JP2017160370A - Phthalocyanine pigment, coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phthalocyanine pigment that has excellent fastness (heat resistance, light fastness, solvent resistance) and, when used for a color filter or the like, is excellent in color properties (lightness) and the contrast ratio, without causing unusual matter due to association, aggregation or the like of molecules with each other even in a high temperature environment above 230°C.SOLUTION: The invention provides: a phthalocyanine pigment having a specific structure represented by general formula (1) or the like; and a coloring composition and a color filter using the phthalocyanine pigment.SELECTED DRAWING: None

Description

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

  In recent years, materials for forming color images have become mainstream as image recording materials. Specific examples of color image recording materials are ink jet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer silver halide photosensitive materials, printing inks, and recording pens. ing. Further, color filters are used for recording and reproducing color images in image pickup devices such as CCDs in photographing apparatuses and in LCDs, PDPs, organic electroluminescence, and electronic paper (electronic paper) in displays. In these color image recording materials and color filters, so-called additive color mixing and subtractive color mixing three primary colors (dyes and pigments) are used to display or record full color images. However, the fact is that there are no dyes that have absorption characteristics and color characteristics that can realize a preferable color gamut and that meet various usage conditions, and improvement is strongly desired.

  The dyes used in each of the above applications have different color characteristics and required quality for each application, but from the viewpoint of the light resistance and heat resistance of the recorded material, pigments are mainly used as the dye. ing. For example, in a color filter application, C.I. I. Pigment Green 36, 58, etc. are used.

  In the production of a green filter in a color filter, it is common to use various phthalocyanine compounds as colorants, and many color filter compositions containing these have been proposed. Of these, many colorants for color filters using copper phthalocyanine compounds and zinc phthalocyanine compounds have been proposed.

  Patent Document 1 proposes a color filter composition using a halogenated phthalocyanine compound substituted with at least four halogen atoms as a green colorant.

  In Patent Document 2, as a green pigment, a halogenated copper phthalocyanine pigment and a central metal are selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. There has been proposed a color filter composition comprising a green colorant composed of at least one halogenated dissimilar metal phthalocyanine pigment.

  These phthalocyanine compounds are all materials for producing a high brightness color filter. However, in recent years, the demand for high brightness has been further increased, and the brightness using these proposed colorants has been insufficient.

  Patent Document 3 discloses a pigment composition that maintains a clear hue, high light resistance, and high heat resistance by using a blue aluminum phthalocyanine pigment containing no halogen and a green pigment containing halogen. Yes.

  Patent Document 4 discloses that a color composition and a purity of a color composition for a green color filter segment can obtain high brightness with high chromaticity even with a relatively small content by using an aluminum phthalocyanine pigment as a main pigment. A technique that achieves both is disclosed.

  In addition to the monomeric aluminum phthalocyanine pigment described in Patent Document 4, a dimerized pigment has been proposed as the aluminum phthalocyanine pigment. In Patent Document 5, a bis (phthalocyanylaluminum) tetraphenyldisiloxane pigment obtained by dimerizing an aluminum phthalocyanine pigment with diphenylchlorosilane, or a bis (phthalocyanylaluminum) phenylphosphonate dimerized using phenylphosphonic acid. Pigments are disclosed.

  However, the pigment compositions containing these aluminum phthalocyanine compounds are not sufficient in heat resistance at 230 ° C. or higher and long-term light resistance, which are required for color filter applications, and the spectral shape changes. was there. Furthermore, the present situation is that the problems such as high viscosity of the colored composition and generation of foreign matters on the coating film due to poor dispersibility have not been sufficiently improved.

JP 2002-131521 A JP 2002-250812 A JP 2003-4930 A JP 2004-333817 A Japanese Unexamined Patent Publication No. 57-90058

  The problems to be solved by the present invention are excellent in fastness (heat resistance, light resistance, solvent resistance), excellent in color characteristics (brightness) and contrast ratio, and between molecules even in a high temperature environment exceeding 230 ° C. An object of the present invention is to provide a phthalocyanine pigment useful as a colorant with less generation of foreign matter due to association or aggregation. In addition, the above phthalocyanine pigments are used to provide excellent fastness (heat resistance, light resistance, solvent resistance), color characteristics (brightness) and contrast ratio when used in color filter applications, and generation of foreign matter. The object is to provide a low coloring composition and a high-quality color filter using the same.

  That is, the present invention relates to a phthalocyanine pigment represented by the following general formula (1) or the following general formula (2).

(In General Formula (1), X ₁ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15. And the halogen distribution width is at least 4. M ₁ represents Ga or In, Y ₁ represents a hydroxyl group, —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , — OS (═O) ₂ R ₄ R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents an alkoxyl group which may have a group or an aryloxy group which may have a substituent, and R ₃ may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. .R ₄ representing an cycloalkyl group which may have an aryl group or a substituted group may have a substituent heterocyclic group, water It represents groups, an optionally substituted alkyl group, a heterocyclic group which may have an aryl group or a substituted group may have a substituent.)

(In General Formula (2), X ₂ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₂ is 6 to 15. And the halogen distribution width is at least 4. M ₂ represents Si, Ge, or Sn, and Y ₂ and Y ₃ each independently represent a hydroxyl group, —OP (═O) R ₁ R ₂ , — _{OC (= O) R 3,} .R 1 and R ₂ represents a -OS (= O) ₂ R ₄ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, a substituent An aryl group that may have, an alkoxyl group that may have a substituent, or an aryloxy group that may have a substituent, R ₃ represents a hydrogen atom or an alkyl group that may have a substituent. A cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. )

In the general formula (1), X ₁ is a chlorine atom or a bromine atom, Y ₁ is —OP (═O) R ₁ R ₂ , and in the general formula (2), X ₂ is The above phthalocyanine pigment is a chlorine atom or a bromine atom, and Y ₂ and Y ₃ are —OP (═O) R ₁ R ₂ .

In the general formula (1), X ₁ is a bromine atom, Y ₁ is —OP (═O) (OC ₆ H ₅ ) ₂ , and in the general formula (2), X ₂ is The phthalocyanine pigment is a bromine atom, and Y ₂ and Y ₃ are —OP (═O) (OC ₆ H ₅ ) ₂ .

  The present invention also relates to a colored composition containing a colorant, a binder resin and an organic solvent, wherein the colorant contains the phthalocyanine pigment.

  Moreover, this invention relates to the said coloring composition in which the said coloring agent contains at least one of a green pigment | dye and a yellow pigment | dye further.

  In the present invention, the green pigment may be C.I. I. Pigment Green 7, 36 and 58, which is at least one selected from the group consisting of C.I. I. Pigment Yellow 138, 139, 150 and 185, which is at least one selected from the group consisting of the above.

  Moreover, this invention relates to the said coloring composition which contains at least one of a photopolymerizable monomer and a photoinitiator further.

  In the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, the at least one green filter segment is formed of the colored composition. Relates to the color filter.

  According to the present invention, the phthalocyanine pigment represented by the general formula (1) or the general formula (2) is excellent in fastness (heat resistance, light resistance, solvent resistance), and has high brightness and high contrast ratio. Thus, it is possible to provide a colorant that generates less foreign matter due to association or aggregation of molecules even in a high temperature environment exceeding 230 ° C. In addition, the coloring composition containing the phthalocyanine pigment of the present invention as a colorant provides excellent fastness (heat resistance, light resistance, solvent resistance), high brightness and high contrast ratio, and a high temperature exceeding 230 ° C. It is possible to provide a high-quality color filter in which the generation of foreign matters due to the association or aggregation of molecules is small even under such an environment.

Hereinafter, the present invention will be described in detail.
In the present specification, the expression “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly explained. Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. Represent. In the present specification, “CI” means color index (CI).

<Phthalocyanine pigment>
The phthalocyanine pigment of the present invention is represented by the general formula (1) or the general formula (2), and can be suitably used as a colorant used for the coloring composition, particularly as a green colorant.

(In General Formula (1), X ₁ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15. And the halogen distribution width is at least 4. M ₁ represents Ga or In, Y ₁ represents a hydroxyl group, —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , — OS (═O) ₂ R ₄ R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents an alkoxyl group which may have a group or an aryloxy group which may have a substituent, and R ₃ may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. .R ₄ representing an cycloalkyl group which may have an aryl group or a substituted group may have a substituent heterocyclic group, water It represents groups, an optionally substituted alkyl group, a heterocyclic group which may have an aryl group or a substituted group may have a substituent.)

(In General Formula (2), X ₂ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₂ is 6 to 15. And the halogen distribution width is at least 4. M ₂ represents Si, Ge, or Sn, and Y ₂ and Y ₃ each independently represent a hydroxyl group, —OP (═O) R ₁ R ₂ , — _{OC (= O) R 3,} .R 1 and R ₂ represents a -OS (= O) ₂ R ₄ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, a substituent An aryl group that may have, an alkoxyl group that may have a substituent, or an aryloxy group that may have a substituent, R ₃ represents a hydrogen atom or an alkyl group that may have a substituent. A cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. )

  In the general formulas (1) and (2), examples of the “halogen” include fluorine, bromine, chlorine, and iodine. Bromine and chlorine are preferable, and bromine is particularly preferable.

When the average value of the number of substitutions of the halogen atom represented by X ₁ in the general formula (1) or X ₂ in the general formula (2) is 6 to 15, it is easy to obtain various desired characteristics. . The average value of the number of substituents of the halogen atom is preferably 7 to 15 from the viewpoint of fastness, and more preferably 8 to 15 from the viewpoint of hue and fastness.
The halogen distribution width is 4 or more, preferably 4 to 9, and more preferably 5 to 8. When the halogen distribution width is 4 or more, association and aggregation of phthalocyanine molecules tend to be remarkably suppressed. Therefore, when the halogen distribution width is within the above range, it greatly contributes to the suppression of the increase in particle size and the decrease in contrast caused by the association and aggregation between molecules, and it becomes easy to obtain various desired characteristics.
Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigments represented by the general formulas (1) and (2). In the mass spectrum obtained by mass spectrometry, the halogen distribution width was obtained by integrating the signal intensity (each peak value) of the molecular ion peak corresponding to the molecular weight of each component of aluminum phthalocyanine according to the number of halogen substitutions and each peak value. A value (total peak value) was calculated, and 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 or more halogen atoms may be used in combination as long as the average number of substitutions and the distribution range are within the above ranges. In this case, it is particularly preferable to use bromine and chlorine in combination.

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 and R ₂ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- Examples thereof include 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.

As the aryloxy group in R ₁ and R _2, an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group or a p-methylphenoxy group, or a condensed aromatic hydrocarbon such as a naphthaloxy group or 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.

Examples of the cycloalkyl group in R ₃ include a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, a monocyclic aliphatic hydrocarbon group such as a 4-tert-butylcyclohexyl group, a bornyl group, an adamantyl group, and the like. A condensed aliphatic hydrocarbon group is mentioned. Moreover, a C5-C12 cycloalkyl group is preferable.
Examples of the substituent of the cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group in R ₃ and R ₄ include aliphatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, and aromatic heterocyclic groups. Moreover, a C4-C12 heterocyclic group is preferable and a C5-C13 heterocyclic group is preferable.
Examples of the substituent of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

As one embodiment, among the phthalocyanine pigments represented by the general formula (1) and the general formula (2), at least one of R ₁ and R ₂ has a substituent from the viewpoint of dispersibility and color characteristics. An aryl group that may be substituted or an aryloxy group that may have a substituent is preferable. More preferably, R ₁ and R ₂ are both aryl groups or aryloxy groups. More preferably, R ₁ and R ₂ are both a phenyl group or a phenoxy group. Moreover, it is preferable that R < ₃ > and R < ₄ > are the aryl groups which may have a substituent, or the heterocyclic group which may have a substituent.

Y ₁ in the general formula (1) and Y ₂ and Y ₃ in the general formula (2) are preferably —OP (═O) R ₁ R ₂ .

As typical examples of Y ₁ in the general formula (1), Y ₂ and Y ₃ in the general formula (2), the following structures may be mentioned (* represents M ₁ in the general formula (1), or This represents the bonding position of the substituent with M ₂ in the general formula (2)), and the present invention is not limited to these. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

<Method for producing phthalocyanine pigment>
In the phthalocyanine pigment represented by the general formula (1) of the present invention, the compound in which Y ₁ is a hydroxyl group is obtained by halogenating the phthalocyanine compound represented by the following general formula (3) and then hydrolyzing it. (General formula (4)). On the other hand, the compound in which Y ₁ is a substituent other than a hydroxyl group uses a phthalocyanine pigment represented by the general formula (4) as a starting material. A phthalocyanine pigment represented by the general formula (4) and an acid represented by Z ₁ P (═O) R ₁ R ₂ , Z ₂ C (═O) R ₃ or Z ₃ S (═O) ₂ R ₄ By reacting with a compound, a phthalocyanine pigment having a desired substituent can be obtained. Z < ₁ > -Z < ₃ > in the said acidic compound represents a halogen atom or a hydroxyl group, and R < ₁ > -R < ₄ > is synonymous with R < ₁ > -R < ₄ > in General formula (1), respectively.

(In the formula, X ₁ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15, and the halogen distribution. (The width is 4 or more. M ₁ represents Ga or In. Y ₃ represents a halogen atom or a hydroxyl group. Y ₄ represents a hydroxyl group.)

In the phthalocyanine pigment represented by the general formula (2) of the present invention, the compound in which Y ₂ and / or Y ₃ is a hydroxyl group is hydrolyzed after the phthalocyanine compound represented by the following general formula (5) is halogenated. (General formula (6)). On the other hand, the compound in which Y ₂ and / or Y ₃ is a substituent other than a hydroxyl group uses a phthalocyanine pigment represented by the general formula (6) as a starting material. A phthalocyanine pigment represented by the general formula (6) and an acid represented by Z ₁ P (═O) R ₁ R ₂ , Z ₂ C (═O) R ₃ or Z ₃ S (═O) ₂ R ₄ By reacting with a compound, a phthalocyanine pigment having a desired substituent can be obtained. Z < ₁ > -Z < ₃ > in the said acidic compound represents a halogen atom or a hydroxyl group, and R < ₁ > -R < ₄ > is synonymous with R < ₁ > -R < ₄ > in General formula (1), respectively.

(In the formula, X ₂ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₂ is 6 to 15, and the halogen distribution. The width is 4 or more, M ₂ represents Si, Ge, or Sn, Y ₅ and Y ₆ represent a halogen atom or a hydroxyl group, and Y ₇ and Y ₈ represent a hydroxyl group.

  The halogenation of the phthalocyanine compound represented by the general formula (3) or the general formula (5) is, for example, chlorosulfone described in “The Phthalocyanines Volume II Manufacture and Applications” (CRC Press, Inc., 1983) and the like. It can be produced by a method such as an acid method or a melting method.

  In the chlorosulfonic acid method, a phthalocyanine compound represented by the general formula (3) or the general formula (5) is dissolved in a sulfur oxide solvent such as chlorosulfonic acid or sulfuric acid, and a halogenating agent is added thereto. The method of halogenating is mentioned. The reaction at this time is preferably performed at a temperature of 20 to 120 ° C., and is preferably performed in a range of 1 to 10 hours.

  As the melting method, for example, as disclosed in JP-A-51-64534 (US Pat. No. 4,077,974), an aluminum halide such as aluminum chloride or aluminum bromide, or a halogenation such as titanium tetrachloride. One or two of various halogenating agents such as alkali metal halides or alkaline earth metal halides (hereinafter referred to as alkali (earth) metal halides) such as titanium, sodium chloride and sodium bromide, thionyl chloride, etc. Examples thereof include a method of halogenating the phthalocyanine represented by the general formula (3) or the general formula (5) in a melt of about 10 to 170 ° C. composed of the above mixture.

The halogenating agent used for halogenation means a fluorinating agent, a chlorinating agent, a brominating agent and an iodinating agent. For example, examples of the fluorinating agent include fluoroxytrifluoromethane, cesium fluoride sulfate, acetyl hypofluorite, N-fluorosulfonamide, diethylaminosulfur trifluoride, and N-fluoropyridinium salt.
As chlorinating agents, chlorine (Cl ₂ ), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone 2,3,4,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethylammonium chloride, benzeneselenenyl chloride and the like.
Examples of brominating agents include bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexane. Sa-2,5-dienone, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethylhydantoin, etc. Is mentioned.
Examples of the iodinating agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, N-iodosuccinimide, and the like. .

  Moreover, since the phthalocyanine represented by General Formula (4) or General Formula (6) has properties as a pigment, it may be used as it is. In one embodiment, the phthalocyanine represented by the general formula (4) or the general formula (6) is a starting material for a desired pigment. In such an embodiment, in order to improve the reaction efficiency with the acidic compound, the general formula (4) or the general formula (6) is used by a method such as an acid pasting method or a solvent salt milling method prior to the reaction. It is desirable to refine the phthalocyanine represented. By making the phthalocyanine represented by the general formula (4) or the general formula (6) in advance, it becomes easy to obtain a phthalocyanine pigment produced using the phthalocyanine in a fine state. When the phthalocyanine pigment thus miniaturized is used as a coloring composition, it becomes easy to obtain high brightness and high contrast.

  Moreover, reaction of the phthalocyanine represented by General formula (4) or General formula (6) and the said acidic compound can be advanced by mixing and stirring in an organic solvent, for example. Next, the desired phthalocyanine pigment can be obtained by removing the organic solvent.

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

  As a method for removing the organic solvent after completion of the reaction, a method known in the art can be used. In one embodiment, it is desirable that after suction filtration or pressure filtration, the organic solvent is compatible with the organic solvent used and washed with a low-boiling organic solvent, and then dried and removed. In the case of a water-soluble organic solvent, it is desirable to remove it by washing with water after mixing with water.

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

  The acid pasting method is a method of obtaining a fine colorant by adding a pigment in sulfuric acid and dissolving it, and then dropping and depositing a sulfuric acid solution in a large amount of water. By optimizing the amount of water used for precipitation, the temperature, etc., it is possible to obtain pigment particles having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range. it can.

  The solvent salt milling method is a method of heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment particles are crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent easily evaporates, those having a high boiling point of 120 ° C. or higher are preferred from the viewpoint of safety. Examples of such a water-soluble organic solvent include 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 or the like is used. These water-soluble organic solvents are preferably used in the range of 5 to 1000% by weight, more preferably 50 to 500% by weight, based on the total weight of the phthalocyanine pigment (100% by weight).

  When performing the solvent salt milling treatment, 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 weight based on the total weight of the phthalocyanine pigment (100% by weight).

  The phthalocyanine pigment of the present invention may be used in combination of two or more phthalocyanine pigments according to the intended use. In this case, phthalocyanine pigments produced separately may be mixed and used. Or you may use what was manufactured by synthesize | combining or refine | miniaturizing two or more types of phthalocyanine pigments simultaneously.

<Coloring composition>
The coloring composition of the present invention contains a colorant, a binder resin, and an organic solvent, and the colorant contains a phthalocyanine pigment represented by the general formula (1) or the general formula (2). In one embodiment, the coloring composition has a green color derived from the phthalocyanine pigment represented by General Formula (1) or General Formula (2) used as a colorant. The coloring composition of the present invention contains an additional dye as a colorant for adjusting the chromaticity and the like within a range not impairing the effect of the phthalocyanine pigment represented by the general formula (1) or (2). But you can.

<Colorant>
(Green pigment)
In one embodiment of the present invention, in order to further adjust the chromaticity, the coloring composition is a range other than the phthalocyanine pigment represented by the general formula (1) or the general formula (2) as long as the effects of the present invention are not impaired. A green pigment may be contained. 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- Examples include zinc phthalocyanine pigments described in JP 19383, JP 2007-320986 A, JP 2004-70342 A, and aluminum phthalocyanine pigments described in JP 4893859 A. 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)
In order to further adjust the chromaticity, the colored composition of the present invention may contain a yellow pigment as long as the effects of the present invention are not impaired. 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, 181 182,185,187,188,192,193,194,196,198,199,213,214, 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.

  Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , 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 a green dye is used in combination with the phthalocyanine pigment represented by the general formula (1) or the general formula (2), from the viewpoint of brightness and hue, the green dye / the general formula (1) or the general formula (2) The mass ratio of the represented phthalocyanine pigment is preferably in the range of 10/90 to 70/30. More preferably, it is the range of 20 / 80-40 / 60, More preferably, it is the range of 20 / 80-35 / 65.

  When a yellow dye is used in combination with the phthalocyanine pigment represented by the general formula (1) or the general formula (2), the yellow dye / the general formula (1) or the general formula (2) is used from the viewpoint of brightness and hue. The mass ratio of the phthalocyanine pigment to be used is preferably in the range of 70/30 to 10/90. More preferably, it is the range of 70 / 30-25 / 75, More preferably, it is the range of 70 / 30-40 / 60.

(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. In one embodiment, it is more preferably in the range of 20 to 60 nm, and further preferably in the range of 30 to 50 nm.

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

<Binder resin>
Binder resin should just disperse colorants, such as a pigment and a pigment | dye, especially the phthalocyanine pigment represented by General formula (1) or General formula (2). Specific examples of the binder resin include a thermoplastic resin and a thermosetting resin.

(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.

(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.

When producing a color filter using a coloring composition, the binder resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is preferable.
The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to 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.

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

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

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

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

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

  From the above viewpoint, the vinyl alkali-soluble resin obtained by polymerizing the acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mgKOH / g and a weight average molecular weight (Mw) of 10,000 to 80000. It is preferable. In one embodiment, the resin may be a copolymer of methacrylic acid, 2-hydroxyethyl (meth) acrylate, and other monomers such as n-butyl methacrylate.

  As another embodiment, when constituting a photosensitive coloring composition as an alkali development type color resist for a color filter, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin, In particular, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. When the above resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, no coating film foreign matter is generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When the above-mentioned linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped by the resin and has a degree of freedom in a mixture of resin and colorant. As a result, the colorant component easily aggregates and precipitates. In contrast, when an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used, the colorant is easily trapped in the resin in a mixture of the resin and the colorant. For this reason, in the solvent resistance test, it is difficult for the pigment to elute and the colorant component does not easily aggregate and precipitate. In addition, when the film is formed by exposure with active energy rays, the colorant molecules are fixed by the three-dimensional crosslinking of the resin, and the colorant component aggregates and precipitates even if the solvent is removed in the subsequent development process. It is estimated that it becomes difficult to do.

  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, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with 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. Remaining by using a tricarboxylic anhydride such as trimellitic anhydride or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, if necessary, such as increasing the number of carboxyl groups An anhydride 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.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dissolved in a monomer, a resin, and the like, and further applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, 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, Examples include tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, and isophorone.
Furthermore, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol 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 group Cole 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 group Coal 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, Examples thereof include methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester.
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. In one embodiment, the organic solvent is used in an amount of preferably 500 to 2000 parts by mass, more preferably 500 to 1000 parts by mass with respect to 100 parts by mass of the total mass of the colorant.

<Method for producing colored composition>
In the coloring composition of the present invention, a colorant containing a phthalocyanine pigment represented by the general formula (1) or the general formula (2) is added to a colorant carrier composed of the binder resin and, if necessary, a solvent. Preferably, it can be produced by finely dispersing together with a dispersing aid such as a pigment derivative using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. In addition, when the solubility of the phthalocyanine pigment represented by the general formula (1) or (2) is high, specifically, the solubility in the organic solvent to be used is high, and it is dissolved by stirring and foreign matter is confirmed. If not, it is not necessary to finely disperse and manufacture as described above.

  In addition, the coloring composition of the present invention is a mixture of a pigment, a phthalocyanine pigment represented by the general formula (1) or (2), and other colorants separately dispersed in a colorant carrier such as a binder resin. Can also be manufactured.

[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 in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. These may 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.

The following is mentioned as a commercially available resin-type dispersing agent.
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181 manufactured by Big Chemie Japan 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, Or Lactimon, Lactimon-WS or Bykumen etc.
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Nippon Lubrizol 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.
EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by BASF 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. Ajisper PA111, PB711, PB821, PB822, PB824, etc.

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

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

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

<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 phthalocyanine pigment represented by the general formula (1) or the general formula (2). It is more preferable that it is 10-150 mass parts from a viewpoint.

As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specific examples include the following.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo [2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2 -Acetophenones such as methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other phenylglyoxylic methyl esters.
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) and Esacure 1001M (Lamberti).
In addition, triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, JP-A-59-1504 and JP-A-61-243807 Organic peroxides, diazonium compound publications described in JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and USP-3567453, USP-2848328, USP-No. No. 2852379 and USP 2940853, azide compounds described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610 Ortho-quinonediazides, Japanese Patent Publication No. 55-39162, Various onium compounds including iodonium compounds described in JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977), JP-A-59-142205 Of the azo compound.
Furthermore, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science (J. IMAGE. SCI.)”, Volume 30, 174. (1986), titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85 to 277 (1988). ) And a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, an aluminate complex described in JP-A-3-209477, a borate compound described in JP-A-2-157760, JP-A-55-127550 and special 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide, organic halogen compound described in JP-A-59-107344, sulfonium described in JP-A-5-255347 Complexes or oxosulfonium complexes, aminoketone compounds described in JP-A-54-99185, JP-A-63-264560 and JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261661, JP 2000-80068, JP 2001-233842, JP 2004-534797, JP 2006-342166, JP 2008-094770, JP 2009-40762, JP 2010-15025, JP 2010-189279, JP2010-189 No. 80, JP 2010-526846, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP4202697 (1980), and JP-A-61-2558 An ester compound etc. are mentioned.

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

<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. More specifically, the photopolymer monomer is a compound having one or more photopolymerizable groups in the molecule, and its molecular weight is typically 1000 or less.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce 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.

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

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

<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 And dyes and sensitizers described in “Functional Materials” (1986, CMC). However, it is not limited to these, and other dyes and sensitizers that absorb light in the ultraviolet to near infrared region may be used. Two or more of these may be used in any ratio as required.
Among the sensitizers exemplified above, the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4 -Propoxy thioxanthone etc. can be mentioned. 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. be able to. Examples of coumarins include coumarin 1, coumarin 338, coumarin 102, and the like. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). However, it is not limited to these.

  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 contained in a coloring photosensitive composition, and a photocurable viewpoint. It is more preferable that it is 5-50 mass parts. In one embodiment, it is preferable to use a benzophenone derivative from the viewpoint of patterning sensitivity. For example, trade name “EAB-F” manufactured by Hodogaya Chemical Co., Ltd. can be used.

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that 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. If the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution decreases.

<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. The content of the leveling agent is usually preferably used in a proportion of 0.003 to 0.5% by mass in a total of 100% by mass of the coloring composition.

  A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. More specifically, it preferably has the characteristics that it has a hydrophilic group but has low solubility in water and has a low surface tension reducing ability when added to a colored composition. In addition, those having good wettability to the glass plate despite the low surface tension lowering ability are useful, and those that can sufficiently suppress the chargeability in an addition amount that does not cause coating film defects due to foaming. It 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 polyoxyalkylene alkyl ethers such as polyethylene glycol monolaurate; amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaines 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.

  Although it does not specifically limit, in one Embodiment, a coloring composition contains the coloring agent containing the phthalocyanine pigment represented by General formula (1) or General formula (2), Binder resin, and the organic solvent. . Here, it is preferable to use a vinyl alkali-soluble resin prepared using an acidic group-containing ethylenically unsaturated monomer as the binder resin. In another embodiment, the coloring composition further contains a photopolymerization initiator and a photopolymerizable monomer in addition to the above components. In another embodiment, the coloring composition further contains a sensitizer in addition to the above components. In these embodiments, in particular, a vinyl alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer is used as the binder resin, and a plurality of photopolymerizable groups are contained in one molecule as the photopolymerizable monomer. It is preferable to use a polyfunctional monomer having. Here, as the binder resin, it is more preferable to use a copolymer of a (meth) acrylic polymerizable monomer having an acidic group and another polymerizable monomer. According to such embodiment, it becomes easy to obtain the coloring composition excellent in developability, pattern sensitivity, and glass adhesiveness.

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

<Color filter>
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. 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 this invention can be manufactured by the printing method or the photolithographic method using the said coloring composition.

  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. In addition, control of the fluidity of the ink on the printing press is also important, and the ink viscosity 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. Thereafter, the film is immersed in a solvent or an alkali developer or sprayed with a developer or the like to remove uncured portions to form a desired pattern. By repeating the same operation for other colors, a color filter can be manufactured. 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.

The following examples relate to phthalocyanine pigments. The pigment produced in each example was evaluated as follows.
<Evaluation of pigment>
(Identification of phthalocyanine)
The identification of phthalocyanine is the coincidence between the molecular ion peak of the mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics) and the mass number obtained by calculation, and The ratio of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin Elmer) was matched with the theoretical value.

(Average number of halogen atom substitutions)
The average value of the number of halogen atoms substituted is analyzed by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX) of a liquid in which the pigment is burned by the oxygen combustion flask method and the combustion product is absorbed in water. Then, the amount of halogen was quantified and obtained by converting to the average value of the number of halogen atom substitutions.

(Halogen distribution width in pigment)
The halogen distribution width is the signal intensity of each molecular ion peak corresponding to each component (each peak value) in a mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics). ) And a value obtained by integrating each peak value (total peak value), and 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.

(Volume average primary particle size (MV))
The volume average primary particle size (MV) was obtained 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, 100 arbitrary pigments or colorant particles were selected, and the average value of the minor axis diameter and major axis diameter of the primary particles was defined as the particle diameter (d) of the colorant particles. Next, each pigment or colorant was regarded as a sphere having the previously determined particle diameter (d), and the volume (V) of each particle was determined. This operation was performed for 100 pigment or colorant particles, and the calculation was performed using the following formula (1).

Formula (1)
MV = Σ (V · d) / Σ (V)

<Manufacture of phthalocyanine pigments>
[Example 1]
(Production of phthalocyanine pigment (P-1))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 85 parts of gallium trichloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 203 parts of chlorogallium phthalocyanine (see the following chemical formula (7)).
Elemental analysis was performed on the obtained chlorogallium phthalocyanine. As a result, the calculated value (C) 62.22%, (H) 2.61%, and (N) 18.14% were compared with the actually measured value (C) 62. It was 4%, (H) 2.7%, and (N) 18.0%, and it was identified as the target compound.

  Next, in a reaction vessel, 100 parts of the chlorogallium phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 185 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added and stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the resulting precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing, water washing, drying and 139 parts of phthalocyanine. A pigment (P-1) was obtained. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-1), it was an average of 8.3, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum to identify the target compound. did. The halogen distribution width was 8. The obtained phthalocyanine pigment (P-1) had a volume average primary particle size of 42 nm.

[Example 2]
(Production of phthalocyanine pigment (P-2))
In the production of the phthalocyanine pigment (P-1), except that 85 parts of gallium trichloride are changed to 107 parts of indium trichloride and 185 parts of 1,3-dibromo-5,5-dimethylhydantoin are changed to 161 parts of N-bromosuccinimide. Produced 116 parts of a phthalocyanine pigment (P-2) in the same manner as in Example 1. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-2), it was an average of 6.0, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 5. The resulting phthalocyanine pigment (P-2) had a volume average primary particle size of 45 nm.

[Example 3]
(Production of phthalocyanine pigment (P-3))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 107 parts of silicon tetrachloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 8 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 188 parts of dichlorosilicon phthalocyanine (see the following chemical formula (8)).
Elemental analysis was performed on the obtained dichlorosilicon phthalocyanine. As a result, the calculated value (C) 62.85%, (H) 2.64%, and (N) 18.32% were measured (C) 62.85%. It was 6%, (H) 2.5%, (N) 18.2%, and was identified as the target compound.

  Next, in a reaction vessel, 100 parts of the dichlorosilicon phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 234 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was 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, followed by drying to 161 parts of phthalocyanine. A pigment (P-3) was obtained. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-3), it was 10.2 on average, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 8. The obtained phthalocyanine pigment (P-3) had a volume average primary particle size of 41 nm.

[Example 4]
(Production of phthalocyanine pigment (P-4))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 126 parts of tin tetrachloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 10 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 215 parts of dichlorotin phthalocyanine (see the following chemical formula (9)).
Elemental analysis was performed on the obtained dichlorotin phthalocyanine. As a result, the calculated value (C) 54.74%, (H) 2.30%, (N) 15.96%, and the actual value (C) 54.74%. 6%, (H) 2.3%, (N) 15.8%, and identified as the target compound.

  Next, in a reaction vessel, 406 parts of aluminum bromide, 94 parts of sodium bromide and 10 parts of ferric bromide were heated and melted, and 100 parts of the above dichlorotin phthalocyanine was added at 140 ° C. The temperature was raised to 160 ° C. and 137 parts of bromine was added dropwise. The above reaction solution is poured into 5000 parts of water, treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing and hot water washing, and then dried to obtain crude bromination. 213 parts of tin phthalocyanine were obtained. The obtained crude brominated tin phthalocyanine was dissolved in 1900 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution was poured into 12000 parts of water with stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% sodium hydroxide aqueous solution, washed with warm water, dried, and 200 parts of phthalocyanine pigment (P-4). ) Was manufactured. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-4), it was 12.2 on average, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 9. The obtained phthalocyanine pigment (P-4) had a volume average primary particle size of 39 nm.

[Example 5]
(Production of phthalocyanine pigment (P-5))
In the production of the phthalocyanine pigment (P-4), 223 parts of a phthalocyanine pigment was obtained in the same manner as in Example 4 except that 126 parts of tin tetrachloride was changed to 104 parts of germanium tetrachloride and 178 parts of bromine were changed to 183 parts of bromine. (P-5) was produced. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-5), it was an average of 14.1 and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 6. The obtained phthalocyanine pigment (P-5) had a volume average primary particle size of 36 nm.

[Example 6]
(Production of phthalocyanine pigment (P-6))
101 parts of phthalocyanine pigment in the same manner as in Example 3 except that 234 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 101 parts of trichloroisocyanuric acid in the production of the phthalocyanine pigment (P-3). (P-6) was produced. When the number of chlorine substitutions was calculated for the obtained phthalocyanine pigment (P-6), it was an average of 7.7, and the peak corresponding to the same molecular weight was also confirmed from the mass spectrum and identified as the target compound. did. The halogen distribution width was 7. The obtained phthalocyanine pigment (P-6) had a volume average primary particle size of 42 nm.

[Example 7]
(Production of phthalocyanine pigment (P-7))
406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of the above chlorogallium phthalocyanine was added at 140 ° C. The temperature was raised to 160 ° C. and 69 parts of chlorine was blown in. The above reaction solution is poured into 5000 parts of water, treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried and crude chlorination. 145 parts of gallium phthalocyanine were obtained. The obtained crude chlorinated gallium phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution was poured into 7200 parts of water with stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% sodium hydroxide aqueous solution, washed with warm water, dried, and 139 parts of phthalocyanine pigment (P-7). ) Was manufactured. When the number of chlorine substitutions was calculated for the obtained phthalocyanine pigment (P-7), the average was 11.8, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 9. The obtained phthalocyanine pigment (P-7) had a volume average primary particle size of 40 nm.

[Example 8]
(Production of phthalocyanine pigment (P-8))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 107 parts of indium trichloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 7 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 218 parts of chloroindium phthalocyanine (see the following chemical formula (10)).
Elemental analysis was performed on the obtained chloroindium phthalocyanine. As a result, the calculated value (C) was 57.9%, (H) was 2.43%, and (N) was 16.91%. It was 0%, (H) 2.3%, (N) 16.7%, and it was identified as the target compound.

  Next, in a reaction vessel, 406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of the chloroindium phthalocyanine was added at 140 ° C. The temperature was raised to 160 ° C. and 86 parts of chlorine was blown in. The above reaction solution is poured into 5000 parts of water, treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried and crude chlorination. 163 parts of indium phthalocyanine were obtained. The obtained crude chlorinated indium phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution was poured into 7200 parts of water with stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% aqueous sodium hydroxide, washed with warm water, dried, and 152 parts of phthalocyanine pigment (P-8). ) Was manufactured. As a result of calculating the number of chlorine substitutions for the obtained phthalocyanine pigment (P-8), it was 15.0 on average, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 4. The volume average primary particle diameter of the obtained phthalocyanine pigment (P-8) was 37 nm.

[Example 9]
(Production of phthalocyanine pigment (P-9))
Example 1 except that in the production of the phthalocyanine pigment (P-1), 185 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 185 parts of 1,3-diiodo-5,5-dimethylhydantoin. 154 parts of a phthalocyanine pigment (P-9) was produced in the same manner as described above. When the number of iodine substitutions was calculated for the obtained phthalocyanine pigment (P-9), the average was 6.1, and the peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 5. The obtained phthalocyanine pigment (P-9) had a volume average primary particle size of 47 nm.

[Example 10]
(Production of phthalocyanine pigment (P-10))
In a reaction vessel, 100 parts of the chlorogallium phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 25 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 185 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added and stirred at 25 ° C. for 5 hours. Subsequently, this 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, followed by drying to 151 parts of phthalocyanine. A pigment (P-10) was obtained. When the number of chlorine and bromine substitutions was calculated for the obtained phthalocyanine pigment (P-10), the chlorine average was 2.2 and the bromine average was 7.8. From the mass spectrum, peaks corresponding to the same molecular weight were obtained. Confirmed and identified as the desired compound. The halogen distribution width was 16. The obtained phthalocyanine pigment (P-10) had a volume average primary particle size of 41 nm.

[Example 11]
(Production of phthalocyanine pigment (P-11))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 104 parts of germanium tetrachloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 10 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 202 parts of dichlorogermanium phthalocyanine (see the following chemical formula (11)).
When elemental analysis was performed on the obtained dichlorogermanium phthalocyanine, the measured value (C) 58.58% was calculated against the calculated value (C) 58.58%, (H) 2.46%, and (N) 17.08%. 4%, (H) 2.4%, and (N) 16.9%, which were identified as the target compound.

  Next, in a reaction vessel, 100 parts of dichlorogermanium phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 71 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 129 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the resulting precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying and 133 parts of phthalocyanine. A pigment (P-11) was obtained. When the number of substitutions of chlorine and bromine was calculated for the obtained phthalocyanine pigment (P-11), the average of chlorine was 5.9 and the average of bromine was 6.1, and from the mass spectrum, peaks corresponding to the same molecular weight were obtained. Confirmed and identified as the desired compound. Further, the hahalogen distribution width was 20. The obtained phthalocyanine pigment (P-11) had a volume average primary particle size of 43 nm.

[Example 12]
(Production of phthalocyanine pigment (P-12))
In a reaction vessel, 100 parts of dichlorotin phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 22 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 162 parts of 1,3-diiodo-5,5-dimethylhydantoin was gradually added and stirred at 25 ° C. for 5 hours. Subsequently, this 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, water washing, drying and 148 parts phthalocyanine. A pigment (P-12) was obtained. When the number of chlorine and bromine substitutions was calculated for the obtained phthalocyanine pigment (P-12), the average chlorine was 2.0 and the average iodine was 6.0. From the mass spectrum, peaks corresponding to the same molecular weight were obtained. Confirmed and identified as the desired compound. The halogen distribution width was 12. The obtained phthalocyanine pigment (P-12) had a volume average primary particle size of 46 nm.

[Example 13]
(Production of phthalocyanine pigment (P-13))
To the reaction vessel, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the phthalocyanine pigment (P-1) obtained in Example 1 and 31 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 107 parts of a phthalocyanine pigment (P-13).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-13), it was an average of 8.2, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 8. The obtained phthalocyanine pigment (P-13) had a volume average primary particle size of 33 nm.

[Example 14]
(Production of phthalocyanine pigment (P-14))
To the reaction vessel was added 1000 parts of 1-pentanol, 100 parts of the phthalocyanine pigment (P-2) obtained in Example 2, and 34 parts of diphenyl phosphate, and the mixture was cooled to 5 ° C. and reacted for 4 hours. Subsequently, the reaction solution was heated to 120 ° C. and stirred for 2 hours. After cooling to room temperature, the product was filtered, washed with 1000 parts of methanol, and dried under reduced pressure at 40 ° C. overnight to obtain 109 parts of phthalocyanine pigment (P-14).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-14), it was an average of 6.0, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 5. The obtained phthalocyanine pigment (P-14) had a volume average primary particle size of 41 nm.

[Example 15]
(Production of phthalocyanine pigment (P-15))
To the reaction vessel, 1000 parts of ethylene glycol, 100 parts of the phthalocyanine pigment (P-3) obtained in Example 3 and 46 parts of diphenyl phosphate were added, cooled to 5 ° C., and reacted for 4 hours. Subsequently, the reaction solution was heated to 145 ° C. and stirred for 2 hours. After cooling to room temperature, the product was filtered, washed with 1000 parts of methanol, and then dried under reduced pressure at 40 ° C. overnight to obtain 121 parts of a phthalocyanine pigment (P-15).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-15), it was 10.1 on average, a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 7. The volume average primary particle diameter of the obtained phthalocyanine pigment (P-15) was 32 nm.

[Example 16]
(Production of phthalocyanine pigment (P-16))
To the reaction vessel, 2000 parts of dimethyl sulfoxide, 100 parts of the phthalocyanine pigment (P-4) obtained in Example 4 and 39 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, this solution was poured into 12000 parts of water. The reaction product was filtered, washed with 24000 parts of water, and then dried overnight at 60 ° C. under reduced pressure to obtain 116 parts of phthalocyanine pigment (P-16).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-16), the average was 12.0, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 9. The obtained phthalocyanine pigment (P-16) had a volume average primary particle size of 37 nm.

[Example 17]
(Production of phthalocyanine pigment (P-17))
To a reaction vessel, 1000 parts of ethylene glycol monoethyl ether, 100 parts of the phthalocyanine pigment (P-5) obtained in Example 5 and 36 parts of diphenyl phosphate were added, cooled to 5 ° C., and reacted for 4 hours. Subsequently, the reaction solution was heated to 130 ° C. and stirred for 2 hours. After cooling to room temperature, the product was filtered, washed with 1000 parts of methanol, and dried under reduced pressure at 40 ° C. overnight to obtain 114 parts of phthalocyanine pigment (P-17).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-17), it was 14.2 on average, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 6. The volume average primary particle diameter of the obtained phthalocyanine pigment (P-17) was 35 nm.

[Examples 18 to 34]
(Production of phthalocyanine pigments (P-18) to (P-34))
In the production of the phthalocyanine pigment (P-13), the same operation as in Example 13 was carried out, except that the raw material phthalocyanine pigment and acidic compound were changed to the conditions described in Table 1, respectively. 18) to (P-34) were obtained. Yield, average value of substitution number of halogen atoms represented by X ₁ or X ₂ , halogen distribution width, and volume average primary particle diameter are as shown in Table 2. From the mass spectrum, peaks corresponding to the same molecular weight are obtained. Confirmed and identified as the desired compound.

  The structural formulas of the phthalocyanine pigments obtained in Examples 1 to 34 are shown below. 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.

<Production of comparative phthalocyanine pigment>
[Comparative Example 1]
In the production of the phthalocyanine pigment (P-13), the phthalocyanine pigment (P-1) used as a starting material was changed to chlorogallium phthalocyanine similar to that in Example 1, and 31 parts of diphenyl phosphate were changed to 52 parts of diphenyl phosphate. Except that, the same operation as in Example 13 was performed to obtain 125 parts of a phthalocyanine pigment (P-35). The obtained phthalocyanine pigment does not have a halogen substituent in the phthalocyanine ring. The obtained phthalocyanine pigment had a volume average primary particle size of 38 nm.

[Comparative Example 2]
To the reaction vessel, 100 parts of 4-bromophthalimide, 132 parts of urea, 2.4 parts of ammonium molybdate, 0.8 part of sodium sulfate, and 200 parts of 1-chloronaphthalene were added and stirred. After heating to 150 ° C., 20.7 parts of silicon tetrachloride and 21.2 parts of urea were added and reacted at 250 ° C. for 7 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried. Next, 1000 parts of 98% sulfuric acid was added to the Erlenmeyer flask. The dried product was added and dissolved therein, followed by stirring at room temperature for 1 hour. Thereafter, sulfuric acid solution was poured into 6000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. Got a part.
Subsequently, the obtained phthalocyanine pigment, 1000 parts of 1-methyl-2-pyrrolidinone and 55 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 85 ° C. for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 108 parts of a phthalocyanine pigment (P-36).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-36), it was an average of 4.0, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 1. The volume average primary particle diameter of the obtained phthalocyanine pigment (P-36) was 55 nm.

[Comparative Example 3]
The number of bromine atoms substituted in the same manner as in Comparative Example 2 except that 100 parts of 4,5-dibromophthalic acid was used instead of 4-bromophthalimide and 19 parts of diphenyl phosphate was used instead of 55 parts of diphenyl phosphate. Of phthalocyanine pigment (P-37) having an average value of 8.0 and a halogen distribution width of 1 was obtained. The obtained phthalocyanine pigment (P-37) had a volume average primary particle size of 52 nm.

[Comparative Example 4]
The average value of the number of substitutions of chlorine atoms in the same manner as in Comparative Example 2 except that 100 parts of 4-chlorophthalic acid was used instead of 4-bromophthalimide and 62 parts of diphenyl phosphate was used instead of 55 parts of diphenyl phosphate. Of 114 and phthalocyanine pigment (P-38) having a chlorine distribution width of 1 was obtained. The obtained phthalocyanine pigment (P-38) had a volume average primary particle size of 56 nm.

[Comparative Example 5]
The number of chlorine atom substitutions was the same as in Comparative Example 2 except that 100 parts of 4,5-dichlorophthalic acid was used instead of 4-bromophthalimide and 53 parts of diphenyl phosphate was used instead of 55 parts of diphenyl phosphate. Of phthalocyanine pigment (P-39) having a mean value of 8.0 and a chlorine distribution width of 1 was obtained. The volume average primary particle diameter of the obtained phthalocyanine pigment (P-39) was 58 nm.

  Hereinafter, structural formulas of the phthalocyanine pigments obtained in Comparative Examples 1 to 5 are shown.

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

<Binder resin production method>
(Preparation of methacrylic 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 further continued for 3 hours to obtain a methacrylic resin solution having a weight average molecular weight (Mw) of 26000.
After the resin solution was cooled 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. Next, in consideration of the measured value, methacrylic resin solution 1 was prepared by adding propylene glycol monoethyl ether acetate to the previously obtained resin solution so that the nonvolatile content was 20% by mass.

<Evaluation of resin>
(Resin polymerization average molecular weight (Mw))
It is a weight average molecular weight (Mw) in terms of polystyrene measured by 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.

(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. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Preparation of resin-type dispersant solution>
EFKA4300 manufactured by BASF, which is a commercially available resin type dispersant, and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a nonvolatile content of 40% by mass, and a resin type dispersant solution 1 was obtained.

<Manufacture of pigment dispersion>
[Example 35]
(Pigment dispersion (GP-1))
The mixture having the following composition 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. Thereafter, the obtained mixture was filtered through a filter having a pore size of 5.0 μm to prepare a pigment dispersion (GP-1) having a nonvolatile component of 20% by mass.
Phthalocyanine pigment (P-1): 11.0 parts Methacrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts Resin-type dispersant solution 1: 5.0 parts

[Examples 36 to 68, Comparative Examples 6 to 10]
(Pigment dispersions (GP-2) to (GP-39))
Pigment dispersions (GP-2) to (GP-39) were produced in the same manner as in Example 35 except that the phthalocyanine pigment (P-1) was changed to the phthalocyanine pigment shown in Table 3.

<Evaluation of pigment dispersion>
The following evaluation was performed about the pigment dispersions (GP-1)-(GP-39) obtained by the Example and the comparative example. The results are shown in Table 3.

(Evaluation of contrast ratio (CR) of coating film)
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.

Apply the pigment dispersion on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dry at 70 ° C. for 20 minutes, then heat at 230 ° C. for 60 minutes and allow to cool. A coated substrate was prepared. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The contrast ratio was determined according to the following criteria.
A: 9000 or more: extremely good B: 6000 or more but less than 9000: good Δ: 3000 or more but less than 6000: practical use ×: less than 3000: poor

(Evaluation of heat resistance of coating film)
Apply the pigment dispersion on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dry at 70 ° C. for 20 minutes, then heat at 230 ° C. for 60 minutes and allow to cool. A coated substrate was prepared. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. [L * (1), a * (1), b * (1)] was measured for the chromaticity of the obtained coating film using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Further, the chromaticity [L * (2), a * (2), b * (2)] after heat treatment at 250 ° C. for 60 minutes is measured, and the color difference ΔE * ab is obtained by the following equation (1). It was.
Formula (1)
ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

The heat resistance was determined according to the following criteria.
A: ΔE * ab = 1 or less: Extremely good ○: ΔE * ab = 1-3: Good Δ: ΔE * ab = 3-5: Practical use ×: ΔE * ab = 5 or more: Bad

(Light resistance evaluation of coating film)
Apply the pigment dispersion on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dry at 70 ° C. for 20 minutes, then heat at 230 ° C. for 60 minutes and allow to cool. A coated substrate was prepared. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. An ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) was applied on the substrate, and the color before and after irradiation with ultraviolet light for 150 hours using a 470 W / m ² xenon lamp was measured. Thus, the color difference ΔE * ab was obtained. The judgment criteria are the same as in the heat resistance evaluation.

(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 500 times, and the number of foreign matters observable in arbitrary 5 fields of view through transmission was measured.
◎: 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

  As in Comparative Example 6, when the phthalocyanine ring was not substituted with halogen, both the contrast ratio and the fastness were low. In Comparative Examples 7 and 9 where the halogen substitution number is 4 and the halogen distribution width is 1, both the contrast ratio and the heat resistance are low, and the halogen substitution number is 8 as in Comparative Examples 8 and 10. When the value is 1, the contrast ratio tended to be low. Examples 35 to 68 of the present invention have a high contrast ratio and fastness (heat resistance and light resistance) in a coloring composition containing a phthalocyanine pigment having an average halogen substitution number of 6 to 15 and a halogen distribution width of 4 or more. Excellent results. Moreover, almost no foreign matter was found. From this result, it can be seen that a combination of a halogen substitution number of 6 or more and a halogen distribution width of 4 or more is effective for achieving both contrast ratio and fastness.

  The following examples relate to a photosensitive coloring composition using a phthalocyanine pigment, and a color filter using the photosensitive coloring composition. In the photosensitive coloring composition, a pigment other than the phthalocyanine pigment and its pigment dispersion were prepared as follows.

<Manufacture of other fine pigments>
(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, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine green pigment (PG58-1).

(Production of fine green pigment (PG7-1))
Phthalocyanine green pigment C.I. I. 200 parts of CI Pigment Green 7 (“GreenGNX” 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, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine green pigment (PG7-1).

(Production of fine green pigment (PG36-1))
Phthalocyanine green pigment C.I. I. 200 parts of 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, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine green pigment (PG36-1).

(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, this kneaded material was put into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine yellow pigment (PY150-1).

(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, this kneaded material was put into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine yellow pigment (PY138-1).

(Production of refined yellow pigment (PY 139-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Pariotol 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, this kneaded material was put into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine yellow pigment (PY139-1).

(Production of refined yellow pigment (PY185-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 185 (BASF "Pariotol Yellow L 1155"), 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, this kneaded material was put into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine yellow pigment (PY185-1).

(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 stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. to obtain 190 parts of fine diketopyrrolopyrrole pigment (PR254-1).

(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, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain an anthraquinone fine red pigment (PR177-1).

(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 into a stainless steel 1 gallon kneader (Inoue Seisakusho). And kneading at 80 ° C. for 6 hours. Next, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for a whole day and night to obtain a fine blue pigment (PB15: 6-1).

(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, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for a whole day and night to obtain a purple fine violet pigment (PV23-1).

<Manufacture of other fine pigment dispersions>
(Production of fine pigment dispersion (GP-40) to (VP-1))
Pigment dispersions (GP-40) to (VP-1) were produced in the same manner as in Example 35 except that the phthalocyanine pigment (P-1) was changed to the finer pigment shown in Table 4.

<Production of photosensitive coloring composition>
[Example 69]
(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): 20.9 parts PY138 / Pigment dispersion (YP-2): 29.1 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (“Aronix” manufactured by Toagosei Co., Ltd.) M-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 Cyclohexanone: 39.0 parts

[Examples 70 to 108, Comparative Examples 11 to 15]
The green photosensitive coloring compositions (GR-2) to (GR-2) to (GR) were respectively the same as in Example 69 except that the total of 50 parts of the pigment dispersion was changed to the components and parts by mass shown in Table 5. -45) was obtained.

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the photosensitive coloring composition obtained by the Example and the comparative example. The results are shown in Table 5.
(Evaluation of brightness)
The photosensitive coloring composition was apply | coated on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness using the spin coater. Next, the coating film was dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes. In this way, a coated substrate was obtained in which the chromaticity of the substrate was x = 0.297 and y = 0.570 in the C light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.
◎: 66.5 or more: Extremely good ○: 65.9 or more and less than 66.5: Good △: 65.3 or more and less than 65.9: Practical use ×: Less than 65.3: Bad

(Evaluation of solvent resistance)
The photosensitive coloring composition 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. Subsequently, after cooling this board | substrate to room temperature, it exposed to the ultraviolet light through the photomask using the 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.
The obtained striped green pixel was immersed in N-methyl-2-pyrrolidone (NMP) and methanol (MeOH) for 15 minutes, and the color difference of the green pixel part before and after immersion was measured. The color difference measurement method, calculation method, and evaluation criteria were the same as in the evaluation of heat resistance and light resistance.

  When the phthalocyanine ring was not substituted with halogen as in Comparative Example 11, both the brightness and solvent resistance were low. In Comparative Examples 12 and 14 where the halogen substitution number is 4 and the halogen distribution width is 1, the brightness and solvent resistance to NMP are low, and the halogen substitution number is 8 as in Comparative Examples 13 and 15. Those with a distribution width of 1 tended to have low brightness. In Examples 69 to 108 of the present invention, the photosensitive coloring composition containing a phthalocyanine pigment having an average halogen substitution number of 6 to 15 and a halogen distribution width of 4 or more has higher brightness than Comparative Examples 11 to 15, and The result was excellent in solvent resistance. From this result, it can be seen that a combination of a halogen substitution number of 6 or more and a halogen distribution width of 4 or more is effective for achieving both brightness and solvent resistance. Moreover, even when the phthalocyanine pigment of the present invention was used in combination with other green pigments and yellow pigments, good results were obtained.

<Production of color filter>
A color filter was prepared using the green photosensitive coloring composition containing the phthalocyanine pigment of the present invention. The used red photosensitive coloring composition and blue photosensitive coloring composition were prepared as follows.
(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).
PR254 / Pigment dispersion (RP-1): 30.0 parts PR177 / Pigment dispersion (RP-2): 20.0 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd.) “Aronix M-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 cyclohexanone: 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).
PB15: 6 • Pigment dispersion (BP-1): 45.0 parts PV23 • Pigment dispersion (VP-1): 5.0 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Toagosei) "Aronix M-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 part cyclohexanone: 39.0 parts

[Example 109]
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-13) of this invention was used, and the green coloring pixel layer was formed like the red coloring pixel layer. Further, similarly, a blue colored pixel layer was formed using the blue photosensitive coloring composition (BR-1) to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

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

Claims (8)

A phthalocyanine pigment represented by the following general formula (1) or the following general formula (2).

(In General Formula (1), X ₁ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15. And the halogen distribution width is at least 4. M ₁ represents Ga or In, Y ₁ represents a hydroxyl group, —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , — OS (═O) ₂ R ₄ R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents an alkoxyl group which may have a group or an aryloxy group which may have a substituent, and R ₃ may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. .R ₄ representing an cycloalkyl group which may have an aryl group or a substituted group may have a substituent heterocyclic group, water It represents groups, an optionally substituted alkyl group, a heterocyclic group which may have an aryl group or a substituted group may have a substituent.)

(In General Formula (2), X ₂ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₂ is 6 to 15. And the halogen distribution width is at least 4. M ₂ represents Si, Ge, or Sn, and Y ₂ and Y ₃ each independently represent a hydroxyl group, —OP (═O) R ₁ R ₂ , — _{OC (= O) R 3,} .R 1 and R ₂ represents a -OS (= O) ₂ R ₄ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, a substituent An aryl group that may have, an alkoxyl group that may have a substituent, or an aryloxy group that may have a substituent, R ₃ represents a hydrogen atom or an alkyl group that may have a substituent. A cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ) In the general formula (1), X ₁ is a chlorine atom or a bromine atom, Y ₁ is —OP (═O) R ₁ R ₂ , and in the general formula (2), X ₂ is a chlorine atom or a bromine atom. The phthalocyanine pigment according to claim 1, wherein Y ₂ and Y ₃ are —OP (═O) R ₁ R ₂ . In the general formula (1), X ₁ is a bromine atom, Y ₁ is —OP (═O) (OC ₆ H ₅ ) ₂ , and in the general formula (2), X ₂ is a bromine atom, Y ₂ and _{Y 3 are, -OP (= O) (OC} 6 H 5) is _2, phthalocyanine pigment according to claim 1 or 2.   The coloring composition containing a coloring agent, binder resin, and an organic solvent, Comprising: The said coloring agent contains the phthalocyanine pigment as described in any one of Claims 1-3.   The coloring composition of Claim 4 in which the said coloring agent contains at least one of a green pigment | dye and a yellow pigment | dye further.   The green pigment is C.I. I. Pigment Green 7, 36 and 58, which is at least one selected from the group consisting of C.I. I. The coloring composition according to claim 5, which is at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and 185.   Furthermore, the coloring composition as described in any one of Claims 4-6 containing at least one of a photopolymerizable monomer and a photoinitiator.   8. A color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment is according to any one of claims 4-7. A color filter formed of the coloring composition.