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . 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 this filter segment is transferred to a desired substrate.

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

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” and “%” represent “part by mass” and “% by mass”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

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

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. And 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.

(Average number of halogen substitutions)
The average number of halogen substitutions in the pigment was analyzed by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX) of the liquid in which the pigment was burned by the oxygen combustion flask method and the combustion product was absorbed in water. The amount of halogen was quantified to obtain the average number of halogen substitutions.

(Halogen distribution width)
The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics). In the mass spectrum obtained by mass spectrometry of the pigment powder, the halogen content is the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value obtained by integrating each peak value (total peak value) Was calculated from the ratio of each peak value to the total peak value. The halogen distribution width was defined as the halogen distribution width by counting the number of peaks in which the ratio of each peak value to the total peak value was 1% or more.

(Colorant analysis)
The identification of the compound contained in the colorant and the determination of the ratio were performed using TOF-MS in the same manner as the identification of the halogen distribution width.

(Volume average primary particle size (MV))
The volume average primary particle size (MV) of the phthalocyanine pigment and the yellow colorant was determined by a transmission electron microscope (TEM) “H-7650” manufactured by Hitachi High-Technologies Corporation and the following calculation formula. First, colorant particles were photographed by TEM. In the obtained image, select 100 arbitrary colorant particles, the average value of the minor axis diameter and major axis diameter of the primary particles is the particle diameter (d) of the colorant particles, and then the individual colorants are selected. The volume (V) of each particle was determined by considering it as a sphere having the determined particle size (d), and this operation was performed on 100 colorant particles, and the calculation was performed using the following equation (1).
Formula (1) MV = Σ (V · d) / Σ (V)

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 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 Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Acrylic resin solution 1 was prepared by adding ether acetate.

<Adjustment of resin-type dispersant>
(Preparation of resin-type dispersant solution 1)
A flask equipped with a condenser and a stirrer was charged with 1.0 part by weight of AIBN (2,2′-azobisisobutyronitrile) and 186 parts by weight of propylene glycol monomethyl ether acetate, followed by 27 parts by weight of methyl methacrylate and butyl methacrylate. 27 parts by mass, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate and 3.6 parts by mass of cumyldithiobenzoate were charged, and the atmosphere was replaced with nitrogen for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization. Next, a solution obtained by dissolving 1.0 part by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate in 70 parts by mass of propylene glycol monomethyl ether acetate and replacing with nitrogen for 30 minutes is added to this reaction solution, and living radical polymerization is performed at 60 ° C. for 24 hours. As a result, a solution of the block copolymer was obtained. By adding 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether to the obtained block copolymer solution, reacting at 80 ° C. for 2 hours and adjusting the solid content concentration to 40%, the resin type Dispersant solution 1 was obtained. Resin Type Dispersant 1 is an A block having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, and a B block having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate. Is a block copolymer. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloyloxyethylbenzyldimethylammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34/4/18/18 / 14/12 (mass ratio).

<The manufacturing method of the phthalocyanine compound represented by General formula (1)>
[Production Example 1]
(Production of phthalocyanine pigment PC-1)
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of hydroxyaluminum phthalocyanine (P-1) and 99.1 parts of N-bromosuccinimide (NBS) were added and stirred, and reacted at 20 ° C. for 3 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was filtered, washed with water, and dried to obtain a phthalocyanine pigment (PC-1). The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 2]
(Production of phthalocyanine pigment PC-2)
Reaction of 50 parts of hydroxyaluminum phthalocyanine (P-1) with 50 parts of chloroaluminum phthalocyanine (P-2) and 99.1 parts of NBS with 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) Except having changed time from 3 hours to 4 hours, operation similar to manufacture example 1 was performed and the phthalocyanine compound (PC-2) was obtained. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 3]
(Method for producing phthalocyanine pigment PC-3)
A phthalocyanine compound (PC-3) was obtained in the same manner as in Production Example 2, except that the amount of DBDMH and the reaction time were changed to the conditions described in Table 1, respectively. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 4]
(Method for producing phthalocyanine pigment PC-4)
203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and 50 parts of chloroaluminum phthalocyanine (P-2) was added at 140 ° C. The temperature was raised to 160 ° C., and the reaction was carried out at 160 ° C. for 6 hours while blowing 173.7 parts of bromine. The above reaction mixture was poured into 2500 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. The residue was washed with 1% hydrochloric acid aqueous solution, warm water, 1% sodium hydroxide aqueous solution and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Thereafter, the sulfuric acid solution was poured into 9800 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. Next, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added to the beaker, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water and dried to obtain a phthalocyanine pigment (PC-4). The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Examples 5 and 6]
(Method for producing phthalocyanine pigment PC-5, 6)
A phthalocyanine pigment (PC-5, PC-6) was obtained in the same manner as in Production Example 4 except that the amount of bromine and the reaction time were changed to the conditions described in Table 1, respectively. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 7]
(Method for producing phthalocyanine pigment PC-7)
In a three-necked flask, 250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added and stirred at 150 ° C. for 30 minutes. Thereto, 50 parts of hydroxyaluminum phthalocyanine (P1) was added and stirred at 155 ° C. for 30 minutes to dissolve. Further, 58.5 parts of trichloroisocyanuric acid was added and stirred at 190 ° C. for 5 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a phthalocyanine pigment (PC-7). The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 8]
(Method for producing phthalocyanine pigment PC-8)
A phthalocyanine pigment (PC-8) was obtained in the same manner as in Production Example 7 except that the amount of trichloroisocyanuric acid and the reaction time were changed to the conditions described in Table 1, respectively. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 9]
(Method for producing phthalocyanine pigment PC-9)
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 45.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 210.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the formed precipitate is treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying, 165.7 parts. Phthalocyanine pigment (PC-9) was obtained. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 10]
(Method for producing phthalocyanine pigment PC-10)
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 125.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 155.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, and the mixture was stirred at 25 ° C. for 5 hours. Subsequently, the sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and then dried to 157.1 parts. Phthalocyanine pigment (PC-10) was obtained. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

[Production Example 11]
(Method for producing phthalocyanine pigment PC-11)
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 45.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 205.0 parts of 1,3-diiodo-5,5-dimethylhydantoin (DIDMH) was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the produced precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and dried to obtain 145.3 parts. Phthalocyanine pigment (PC-11) was obtained. The yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width were as shown in Table 1.

<Method for producing colorant>
[Example 1] (Production method of colorant PG-1)
To a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of PC-1, 11.5 parts of diphenyl phosphate and 1.6 parts of diphenylphosphinic acid were added, heated to 90 ° C., and reacted for 8 hours. . After cooling this to room temperature, this reaction solution was poured into 4000 parts of water. The product was filtered, washed with methanol, and dried to obtain a colorant (PG-1). The molar ratio of the main component of the colorant and the volume average primary particle diameter are shown in Table 2.

[Examples 2 to 21] (Method for producing colorant PG-2 to 21)
Except that the phthalocyanine pigment (PC-2 to PC-11) and the reaction reagent were changed to the conditions described in Table 2, the same operation as in Example 1 was performed, respectively, and the colorant (PG-2 to PG-21), respectively. Got. The molar ratio of the main component of the colorant and the volume average primary particle diameter are shown in Table 2.

[Comparative Example 1]
Example 1 except that PC-1 of the colorant PG-1 was changed to P-1, diphenyl phosphate 11.5 parts to 21.4 parts, and diphenylphosphinic acid 1.6 parts to 2.9 parts. The same operation was performed to obtain a colorant PG-22 (PCY-30 / PCY-31 (molar ratio 90.1: 9.9)). The yield was 54.3 parts, and the volume average primary particle size was 30 nm.

[Comparative Example 2]
The same as Example 1 except that PC-1 of the colorant PG-1 was changed to PC-3, 11.5 parts of diphenyl phosphate to 10.2 parts, and 1.6 parts of diphenylphosphinic acid to 0 parts. Operation was performed to obtain a colorant PG-23 (PCY-5). The yield was 52.1 parts, and the volume average primary particle size was 27 nm.

[Comparative Example 3]
The same as Example 1 except that PC-1 of the colorant PG-1 was changed to PC-3, 11.5 parts of diphenyl phosphate to 0 part, and 1.6 parts of diphenylphosphinic acid to 8.9 parts. Operation was performed to obtain PCY-6. The yield was 51.3 parts, and the volume average primary particle size was 27 nm. 471.2 parts of PCY-5 and 51.3 parts of PCY-6 were mixed so as to be uniformly mixed to obtain PG-24.

  The structural formulas of the phthalocyanine compounds (PCY-1 to 31) are shown below. However, in the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of the number of halogen atoms substituted.

<Others / Manufacturing method of fine pigment>
(Production of refined green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Production of fine green pigment (PG7-1))
Phthalocyanine 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 into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG7-1) was obtained.

(Production of fine green pigment (PG36-1))
Phthalocyanine green pigment C.I. I. 200 parts of CI Pigment Green 36 (“Green 8G” manufactured by CLARIANT), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG36-1) was obtained.

(Production 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 into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Production of refined yellow pigment (PY138-1))
Quinophthalone yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (“Paliotol Yellow L 0962HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY138-1) was obtained.

(Production of fine yellow pigment (Y5267696-1))
According to the synthesis method described in Japanese Patent No. 5267696, a quinophthalone compound represented by the following formula (1) was obtained. 200 parts of this quinophthalone compound, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , A fine yellow pigment (Y5267696-1) was obtained.

Formula (1)

(Production of refined yellow pigment (PY 139-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Paliotol Yellow L 2146HD” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY139-1) was obtained.

(Production of fine red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of Pigment Red 254 (“B-CF” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined diketopyrrolopyrrole pigment (PR254-1) was obtained.

(Production of refined red pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Production of refined blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor “LIONOL BLUE ES”, specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine blue pigment (PB15: 6-1) was obtained.

(Production of refined purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple refined purple pigment (PV23-1) was obtained.

<Manufacture of pigment dispersion>
About the pigment created above, the pigment dispersion which is one aspect | mode of a coloring composition was manufactured.
[Example 22]
(Pigment dispersion (GP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a pigment dispersion (GP-1) having a non-volatile component of 20% by mass.
Colorant (PG-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 23 to 42, Comparative Examples 4 to 6]
(Pigment dispersion (GP-2 to 24))
Pigment dispersions (GP-2 to 24) were prepared in the same manner as in Example 21, except that the colorant (PG-1) was changed to (PG-2) to (PG-24), respectively.

<Evaluation of pigment dispersion (coloring composition)>
The following evaluation was performed about the obtained pigment dispersion. The results are shown in Table 3.
(Initial viscosity)
The viscosity of the pigment dispersion was evaluated based on the following criteria by measuring the initial viscosity at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).
A: Less than 10 mPa · s: Extremely good O: 10 mPa · s or more, less than 15 mPa · s: Good Δ: 15 mPa · s or more, less than 20 mPa · s: Practical use ×: In the case of 20 mPa · s or more: Defect

(Viscosity with time)
The obtained pigment dispersion was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the colored composition after the aging was measured by the same method as the viscosity measurement and stored at 40 ° C. for 1 week. The rate of change in viscosity before and after the calculation was calculated and evaluated according to the following criteria.
A: When the viscosity change rate is less than ± 10% and no precipitate is formed: Very good O: When the viscosity change rate is ± 10% or more and less than 15% and no precipitate is formed: Good Δ: Viscosity change When the rate is ± 15% or more and less than 20% and no precipitate is formed: Practical use ×: When the viscosity change rate exceeds ± 20% or even when the viscosity change rate is within ± 20% If it has occurred: Defect

(Contrast ratio of coating film (CR))
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low. A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

The obtained pigment material dispersions were applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 230 ° C. for 60 minutes. The coating film substrate was produced by allowing to cool. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The contrast ratio (CR) of the obtained coated substrate was measured and evaluated according to the following criteria.
◎: 20000 or more: Extremely good ○: 15000 or more and less than 20000: Good Δ: 10,000 or more and less than 15000: Practical use

(Foreign substance evaluation)
Evaluation of the generation of foreign matter was performed by applying a colored composition on a transparent substrate so that the dried coating film was about 2.0 μm, and heating and cooling in an oven at 250 ° C. for 60 minutes. The number of foreign objects in the inside was counted. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was set to 500 times, the number of foreign matters observable in arbitrary five fields of view was measured by transmission, and evaluated according to the following criteria.
◎: The number of foreign matters is less than 3: Extremely good ○: The number of foreign matters is 3 or more and less than 20: Good Δ: The number of foreign matters is 21 or more and less than 100: Practical use ×: The number of foreign matters is 100 More than: bad

  From the comparison of GP-1 to 11 and GP-22, the halogen number of phthalocyanine is preferably 6 or more, and the halogen is preferably a bromine-substituted phthalocyanine rather than a chlorine atom or a phthalocyanine in which a chlorine atom and an iodine atom are combined. It was shown that 8 or more is the most preferable. In the two types of phosphoric acid compounds to be reacted with phthalocyanine, comparison between GP-3 and GP-12 to 16 indicates that a combination of a phosphoric acid ester compound and a phosphinic acid compound is preferable. Moreover, 55: 45-65: 35 are preferable and 75: 25-85: 15 are more preferable in the molar ratio of the phthalocyanine of a phosphoric acid aryl ester compound and an aryl phosphate compound from comparison of GP-3 and GP-17-21. 85:15 to 95: 5 has been shown to be most preferred. In addition, PCY-5 alone GP-23 reacted with a phosphoric acid ester compound is inferior in foreign matter evaluation / initial viscosity / viscosity viscosity / CR to the product of the present invention. After synthesizing PCY-6, PCY-5 is mixed. It is clear that it is important to react the two types of phosphoric acid compounds of the present invention with phthalocyanine, because the GP-24 is obviously inferior in terms of molar ratio compared to the equivalent GP-3. became.

<Manufacture of other pigment dispersions>
(Pigment dispersion (GP-25))
A pigment dispersion (GP-25) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to (PG58-1).

(Pigment dispersion (GP-26))
A pigment dispersion (GP-26) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to (PG7-1).

(Pigment dispersion (GP-27))
A pigment dispersion (GP-27) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to (PG36-1).

(Pigment dispersion (YP-1))
A pigment dispersion (YP-1) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PY150-1.

(Pigment dispersion (YP-2))
A pigment dispersion (YP-2) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PY138-1.

(Pigment dispersion (YP-3))
A pigment dispersion (YP-3) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to Y52667696-1.

(Pigment dispersion (YP-4))
A pigment dispersion (YP-4) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PY139-1.

(Pigment dispersion (RP-1))
A pigment dispersion (RP-1) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PR254-1.

(Pigment dispersion (RP-2))
A pigment dispersion (RP-2) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PR177-1.

(Pigment dispersion (BP-1))
A pigment dispersion (BP-1) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PB15: 6-1.

(Pigment dispersion (VP-1))
A pigment dispersion (VP-1) was produced in the same manner as in Example 22 except that the colorant (PG-1) was changed to PV23-1.

<Production of photosensitive coloring composition>
Using the pigment dispersion, a photosensitive coloring composition which is an embodiment of the coloring composition of the present invention was prepared and evaluated.
[Example 43]
(Green photosensitive coloring composition (GR-1))
A 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): 22.2 parts Pigment dispersion (YP-2): 27.8 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts Dipentaerythritol hexaacrylate Photopolymerization initiator (" IRGACURE 907 "manufactured by BASF): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.): 0 .3 parts PGMAC: 39.0 parts

[Examples 44 to 69, Comparative Examples 7 to 9]
The green photosensitive coloring compositions (GR-2 to 30) were respectively obtained in the same manner as in Example 43 except that the breakdown of the total 50 parts of the pigment dispersion was changed to the types and parts by mass shown in Table 4, respectively. Obtained.

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the obtained photosensitive coloring composition. The results are shown in Table 4.
(Foreign substance evaluation)
The green photosensitive coloring composition (GR-1 to 30) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater and dried at 70 ° C. for 20 minutes in a clean oven. . Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Thereafter, 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, a heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate. A coated substrate was obtained in which the chromaticity of the obtained substrate was x = 0.297 and y = 0.570 in a C light source. The number of foreign substances on the coated substrate was measured. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was set to 500 times, the number of foreign matters observable in arbitrary five fields of view was measured by transmission, and evaluated according to the following criteria.
◎: The number of foreign matters is less than three: Extremely good ○: The number of foreign matters is 3 or more and less than 20: Good Δ: The number of foreign matters is 21 or more and less than 100: Practical use ×: The number of foreign matters is 100 More than: bad

(Evaluation of contrast ratio (CR) of coating film)
The contrast ratio of the green photosensitive coloring composition substrate was evaluated in the same manner as the pigment dispersion substrate. The contrast ratio was determined according to the following criteria and evaluated according to the following criteria.
◎: 20000 or more: Extremely good ○: 15000 or more and less than 20000: Good Δ: 10,000 or more and less than 15000: Practical use

  Similar to the evaluation results of the pigment dispersion, the product of the present invention was found to be very excellent in foreign matter / CR evaluation as compared with the comparative example, and the effect was proved.

<Production of color filter>
(Red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore diameter of 1 μm to prepare a red photosensitive coloring composition (RR-1).
Pigment dispersion (RP-1) / Pigment dispersion: 30.0 parts Pigment dispersion (RP-2) / Pigment dispersion: 20.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ( "Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) ): 0.3 part PGMAC: 39.0 parts

(Blue photosensitive coloring composition (BR-1))
A 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).
Pigment dispersion (BP-1): 45.0 parts Pigment dispersion (VP-1): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts Photopolymerization initiator (" Irgacure 907 "manufactured by BASF): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts PGMAC: 39.0 parts

  The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Thereafter, 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, a 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-2) of the present invention is used to form a green coloring pixel layer in the same manner as the red coloring pixel layer, and the blue photosensitive coloring composition (BR-1) is further formed. A blue colored pixel layer was formed using it to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the green coloring composition of the present invention was excellent in viscosity, foreign matter and CR ratio, and the effect of the present invention was proved.

Claims (5)

A method for producing a colorant obtained by reacting a phthalocyanine compound represented by the following general formula (1) with a phosphoric acid compound, wherein at least 2 of the following general formulas (2) and (3) are used as the phosphoric acid compound: A method for producing a colorant, characterized by using various types of phosphoric acid compounds.
General formula (1)
[In General Formula (1), X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X is 6 to 15, and the halogen distribution width is 4 or more. Y is —OH or —Cl. ]
[In General Formulas (2) and (3), R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, An alkoxyl group which may have a substituent or an aryloxy group which may have a substituent is represented. However, general formula (2) and general formula (3) are different compounds. ] A method for producing a colored composition containing at least a colorant, a binder resin and an organic solvent, wherein the colorant is obtained by reacting a phthalocyanine compound represented by the following general formula (1) with a phosphate compound. A method for producing a colored composition, characterized in that at least two types of phosphoric acid compounds of the following general formulas (2) and (3) are used as the phosphoric acid compound.
General formula (1)
[In General Formula (1), X represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X is 6 to 15, and the halogen distribution width is 4 or more. Y is —OH or —Cl. ]
[In General Formulas (2) and (3), R _{1 to} R ₄ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, An alkoxyl group which may have a substituent or an aryloxy group which may have a substituent is represented. However, general formula (2) and general formula (3) are different compounds. ]   The manufacturing method of the coloring composition of Claim 2 in which a coloring agent contains a green pigment | dye and / or a yellow pigment | dye further.   The green pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. Pigment Green 58 is at least one selected from the group consisting of C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. The method for producing a coloring composition according to claim 3, which is at least one selected from the group consisting of CI Pigment Yellow 185. Furthermore, the manufacturing method of the coloring composition as described in any one of Claims 2-4 containing a photopolymerizable monomer and / or a photoinitiator.