JP6753085B2 - Phthalocyanine pigments, coloring compositions and color filters - Google Patents

Description

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

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

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

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

Patent Document 1 proposes a composition for a color filter 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 copper halide 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. A composition for a color filter has been proposed, which comprises a green colorant composed of at least one halogenated dissimilar metal phthalocyanine pigment.

All of these phthalocyanine compounds are materials for producing high-brightness color filters. However, in recent years, the demand for high brightness has become even higher, and the compositions using these proposed colorants have insufficient lightness.

Patent Document 3 discloses a pigment composition that maintains a clear hue, high light resistance, and high heat resistance by using a halogen-free blue aluminum phthalocyanine pigment and a halogen-containing green pigment. There is.

According to Patent Document 4, in a coloring composition for a green color filter segment, by using an aluminum phthalocyanine pigment as a main pigment, high chromaticity and high brightness can be obtained even with a relatively small content, and color density and color purity can be obtained. The technology that achieves both of these is disclosed.

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

However, the pigment composition containing these aluminum phthalocyanine compounds has a problem that the heat resistance at 230 ° C. or higher and the light resistance for a long time, which are required for color filter applications, are not sufficient, and the spectral shape changes. was there. Further, the current situation is that problems such as high viscosity of the coloring composition and generation of foreign substances on the coating film due to poor dispersibility have not been sufficiently improved.

JP-A-2002-131521 JP-A-2002-250812 Japanese Unexamined Patent Publication No. 2003-4930 Japanese Unexamined Patent Publication No. 2004-333817 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 molecules of molecules even in a high temperature environment exceeding 230 ° C. It is an object of the present invention to provide a phthalocyanine pigment useful as a colorant, which is less likely to generate foreign substances due to association or aggregation. In addition, using the above-mentioned phthalocyanine pigment, it has excellent fastness (heat resistance, light resistance, solvent resistance), excellent color characteristics (brightness) and contrast ratio when used for color filter applications, and further, foreign matter generation. It is to provide a small amount of 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 the 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. Yes, the halogen distribution width is 4 or more. M ₁ indicates Ga or In. Y ₁ is a hydroxyl group, −OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , − OS (= O) ₂ Represents R _4. R ₁ and R ₂ independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substitution. Represents an alkoxyl group which may have a group or an aryloxy group which may have a substituent. R ₃ may have a hydrogen atom, an alkyl group which may have a substituent, and a substituent. Represents a cycloalkyl group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent. R ₄ has a hydroxyl group, an alkyl group which may have a substituent, and a substituent. Represents a heterocyclic group that may have an aryl group or a substituent.)

(In the 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. Yes, the halogen distribution width is 4 or more. M ₂ indicates Si, Ge, or Sn. Y ₂ and Y ₃ are independently hydroxylated, −OP (= O) R ₁ R ₂ , − It represents OC (= O) R ₃ , -OS (= O) ₂ R _4. R ₁ and R ₂ independently have a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, and a substituent. Represents an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R ₃ is a hydrogen atom and an alkyl group which may have a substituent. , A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. R ₄ has a hydroxyl group and a substituent. It represents an alkyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.)

Further, in the present invention, 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. It relates to the above-mentioned phthalocyanine pigment which is a chlorine atom or a bromine atom and Y ₂ and Y ₃ are −OP (= O) R ₁ R ₂ .

Further, in the present invention, 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. It relates to the above-mentioned phthalocyanine pigment which 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 coloring composition containing a colorant, a binder resin and an organic solvent, wherein the colorant contains the phthalocyanine pigment.

The present invention also relates to the above coloring composition, wherein the coloring agent further contains at least one of a green pigment and a yellow pigment.

Further, in the present invention, the green dye is C.I. I. Pigment Green is at least one selected from the group consisting of 7, 36 and 58, and the yellow pigment is C.I. I. Pigment Yellow 138, 139, 150 and 185. The coloring composition is at least one selected from the group.

The present invention further relates to the above-mentioned coloring composition, which further contains at least one of a photopolymerizable monomer and a photopolymerization initiator.

Further, in the present invention, in a color filter including 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 by the coloring composition. Regarding color filters.

According to the present invention, the phthalocyanine pigment represented by the general formula (1) or the general formula (2) has excellent fastness (heat resistance, light resistance, solvent resistance), high brightness and high contrast ratio. It is possible to provide a colorant that produces less foreign matter due to association or aggregation of molecules even in a high temperature environment exceeding 230 ° C. Further, the coloring composition containing the phthalocyanine pigment of the present invention as a colorant has 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 foreign matter is less generated due to association and aggregation of molecules even in the above environment.

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

<Parthalocyanine 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 in a coloring composition, particularly a green colorant.

(In the 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. Yes, the halogen distribution width is 4 or more. M ₁ indicates Ga or In. Y ₁ is a hydroxyl group, −OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , − OS (= O) ₂ Represents R _4. R ₁ and R ₂ independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substitution. Represents an alkoxyl group which may have a group or an aryloxy group which may have a substituent. R ₃ may have a hydrogen atom, an alkyl group which may have a substituent, and a substituent. Represents a cycloalkyl group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent. R ₄ has a hydroxyl group, an alkyl group which may have a substituent, and a substituent. Represents a heterocyclic group that may have an aryl group or a substituent.)

(In the 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. Yes, the halogen distribution width is 4 or more. M ₂ indicates Si, Ge, or Sn. Y ₂ and Y ₃ are independently hydroxylated, −OP (= O) R ₁ R ₂ , − It represents OC (= O) R ₃ , -OS (= O) ₂ R _4. R ₁ and R ₂ independently have a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, and a substituent. Represents an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R ₃ is a hydrogen atom and an alkyl group which may have a substituent. , A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. R ₄ has a hydroxyl group and a substituent. It represents an alkyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.)

Examples of the "halogen" in the general formula (1) and the general formula (2) include fluorine, bromine, chlorine and iodine, and bromine and chlorine are preferable, and bromine is particularly preferable.

When the average value of the number of substitutions of the halogen atoms represented by X ₁ in the general formula (1) or X ₂ in the general formula (2) is 6 to 15, it becomes 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, the 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 due to the association and aggregation of molecules, and it becomes easy to obtain various desired characteristics.
Here, the "halogen distribution width" is the distribution of the number of halogens substituted with the phthalocyanine pigments represented by the general formulas (1) and (2). The halogen distribution width is obtained by integrating the signal intensity (each peak value) of the molecular ion peak corresponding to the molecular weight of aluminum phthalocyanine of each component according to the number of halogen substitutions and each peak value in the mass spectrum obtained by mass spectrometry. The value (all peak values) was calculated, and the number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted and used as the halogen distribution width. In addition, two or more types of halogen atoms may be used in combination as long as they are within the range of the average number of substitutions and the distribution width described above. In this case, it is particularly preferable to use bromine and chlorine together.

Alkyl groups in R _{1 to} R ₄ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group and stearyl group. , 2-Ethylhexyl group and other linear or branched alkyl groups are mentioned, and alkyl groups having 1 to 6 carbon atoms are preferable.
Examples of the substituent of the alkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group such as a methoxy group, an aryl group such as a phenyl group and a trill group, and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group and a 2-butoxy. Ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl The group etc. can be mentioned.

Examples of the aryl group in R _{1 to} R ₄ include a monocyclic aromatic hydrocarbon group such as a phenyl group and a p-tolyl group, and a condensed aromatic hydrocarbon group such as a naphthyl group and an anthryl group. A hydrocarbon group is preferred. Further, an aryl group having 6 to 12 carbon atoms is preferable.
Examples of the substituent of the aryl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the aryl group having a substituent include a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group and a 2-dimethylaminophenyl group. Examples thereof include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

The alkoxyl groups in R ₁ and R ₂ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group and 2,3-dimethyl-3-3. Examples thereof include a linear or branched alkoxyl group such as a pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group and a 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 a halogen atom such as chlorine, fluorine and bromine, an aryl group such as an alkoxyl group, a phenyl group and a trill group, and a nitro group. 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 thereof include a ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, a benzyloxy group and the like.

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

Examples of the cycloalkyl group in R ₃ include a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group and a 4-tert-ptylcyclohexyl group, and a boronyl group and an adamantyl group. Condensed aliphatic hydrocarbon groups can be mentioned. Further, a cycloalkyl group having 5 to 12 carbon atoms is preferable.
Examples of the substituent of the cycloalkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group, a 4-hydroxycyclohexyl group and the like.

Examples of the heterocyclic group in R ₃ and R ₄ include an aliphatic heterocyclic group such as a pyridyl group, a pyrazil group, a piperidino group, a pyranyl group, a morpholino group and an acridinyl group, and an aromatic heterocyclic group. Further, a heterocyclic group having 4 to 12 carbon atoms is preferable, and a heterocyclic group having 5 to 13 ring members is preferable.
Examples of the substituent of the heterocyclic group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group and a nitro group. 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, an N-methylpyrrrolyl group and the like.

In one embodiment, among the phthalocyanine pigments represented by the general formulas (1) and (2), at least one of R ₁ and R ₂ has a substituent from the viewpoint of dispersibility and color characteristics. It is preferably an aryl group which may have an aryl group or an aryloxy group which may have a substituent. It is more preferable that both R ₁ and R ₂ are aryl groups or aryloxy groups. It is more preferred that both R ₁ and R ₂ are phenyl or phenoxy groups. Further, it is preferable that R ₃ and R ₄ are an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

The Y ₁ in the general formula (1) and the Y ₂ and Y ₃ in the general formula (2) are preferably −OP (= O) R ₁ R ₂ .

Typical examples of Y ₁ in the general formula (1) and Y ₂ and Y ₃ in the general formula (2) include the structures shown below (* indicates M ₁ in the general formula (1), or M ₁ in the general formula (1). The present invention is not limited to these (representing the bonding position of the substituent with M ₂ in the general formula (2)). The cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

<Manufacturing method of phthalocyanine pigment>
In the phthalocyanine pigment represented by the general formula (1) of the present invention, the compound Y ₁ is a hydroxyl group, after a halogenated phthalocyanine compound represented by the following general formula (3) is obtained by hydrolyzing (General formula (4)). On the other hand, the compound in which Y ₁ is a substituent other than the 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 to Z ₃ in the acidic compound is a halogen atom or a hydroxyl _group, R 1 to R ₄ are the same meanings as _R 1 to R ₄ in the general formula (1).

(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 halogenating the phthalocyanine compound represented by the following general formula (5). (General formula (6)). On the other hand, the compound in which Y ₂ and / or Y ₃ is a substituent other than the hydroxyl group uses a phthalocyanine pigment represented by the general formula (6) as a starting material. The phthalocyanine pigment represented by the general formula (6) and the acidity 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 to Z ₃ in the acidic compound is a halogen atom or a hydroxyl _group, R 1 to R ₄ are the same meanings as _R 1 to R ₄ in the general formula (1).

(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. Y ₇ and Y ₈ represent a hydroxyl group.)

Halogenation of the phthalocyanine compound represented by the general formula (3) or the general formula (5) is described in, for example, "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-based solvent such as chlorosulfonic acid or sulfuric acid, and a halogenating agent is charged therein. A method of halogenation can be mentioned. The reaction at this time is preferably carried out at a temperature of 20 to 120 ° C., preferably in the range of 1 to 10 hours.

As a melting method, for example, as described in Japanese Patent Application Laid-Open No. 51-64534 (US Pat. No. 4,077,974), halogenation such as aluminum chloride, aluminum bromide, and halogenation such as titanium tetrachloride. One or two types of various halogenating agents such as alkali metal halides such as titanium, sodium chloride and sodium bromide or alkaline earth metal halides (hereinafter referred to as alkali (earth) metal halides] and thionyl chloride. A method of halogenating phthalocyanine represented by the general formula (3) or the general formula (5) in a melt of the above mixture at about 10 to 170 ° C. can be mentioned.

The halogenating agent used for halogenation means a fluorinating agent, a chlorinating agent, a brominating agent and an iodizing agent. For example, examples of the fluorinating agent include fluoroxitrifluoromethane, cesium sulfate, acetylhypofluorite, N-fluorosulfonamide, diethylaminosulfatrifluoride, N-fluoropyridinium salt and the like.
Examples of the chlorinating agent include chlorine (Cl ₂ ), N-chlorosuccinimide, sulfyl 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 the brominating agent include bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexy. Sa-2,5-dieneon, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethylhydantoin, etc. Can be mentioned.
Examples of the iodinating agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, N-iodosuccinimide and the like. ..

Further, since the phthalocyanine represented by the general formula (4) or the 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 pacing method or a solvent salt milling method prior to the reaction. It is desirable to refine the represented phthalocyanine. By preliminarily refining the phthalocyanine represented by the general formula (4) or the general formula (6), it becomes easy to obtain a phthalocyanine pigment produced by using the phthalocyanine in a fine state. When the phthalocyanine pigment thus refined is used as the coloring composition, it becomes easy to obtain high brightness and high contrast.

Further, the reaction between the phthalocyanine represented by the general formula (4) or the general formula (6) and the acidic compound can be allowed to proceed by, for example, mixing and stirring in an organic solvent. Then, by removing the organic solvent, a desired phthalocyanine pigment can be obtained.

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

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

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

The solvent salt milling method is a method of heating a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment particles are crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. Examples of such water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid 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 the solvent salt milling treatment is performed, a resin may be added if necessary. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. The amount of the resin used is preferably in the range of 2 to 200% by weight based on the total weight of the phthalocyanine pigment (100% by weight).

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

<Coloring composition>
The coloring composition of the present invention contains a colorant, a binder resin and an organic solvent, and the colorant contains a phthalocyanine pigment represented by the general formula (1) or the general formula (2). In one embodiment, the coloring composition has a green tint derived from the phthalocyanine pigment represented by the general formula (1) or the general formula (2) used as a colorant. The coloring composition of the present invention contains an additional dye as a colorant for the purpose of adjusting the chromaticity, etc., as long as the effect of the phthalocyanine pigment represented by the general formula (1) or the general formula (2) is not impaired. It may be.

<Colorant>
(Green pigment)
In one embodiment of the present invention, the coloring composition is other than the phthalocyanine pigment represented by the general formula (1) or the general formula (2) in order to further adjust the chromaticity, as long as the effect of the present invention is not impaired. It may contain a green pigment. The green pigment is not particularly limited, but generally includes a green pigment or a green dye.
Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, Japanese Patent Application Laid-Open No. 2008- Zinc phthalocyanine pigments described in Japanese Patent Application Laid-Open No. 19383, Japanese Patent Application Laid-Open No. 2007-320986, Japanese Patent Application Laid-Open No. 2004-070342, etc., aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, etc. can be mentioned. Not limited. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment greens 7, 36 and 58.

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

(Yellow pigment)
The coloring composition of the present invention may contain a yellow dye in order to further adjust the chromaticity, as long as the effects of the present invention are not impaired. The yellow pigment is not particularly limited, but generally includes a yellow pigment or a yellow dye.

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

Specific examples of the yellow organic pigment that can be used in the coloring composition are shown below. Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as the quinophthalone pigments described in 192, 193, 194, 196, 198, 199, 213, 214 and Japanese Patent No. 4993026 can be used. In particular, from the viewpoint of heat resistance, light resistance, and lightness of the filter segment, the yellow dye is C.I. I. It is preferably at least one selected from the group consisting of Pigment Yellow 138, 139, 150 and 185.

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

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

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

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

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

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

When a green pigment is used in combination with the phthalocyanine pigment represented by the general formula (1) or the general formula (2), the green dye / general formula (1) or the general formula (2) is used from the viewpoint of brightness and hue. The mass ratio of the represented phthalocyanine pigment is preferably in the range of 10/90 to 70/30. It is more preferably in the range of 20/80 to 40/60, and even more preferably in the range of 20/80 to 35/65.

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

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

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

<Binder resin>
The binder resin may be any one that disperses a colorant such as a pigment or a pigment, particularly a phthalocyanine pigment represented by the general formula (1) or the general formula (2). Specific examples of the binder resin include thermoplastic resins and thermosetting resins.

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

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

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

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

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

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

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

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

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

From the above viewpoint, the vinyl-based alkali-soluble resin obtained by polymerizing the acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mgKOH / g and a weight average molecular weight (Mw) of 1000 to 80,000. 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 a photosensitive coloring composition is formed as an alkali-developable coloring resist for a color filter, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin. In particular, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. When the above resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, foreign matter in the coating film is not generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When the above linear resin having no ethylenically unsaturated double bond in the side chain is used, the colorant is less likely to be trapped by the resin in a liquid in which the resin and the colorant are mixed, and has a degree of freedom. As a result, the colorant component tends to aggregate and precipitate. On the other hand, when an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used, the colorant is likely to be trapped in the resin in a liquid in which the resin and the colorant are mixed. Therefore, in the solvent resistance test, the dye is less likely to elute, and the colorant component is less likely to aggregate and precipitate. Further, when the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film, the colorant molecules are fixed, and even if the solvent is removed in the subsequent developing step, the colorant components are aggregated and precipitated. It is estimated that it will be difficult to do.

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

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

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

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

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

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

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

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

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

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

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

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

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

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a coloring agent containing a phthalocyanine pigment represented by the general formula (1) or the general formula (2) is placed in a coloring agent carrier composed of the binder resin and, if necessary, a solvent. Preferably, it can be produced by finely dispersing it together with a dispersion aid such as a dye derivative by using various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Further, when the phthalocyanine pigment represented by the general formula (1) or the general formula (2) has high solubility, specifically, the phthalocyanine pigment has high solubility in the organic solvent used, is dissolved by stirring, and foreign matter is confirmed. If this is not the case, it is not necessary to manufacture the product in a finely dispersed manner as described above.

Further, in the coloring composition of the present invention, a pigment, a phthalocyanine pigment represented by the general formula (1) or (2), another coloring agent and the like are separately dispersed in a coloring agent carrier such as a binder resin and mixed. Can also be manufactured.

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

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

From the viewpoint of improving dispersibility, the amount of the dye derivative to be blended 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 heat resistance and light resistance, the blending amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant.

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

Examples of commercially available resin-type dispersants include the following.
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, manufactured by Big Chemie Japan. 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, Or Lactimon, Lactimon-WS or Bykumen and the like.
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Japan Lubrizol. 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.
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. Ajispar PA111, PB711, PB821, PB822, PB824, etc.

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

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

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

<Photopolymerization initiator>
The coloring composition of the present invention can contain a photopolymerization initiator. When using the photopolymerization initiator, the blending amount is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the phthalocyanine pigment represented by the general formula (1) or the general formula (2), and is photocurable. From the viewpoint of the above, it is more preferably 10 to 150 parts by mass.

As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specifically, the following can be mentioned.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl Ketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo [2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2 Acetphenones such as −methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Others such as phenylglycolic methyl ester.
More specifically, Irgacure 651, Irgacure 184, DaroCure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure. Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01, Irgacure OXE-02 (BASF), ADEKA OPTMER N1717, ADEKA OPTMER N1919, ADEKA ARCULS NCI- 831 (ADEKA) and Esacure1001M (Lamberti) can be mentioned.
In addition, the triazine derivatives described in JP-A-59-1281, JP-A-61-9621, and JP-A-60-60104, and JP-A-59-1504 and JP-A-61-243807. Organic peroxides, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and Diazonium Compound Publication No. USP No. 3567453, USP No. 2848328, USP No. 2852379 and USP 2940853 organic azide compounds, JP-A-36-22062, JP-A-37-13109, JP-A-38-18015, and JP-A-45-9610. Ortho-quinone diazodes, JP-A-55-39162, JP-A-59-140203, and the iodonium compounds described in "MACROMOLECULES", Vol. 10, p. 1307 (1977). Examples thereof include various onium compounds and azo compounds described in JP-A-59-142205.
Further, Japanese Patent Application Laid-Open No. 1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science (J.IMAG.SCI)", Vol. 30, No. 174. Metal Allen Complex described on page (1986), Titanosens described in JP-A-61-151197, "COORDINATION CHEMISTRY REVIEW", Vol. 84, pp. 85-277 (1988). ) And the transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, the aluminate complex described in JP-A-3-209477, and the borate compound described in JP-A-2-157760. 2,4,5-Triarylimidazole dimer described in JP-A-55-127550 and JP-A-60-202437, carbon tetrabromide, and organic halogen compounds described in JP-A-59-107344. , JP-A-5-255347, sulfonium complex or oxosulfonium complex, JP-A-54-99185, JP-A-63-264560 and JP-A-10-299777, aminoketone compounds, JP-A-2001-264530. No., JP-A-2001-261716, JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534977, JP-A-2006-342166, JP-A-2008-09470, JP-A-2009 -40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010-189280, Japanese Patent Application Laid-Open No. 2010-526846, Japanese Patent Application Laid-Open No. 2010-527338, Japanese Patent Application Laid-Open No. 2010-527339, USP3558309 (1971), USP4202697 No. 6 (1980) and the oxime ester compound described in JP-A-61-24558 can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine, isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the example, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

The following examples relate to phthalocyanine pigments. The evaluation of the pigments produced in each example was carried out as follows.
<Evaluation of pigment>
(Identification of phthalocyanine)
The identification of phthalocyanine is performed by matching the molecular ion peak of the mass spectrum obtained by using a time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by PerkinElmer) with the mass number obtained by calculation. , The ratio of carbon, hydrogen and nitrogen obtained by using an elemental analyzer (2400 CHN elemental analyzer, manufactured by PerkinElmer) was matched with the theoretical value.

(Average number of halogen atom substitutions)
The average number of halogen atom substitutions is obtained by burning the pigment by the oxygen combustion flask method and analyzing the liquid obtained by absorbing the combusted material in water by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX). Then, the amount of halogen was quantified and converted into the average value of the number of substitutions of halogen atoms.

(Halogen distribution width in pigment)
The halogen distribution width is the signal intensity (each peak value) of the molecular ion peak corresponding to each component in the mass spectrum obtained by using a time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by Bruker Daltonics). ) And the value obtained by integrating each peak value (total peak value) were calculated, and the number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted and used as the halogen distribution width.

(Volume average primary particle size (MV))
The volume average primary particle diameter (MV) was calculated by the following formula as a transmission electron microscope (TEM) "H-7650" manufactured by Hitachi High-Technologies Corporation. First, the colorant particles were photographed by TEM. In the obtained image, any 100 pigment or colorant particles were selected, and the average value of the minor axis diameter and the major axis diameter of the primary particles was defined as the particle size (d) of the colorant particles. Next, the volume (V) of each particle was determined by regarding each pigment or colorant as a sphere having the particle size (d) previously determined. This work was performed on 100 pigment or colorant particles, and the calculation was performed using the following formula (1).

Equation (1)
MV = Σ (V · d) / Σ (V)

<Manufacturing of phthalocyanine pigment>
[Example 1]
(Manufacturing of phthalocyanine pigment (P-1))
In the reaction vessel, 225 parts of phthalodinitrile and 85 parts of gallium trichloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. 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 chemical formula (7) below).
Elemental analysis of the obtained chlorogallium phthalocyanine revealed that the measured values (C) 62.22%, (H) 2.61%, and (N) 18.14% were measured values (C) 62. It was 4%, (H) 2.7%, and (N) 18.0%, and it was identified as the target compound.

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

[Example 2]
(Manufacture of phthalocyanine pigment (P-2))
In the production of the phthalocyanine pigment (P-1), 85 parts of gallium trichloride was changed to 107 parts of indium trichloride, and 185 parts of 1,3-dibromo-5,5-dimethylhydantin was 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), the average number was 6.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 5. The volume average primary particle size of the obtained phthalocyanine pigment (P-2) was 45 nm.

[Example 3]
(Manufacture of phthalocyanine pigment (P-3))
In the reaction vessel, 225 parts of phthalodinitrile and 107 parts of silicon tetrachloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 8 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. 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 chemical formula (8) below).
Elemental analysis of the obtained dichlorosilicon phthalocyanine revealed that the measured values (C) 62.85%, (H) 2.64%, and (N) 18.32% were measured values (C) 62. It was 6%, (H) 2.5%, and (N) 18.2%, and it was identified as the target compound.

Then, in the reaction vessel, 100 parts of the above dichlorosilicon phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 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 injected into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, dried, and 161 parts of phthalocyanine. The pigment (P-3) was obtained. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-3), the average number was 10.2, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 8. The volume average primary particle size of the obtained phthalocyanine pigment (P-3) was 41 nm.

[Example 4]
(Manufacture of phthalocyanine pigment (P-4))
In the reaction vessel, 225 parts of phthalodinitrile and 126 parts of tin tetrachloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 10 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. 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 dichlorotinphthalocyanine (see chemical formula (9) below).
Elemental analysis of the obtained dichlorotin phthalocyanine revealed that the measured values (C) 54.74%, (H) 2.30%, and (N) 15.96% were measured. It was 6%, (H) 2.3%, and (N) 15.8%, and it was identified as the target compound.

Then, in the 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 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 injected into 5000 parts of water and treated in the order of filtration, washing with warm water, washing with 1% hydrochloric acid aqueous solution, washing with hot water, washing with 1% sodium hydroxide aqueous solution, and washing with warm water, and then drying to make crude bromine. 213 parts of tin phthalocyanine was 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 is poured into 12,000 parts of water with stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% aqueous sodium hydroxide solution, washed with warm water, and dried to 200 parts of a phthalocyanine pigment (P-4). ) Was manufactured. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-4), the average number was 12.2, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 9. The volume average primary particle size of the obtained phthalocyanine pigment (P-4) was 39 nm.

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

[Example 6]
(Manufacturing of phthalocyanine pigment (P-6))
In the production of the phthalocyanine pigment (P-3), 101 parts of the phthalocyanine pigment was obtained 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. (P-6) was manufactured. When the number of chlorine substitutions was calculated for the obtained phthalocyanine pigment (P-6), the average number was 7.7, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound. did. The halogen distribution width was 7. The volume average primary particle size of the obtained phthalocyanine pigment (P-6) was 42 nm.

[Example 7]
(Manufacturing 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 into it. The above reaction solution is injected into 5000 parts of water and treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, hot water washing, 1% sodium hydroxide aqueous solution washing, and hot water washing, and then dried and crudely chlorinated. 145 parts of gallium phthalocyanine was 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% aqueous sodium hydroxide solution, washed with warm water, and dried to 139 parts of a phthalocyanine pigment (P-7). ) Was manufactured. When the number of chlorine substitutions was calculated for the obtained phthalocyanine pigment (P-7), the average number was 11.8, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound. did. The halogen distribution width was 9. The volume average primary particle size of the obtained phthalocyanine pigment (P-7) was 40 nm.

[Example 8]
(Manufacturing of phthalocyanine pigment (P-8))
In the reaction vessel, 225 parts of phthalodinitrile and 107 parts of indium trichloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 7 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 218 parts of chloroindium phthalocyanine (see chemical formula (10) below).
Elemental analysis of the obtained chloroindium phthalocyanine revealed that the calculated values (C) were 57.99%, (H) was 2.43%, and (N) was 16.91%, while the measured values (C) 58. It was 0%, (H) 2.3%, and (N) 16.7%, and it was identified as the target compound.

Then, in the 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 above chloroindium phthalocyanine was added at 140 ° C. The temperature was raised to 160 ° C. and 86 parts of chlorine was blown into it. The above reaction solution is injected into 5000 parts of water and treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, hot water washing, 1% sodium hydroxide aqueous solution washing, and hot water washing, and then dried and crudely chlorinated. 163 parts of indium phthalocyanine was 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 solution, washed with warm water, dried and dried to 152 parts of the phthalocyanine pigment (P-8). ) Was manufactured. When the number of chlorine substitutions was calculated for the obtained phthalocyanine pigment (P-8), the average number was 15.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 4. The volume average primary particle size of the obtained phthalocyanine pigment (P-8) was 37 nm.

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

[Example 10]
(Manufacturing of phthalocyanine pigment (P-10))
In the reaction vessel, 100 parts of the chlorogallium phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 25 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25 ° C. for 3 hours. Then, 185 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 injected into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, dried, and 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 average chlorine content was 2.2 and the average number of bromine was 7.8. From the mass spectrum, peaks corresponding to the same molecular weight were observed. It was confirmed and identified as the compound of interest. The halogen distribution width was 16. The volume average primary particle size of the obtained phthalocyanine pigment (P-10) was 41 nm.

[Example 11]
(Manufacturing of phthalocyanine pigment (P-11))
In the reaction vessel, 225 parts of phthalodinitrile and 104 parts of germanium tetrachloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 10 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This 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 chemical formula (11) below).
Elemental analysis of the obtained dichlorogermanium phthalocyanine revealed that the measured values (C) 58.58%, (H) 2.46%, and (N) 17.08% were measured values. It was 4%, (H) 2.4%, and (N) 16.9%, and it was identified as the target compound.

Then, in the reaction vessel, 100 parts of the dichlorogermanium phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 71 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25 ° C. for 3 hours. Then, 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 injected into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, dried, and dried with 133 parts of phthalocyanine. A pigment (P-11) was obtained. When the number of chlorine and bromine substitutions was calculated for the obtained phthalocyanine pigment (P-11), the average chlorine and bromine were 5.9, and the average bromine was 6.1. It was confirmed and identified as the compound of interest. The distribution width of hahalogen was 20. The volume average primary particle size of the obtained phthalocyanine pigment (P-11) was 43 nm.

[Example 12]
(Manufacturing of phthalocyanine pigment (P-12))
In the reaction vessel, 100 parts of the above dichlorotin phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 22 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25 ° C. for 3 hours. Then, 162 parts of 1,3-diiodo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution was injected into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, and dried to 148 parts of 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 number of chlorine and bromine was 2.0, and the average number of iodine was 6.0. From the mass spectrum, peaks corresponding to the same molecular weight were observed. It was confirmed and identified as the compound of interest. The halogen distribution width was 12. The volume average primary particle size of the obtained phthalocyanine pigment (P-12) was 46 nm.

[Example 13]
(Manufacture 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, the solution was injected into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours 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), the average number was 8.2, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 8. The volume average primary particle size of the obtained phthalocyanine pigment (P-13) was 33 nm.

[Example 14]
(Manufacturing of phthalocyanine pigment (P-14))
To the reaction vessel, 1000 parts of 1-pentanol, 100 parts of the phthalocyanine pigment (P-2) obtained in Example 2, and 34 parts of diphenyl phosphate were added, cooled to 5 ° C., and reacted for 4 hours. Subsequently, the reaction solution was heated to 120 ° C. and heated 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. for 24 hours to obtain 109 parts of a phthalocyanine pigment (P-14).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-14), the average number was 6.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 5. The volume average primary particle size of the obtained phthalocyanine pigment (P-14) was 41 nm.

[Example 15]
(Manufacturing 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 temperature of the reaction solution was raised to 145 ° C., and the mixture was heated 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. for 24 hours 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), the average number was 10.1, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 7. The volume average primary particle size of the obtained phthalocyanine pigment (P-15) was 32 nm.

[Example 16]
(Manufacturing 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, the solution was injected into 12000 parts of water. The reaction product was filtered, washed with 24,000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 116 parts of a phthalocyanine pigment (P-16).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-16), the average number was 12.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 9. The volume average primary particle size of the obtained phthalocyanine pigment (P-16) was 37 nm.

[Example 17]
(Manufacturing of phthalocyanine pigment (P-17))
To the 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 heated 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. for 24 hours to obtain 114 parts of a phthalocyanine pigment (P-17).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (P-17), the average number was 14.2, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 6. The volume average primary particle size of the obtained phthalocyanine pigment (P-17) was 35 nm.

[Examples 18 to 34]
(Manufacturing of Phthalocyanine Pigments (P-18) to (P-34))
In the production of the above-mentioned phthalocyanine pigment (P-13), the same operations as in Example 13 were carried out except that the raw material phthalocyanine pigment and the acidic compound were changed to the conditions shown in Table 1, respectively. 18)-(P-34) were obtained. Table 2 shows the yield, the average number of halogen atom substitutions represented by X ₁ or X ₂ , the halogen distribution width, and the volume average primary particle size, and the peaks corresponding to the same molecular weight can be obtained from the mass spectrum. It was confirmed and identified as the target 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 the average value of the number of halogen atom substitutions.

<Manufacturing of comparative phthalocyanine pigments>
[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 the same chlorogallium phthalocyanine as in Example 1, and 31 parts of diphenyl phosphate was changed to 52 parts of diphenyl phosphate. The same operation as in Example 13 was carried out to obtain 125 parts of a phthalocyanine pigment (P-35). The obtained phthalocyanine pigment does not have a halogen substituent on the phthalocyanine ring. The volume average primary particle size of the obtained phthalocyanine pigment was 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 parts 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 the mixture was reacted at 250 ° C. for 7 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried. Then 1000 parts of 98% sulfuric acid was added to the Erlenmeyer flask. The dried product was added thereto to dissolve it, and the mixture was stirred at room temperature for 1 hour. After that, sulfuric acid solution was injected into 6000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. I got a part.
Next, 1000 parts of the obtained phthalocyanine pigment, 1-methyl-2-pyrrolidinone and 55 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 85 ° C. for 3 hours, the solution was injected into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours 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), the average number was 4.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and it was identified as the target compound. did. The halogen distribution width was 1. The volume average primary particle size of the obtained phthalocyanine pigment (P-36) was 55 nm.

[Comparative Example 3]
Substitution number of bromine atoms 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. 84 parts of a phthalocyanine pigment (P-37) having an average value of 8.0 and a halogen distribution width of 1 was obtained. The volume average primary particle size of the obtained phthalocyanine pigment (P-37) was 52 nm.

[Comparative Example 4]
The average number of chlorine atom substitutions was the same 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. Obtained 114 parts of a phthalocyanine pigment (P-38) having a chlorine distribution width of 4.0 and a chlorine distribution width of 1. The volume average primary particle size of the obtained phthalocyanine pigment (P-38) was 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. 104 parts of a phthalocyanine pigment (P-39) having an average value of 8.0 and a chlorine distribution width of 1 was obtained. The volume average primary particle size of the obtained phthalocyanine pigment (P-39) was 58 nm.

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

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

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

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

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

<Preparation of resin type dispersant solution>
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 non-volatile content of 40% by mass to obtain a resin-type dispersant solution 1.

<Manufacturing 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 for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. Then, the obtained mixture was filtered through a filter having a pore size of 5.0 μm to prepare a pigment dispersion (GP-1) having a non-volatile component of 20% by mass.
Phthalocyanine pigment (P-1): 11.0 parts 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 prepared 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 pigment dispersions (GP-1) to (GP-39) obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 3.

(Contrast ratio (CR) evaluation of coating film)
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a coloring composition coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing planes of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and if a part of the polarizing surface is displaced, the light is transmitted when the polarizing plates are parallel. When the amount of light emitted is reduced and the polarizing plates are orthogonal, part of the light is transmitted. This transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.

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. The measurement was carried out through a black mask having a 1 cm square hole in the measurement portion.

The pigment dispersion is applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated and allowed to cool at 230 ° C. for 60 minutes. A coating film substrate was prepared in. The contrast ratio (CR) of the obtained coated substrate was measured. The produced 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.
⊚: 9000 or more: extremely good ○: 6000 or more to less than 9000: good Δ: 3000 or more to less than 6000: practically possible ×: less than 3000: defective

(Evaluation of heat resistance of coating film)
The pigment dispersion is applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated and allowed to cool at 230 ° C. for 60 minutes. A coating film substrate was prepared in. The produced coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The chromaticity of the obtained coating film was measured [L * (1), a * (1), b * (1)] 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 was measured, and the color difference ΔE * ab was obtained by the following formula (1). It was.
Equation (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.
⊚: ΔE * ab = 1 or less: extremely good ○: ΔE * ab = 1-3: good Δ: ΔE * ab = 3 to 5: practically usable ×: ΔE * ab = 5 or more: defective

(Evaluation of light resistance of coating film)
The pigment dispersion is applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated and allowed to cool at 230 ° C. for 60 minutes. A coating film substrate was prepared in. The produced 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 attached 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, and the above formula (1) The color difference ΔE * ab was obtained. The judgment criteria are the same as for the heat resistance evaluation.

(Foreign matter evaluation)
The evaluation of the generation of foreign matter was carried out by applying a coloring composition on a transparent substrate so that the dry coating film was about 2.0 μm, heating in an oven at 250 ° C. for 60 minutes, and allowing to cool. The number of foreign substances inside was measured. For evaluation, surface observation was performed using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured by transmission.
⊚: Number of foreign substances is less than 3: Extremely good ○: Number of foreign substances is 3 or more and less than 20: Good Δ: Number of foreign substances is 21 or more and less than 100: Practical ×: Number of foreign substances is 100 More than one: defective

When the phthalocyanine ring was not replaced with a halogen as in Comparative Example 6, both the contrast ratio and the robustness were low. Further, in Comparative Examples 7 and 9 in which the number of halogen substitutions is 4 and the halogen distribution width is 1, both the contrast ratio and the heat resistance are low, and the number of halogen substitutions is 8 as in Comparative Examples 8 and 10, but the halogen distribution width. When the value is 1, the contrast ratio tends to be low. 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 in Examples 35 to 68 of the present invention has a high contrast ratio and fastness (heat resistance, light resistance). The result was excellent. In addition, the occurrence of foreign matter could hardly be confirmed. From this result, it can be seen that a combination having a halogen substitution number of 6 or more and a halogen distribution width of 4 or more is effective for achieving both the contrast ratio and the robustness.

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

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

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

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

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

(Manufacturing of refined yellow pigment (PY138-1))
Kinoftalone yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (BASF's "Pariotor Yellow L 0962HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a fine yellow pigment (PY138-1).

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

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

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

(Manufacturing of refined red pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (BASF's "Chromophtal Red A2B"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain an anthraquinone-based finely divided red pigment (PR177-1).

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

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

<Manufacturing of other fine pigment dispersions>
(Manufacturing of refined pigment dispersions (GP-40) to (VP-1))
Pigment dispersions (GP-40) to (VP-1) were prepared in the same manner as in Example 35, except that the phthalocyanine pigment (P-1) was changed to the refined pigment shown in Table 4.

<Manufacturing of photosensitive coloring composition>
[Example 69]
(Green Photosensitive Coloring Composition (GR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
Pigment dispersion (GP-1): 20.9 parts PY138 / Pigment dispersion (YP-2): 29.1 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (Aronix manufactured by Toa Synthetic Co., Ltd.) M-402 "): 2.0 parts Photopolymerization initiator (BASF" Irgacure 907 "): 1.2 parts Sensitizer (Hodogaya Chemical Industry Co., Ltd." EAB-F "): 0.3 parts Cyclohexanone: 39.0 parts

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

<Evaluation of photosensitive coloring composition>
The photosensitive coloring compositions obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 5.
(Evaluation of lightness)
The photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater. Then, the coating film was dried at 70 ° C. for 20 minutes and then 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 Δ: 65.3 or more and less than 65.9: Practical use ×: Less than 65.3: Defective

(Evaluation of solvent resistance)
The photosensitive coloring composition was applied to a glass substrate on which a black matrix was formed in advance by a spin coating method, and then dried at 70 ° C. for 20 minutes in a clean oven. Then, after cooling this substrate to room temperature, ultraviolet light was exposed through a photomask using an ultra-high pressure mercury lamp.
Then, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
The obtained striped green pixels were immersed in N-methyl-2-pyrrolidone (NMP) and methanol (MeOH) for 15 minutes, and the color difference of the green pixel portion before and after the immersion was measured. The color difference measurement method, calculation method, and evaluation criteria were the same as those for the evaluation of heat resistance and light resistance.

When the phthalocyanine ring was not replaced with a halogen as in Comparative Example 11, both the brightness and the solvent resistance were low. Further, in Comparative Examples 12 and 14 in which the number of halogen substitutions is 4 and the halogen distribution width is 1, the brightness and the solvent resistance to NMP are low, and the number of halogen substitutions is 8 as in Comparative Examples 13 and 15, but halogen. Those having a distribution width of 1 tended to have low brightness. 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 in Examples 69 to 108 of the present invention has higher brightness and higher brightness than Comparative Examples 11 to 15. The result was excellent solvent resistance. From this result, it can be seen that a combination having 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. In addition, good results were obtained even when the phthalocyanine pigment of the present invention was used in combination with another green pigment or yellow pigment.

<Making color filters>
A color filter was prepared using the green photosensitive coloring composition containing the phthalocyanine pigment of the present invention. The red photosensitive coloring composition and the blue photosensitive coloring composition used were prepared as follows.
(Red Photosensitive Coloring Composition (RR-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).
PR254 / pigment dispersion (RP-1): 30.0 parts PR177 / pigment dispersion (RP-2): 20.0 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toa Synthetic Co., Ltd.) "Aronix M-402": 2.0 parts Photopolymerization initiator (BASF "Irgacure 907"): 1.2 parts Sensitizer (Hodogaya Chemical Industry Co., Ltd. "EAB-F"): 0.3 Part Cyclohexanone: 39.0 parts

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

[Example 109]
The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix was previously formed by a spin coating method, and then dried at 70 ° C. for 20 minutes in a clean oven. Then, after cooling this substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultra-high pressure mercury lamp.
Then, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (GR-13) of the present invention was used to form a green colored pixel layer in the same manner as the red colored pixel layer. Further, in the same manner, the blue photosensitive coloring composition (BR-1) was used to form a blue colored pixel layer to obtain a color filter (CF-1). The film thickness of each colored pixel layer was 2.0 μm.

The brightness and contrast ratio of the obtained color filters were evaluated. The measuring method is the same as in the case of evaluation of the pigment dispersion. The color filters using the green coloring composition of the present invention all had high brightness and excellent 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 the 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. Yes, the halogen distribution width is 4 or more. M ₁ indicates Ga or In. Y ₁ is a hydroxyl group, −OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , − OS (= O) ₂ Represents R _4. R ₁ and R ₂ independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substitution. Represents an alkoxyl group which may have a group or an aryloxy group which may have a substituent. R ₃ may have a hydrogen atom, an alkyl group which may have a substituent, and a substituent. Represents a cycloalkyl group, an aryl group which may have a substituent or a heterocyclic group which may have a substituent. R ₄ has a hydroxyl group, an alkyl group which may have a substituent, and a substituent. Represents a heterocyclic group that may have an aryl group or a substituent.)

(In the 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. Yes, the halogen distribution width is 4 or more. M ₂ indicates Si, Ge, or Sn. Y ₂ and Y ₃ are independently hydroxylated, −OP (= O) R ₁ R ₂ , − It represents OC (= O) R ₃ , -OS (= O) ₂ R _4. R ₁ and R ₂ independently have a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, and a substituent. Represents an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R ₃ is a hydrogen atom and an alkyl group which may have a substituent. , A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. R ₄ has a hydroxyl group and a substituent. It represents an alkyl group, 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. The phthalocyanine pigment according to claim 1 or 2, wherein Y ₂ and Y ₃ are −OP (= O) (OC ₆ H ₅ ) ₂ . A coloring composition containing a colorant, a binder resin, and an organic solvent, wherein the colorant contains the phthalocyanine pigment according to any one of claims 1 to 3. The coloring composition according to claim 4, wherein the colorant further contains at least one of a green pigment and a yellow pigment. The green pigment is C.I. I. Pigment Green is at least one selected from the group consisting of 7, 36 and 58, and the yellow pigment is C.I. I. The coloring composition according to claim 5, which is at least one selected from the group consisting of Pigment Yellow 138, 139, 150 and 185. The coloring composition according to any one of claims 4 to 6, further comprising at least one of a photopolymerizable monomer and a photopolymerization initiator. The color filter including 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 described in any one of claims 4 to 7. A color filter formed by the coloring composition of.