KR20190073337A - Phthalocyanine pigment, coloring composition and color filter - Google Patents

Abstract

The present invention relates to a phthalocyanine pigment represented by chemical formula (1) or (2), a coloring composition, and a color filter and, more specifically, to a phthalocyanine pigment excellent in heat resistance, light resistance, and solvent resistance, a coloring composition, and a color filter.

Description

PHOTHALOCYANINE PIGMENT, COLORING COMPOSITION AND COLOR FILTER,

An embodiment of the present invention relates to a novel phthalocyanine pigment. Further, another embodiment relates to a coloring composition comprising the phthalocyanine pigment and a color filter formed from the coloring composition. The color filter can be used for a color liquid crystal display device, an organic EL display device, a color image pickup device, and the like.

In recent years, materials for forming color images have become mainstream as image recording materials. As a color image recording material, specifically, 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. In addition, a color filter is used to record and reproduce a color image in an image pickup device such as a CCD, as an image pickup device, and as an LCD, a PDP, an organic electroluminescence, an electronic paper (electronic paper) have. In these color image recording materials and color filters, pigments (dyes or pigments) of three primary colors of so-called additive color mixing method or subtractive color mixing method are used for displaying or recording full color images. However, there are no pigments suitable for various use conditions, having absorption characteristics and color characteristics capable of realizing a desirable color material active range, and improvement is strongly demanded.

The pigment used for each of the above-mentioned uses differs in the required color qualities and the required quality for each application depending on the use thereof, but in terms of the light resistance and heat resistance of the recorded product, pigments are mainly used as pigments.

In the production of green filters in color filters, various phthalocyanine-based compounds are generally used as colorants, and many compositions for color filters containing them have been proposed. Among them, C.I. A copper phthalocyanine compound represented by Pigment Green 36 or C.I. Many coloring agents for color filters using zinc phthalocyanine compounds represented by Pigment Green 58 have been proposed.

As a coloring agent for a color filter, it has been required so far to achieve a high transmittance (high brightness) and a high contrast of a color filter. In recent years, in addition to these, from the viewpoint of thinning of the color filter and high color reproducibility, there is a growing demand for a colorant having a high coloring power. However, contrary to these trends, conventional copper phthalocyanine compounds or zinc phthalocyanine compounds lack coloring ability. Therefore, it is necessary to develop a colorant having high brightness and high coloring power, and fastness equivalent to that of conventional phthalocyanine compounds .

At present, phthalocyanine pigments of different metals have been attracting attention in order to attain high coloring power.

Patent Document 1 discloses a green pigment in which a halogenated copper phthalocyanine pigment and a center metal are at least one selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, And a green coloring agent composed of a halogenated heterometallic phthalocyanine pigment of the species.

Patent Document 2 discloses a technology that achieves high color densities and color purity with high chromaticity even at a relatively small content by using an aluminum phthalocyanine pigment as a main pigment in a coloring composition for a green color filter segment .

Japanese Patent Application Laid-Open No. 2002-250812 Japanese Patent Application Laid-Open No. 2004-333817

A problem to be solved by the embodiment of the present invention is to provide a color filter which is excellent in fastness (heat resistance, light resistance, and solvent resistance), excellent in color characteristics (brightness) and contrast ratio, And a phthalocyanine pigment useful as a colorant, which is less likely to generate foreign matter. The phthalocyanine pigment is excellent in fastness (heat resistance, light resistance, and solvent resistance) and excellent in color characteristics (lightness and coloring power) and contrast ratio when used as a color filter, A coloring composition, and a high-quality color filter using the same.

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

[Chemical Formula 1]

[In the general formula (1)

X ₁ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₁ is 1 or more and less than 6 and a halogen distribution width is 2 or more.

M ₁ represents Al, Ga or In.

Y ₁ represents -OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , -OS (= O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, 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 represents a hydrogen atom, 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 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

(2)

[In the general formula (2)

X ₂ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₂ is 1 or more and less than 6 and a halogen distribution width is 2 or more.

M ₂ represents Si, Ge or Sn.

Y ₂ and Y ₃ each independently represent -OP (═O) R ₁ R ₂ , -OC (═O) R ₃ , -OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, 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 represents a hydrogen atom, 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 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

In one embodiment of the present invention, X ₁ in the general formula (1) is a chlorine atom or a bromine atom, Y ₁ is -OP (= O) R ₁ R ₂ , , X ₂ is a chlorine atom or a bromine atom, and Y ₂ and Y ₃ are -OP (= O) R ₁ R ₂ .

In one embodiment of the present invention, X ₁ in the general formula (1) is a bromine atom, Y ₁ is -OP (= O) (OC ₆ H ₅ ) ₂ , , X ₂ is a bromine atom, and Y ₂ and Y ₃ are -OP (= O) (OC ₆ H ₅ ) ₂ .

Further, an embodiment of the present invention relates to a coloring composition comprising a colorant, a binder resin and an organic solvent, wherein the colorant contains the phthalocyanine pigment.

Further, an embodiment of the present invention relates to the coloring composition, wherein the coloring agent further contains at least one of a green coloring matter and a yellow coloring matter.

Further, in an embodiment of the present invention, the green pigment is a coloring material selected from the group consisting of C.I. Pigment Green 7, 36, and 58, and the yellow pigment is at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, 185 and a quinophthalone pigment represented by the following general formula (7).

(3)

[In the formula (7), R ¹ to R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent or an aryl group which may have a substituent. Provided that at least one adjacent pair of R ¹ to R ⁴ groups and / or at least one adjacent pair of R ¹⁰ to R ¹³ are integral to form an aromatic ring which may have a substituent .]

Further, one embodiment of the present invention relates to the above colored composition further comprising at least one of a photopolymerizable monomer and a photopolymerization initiator.

Further, an embodiment of the present invention is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, To a color filter formed by a coloring composition.

According to the embodiment of the present invention, it is possible to provide a color filter which is excellent in fastness (heat resistance, light resistance and solvent resistance), excellent in color characteristics (lightness) and contrast ratio, , A phthalocyanine pigment useful as a coloring agent can be provided. The phthalocyanine pigment is excellent in color fastness (lightness and tinting strength) and contrast ratio when used as a color filter and excellent in fastness (heat resistance, light resistance, and solvent resistance) Composition, and a high-quality color filter using the same.

Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, when "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate" or " Acrylate and / or methacrylate "," acrylate and / or methacrylate "," acrylate and / or methacrylate "," acrylate and / Or " acrylamide and / or methacrylamide ". In the present specification, "C.I." means a color index (C.I.).

<Phthalocyanine Pigment>

The phthalocyanine pigment which is an embodiment of the present invention is represented by the general formula (1) or (2), and can be suitably used as a coloring agent used in the coloring composition, particularly, a green coloring agent.

[Chemical Formula 4]

[In the general formula (1)

X ₁ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₁ is 1 or more and less than 6 and a halogen distribution width is 2 or more.

M ₁ represents Al, Ga or In.

Y ₁ represents -OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , -OS (= O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, 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 represents a hydrogen atom, 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 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

[Chemical Formula 5]

[In the general formula (2)

X ₂ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₂ is 1 or more and less than 6 and a halogen distribution width is 2 or more.

M ₂ represents Si, Ge or Sn.

Y ₂ and Y ₃ each independently represent -OP (═O) R ₁ R ₂ , -OC (═O) R ₃ , -OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, 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 represents a hydrogen atom, 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 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

Examples of the "halogen" in the general formulas (1) and (2) include fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred, and bromine being particularly preferred. The pigment represented by the general formula (1) and the pigment represented by the general formula (2) may have one or two or more halogen atoms, respectively.

If the formula (1) X _1, or the general formula (2) the average value of the number of replacement of the halogen atom represented by X ₂ or more and less than 16 in the in the, it is easy to obtain a desired various properties. Among them, 1 to 3 is more preferable from the viewpoint of coloring power.

The halogen distribution width is 2 or more, more preferably 3 or more, and may be 4 or more. The halogen distribution width is preferably 10 or less. When the halogen distribution width is 3 or more and 10 or less, association and aggregation of the phthalocyanine molecules tends to be remarkably suppressed. Accordingly, when the halogen distribution width is within the above-mentioned range, it contributes greatly to the increase of the particle diameter and the suppression of the lowering of the contrast due to the association or aggregation of molecules, and it becomes easy to obtain various desired characteristics.

Here, the "halogen distribution width" is the distribution of halogen atoms substituted in the phthalocyanine pigment represented by the general formula (1) or (2). The halogen distribution width is a value obtained by multiplying the signal intensity (peak value) of the molecular ion peak corresponding to the molecular weight of each phthalocyanine compound according to the halogen substitution number and the peak value (total peak value ), And the number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted to obtain the halogen distribution width. The kind of the halogen atom to be used may be used in combination of two or more as far as they are within the range of the average number and the distribution width of the above-mentioned substituted numbers. In this case, it is particularly preferable to use a combination of bromine and chlorine.

Examples of the alkyl group for R ₁ to R ₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, A straight chain or branched alkyl group such as an alkyl group, an aryl group or a 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable.

Examples of the substituent of the alkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine; An alkoxyl group such as a methoxyl group; Aryl groups such as phenyl and tolyl; Nitro group and the like. The substituent may be plural. Thus, 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, Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group and 2,4-dichlorobenzyl group. .

Examples of the aryl group for R ₁ to R ₄ include monocyclic aromatic hydrocarbon groups such as a phenyl group and a p-tolyl group; A condensed aromatic hydrocarbon group such as a naphthyl group and an anthryl group, and the like, and a monocyclic aromatic hydrocarbon group is preferable. 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; Nitro group and the like. The substituent may be plural. Thus, examples of the aryl group having a substituent include an aryl group having a substituent such as a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, Methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group and anthraquinone group.

Examples of the alkoxyl group for R ₁ and R ₂ include a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, Straight-chain or branched alkoxyl groups such as dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy, Practical skill is preferable.

Examples of the substituent of the alkoxyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine; An alkoxyl group; Aryl groups such as phenyl and tolyl; Nitro group and the like. The substituent may be plural. Accordingly, 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, A 2,2-ditrifluoromethyl propoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group and a benzyloxy group.

Examples of the aryloxy group for R ₁ and R ₂ include an aryloxy group comprising a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group; Naphthoxy group, naphthoxy group, and anthryloxy group, and the like, and an aryloxy group composed of a monocyclic aromatic hydrocarbon group is preferable. Also, an aryloxy group having 6 to 12 carbon atoms is preferred.

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; Nitro group and the like. The substituent may be plural. Thus, 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- And the like.

Examples of the cycloalkyl group for R ₃ include monocyclic aliphatic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, 2,5-dimethylcyclopentyl group and 4-tert-butylcyclohexyl group; And condensed aliphatic hydrocarbon groups such as a vinyl group and an adamantyl group. 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; Nitro group and the like. The substituent may be plural. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group in R ₃ and R ₄ include an aliphatic heterocyclic group such as a pyridyl group, a pyrazyl 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 reduced numbers 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; Nitro group and the like. The substituent may be plural. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group and an N-methylpyrrolyl group.

Among the phthalocyanine pigments represented by the general formula (1) or the general formula (2), at least one of R ₁ and R _{2 is preferably} an aryl group which may have a substituent, Or an aryloxy group which may have a substituent. It is more preferable that R ₁ and R ₂ are both an aryl group or an aryloxy group. More preferably, both R ₁ and R ₂ are a phenyl group or a phenoxy group. It is also 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.

It is preferable that Y ₁ in the general formula (1) and Y ₂ and Y ₃ in the general formula (2) are -OP (= O) R ₁ R ₂ . In the general formulas (1) and (2), R ₁ and R ₂ may be bonded to each other to form a ring.

Representative 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 in the general formula (1) ₁ or the bonding position of a substituent group with M ₂ in the general formula (2)). Cyclic isomers of the exemplified compounds are also included as preferred examples.

[Chemical Formula 6]

In one embodiment of the present invention, the phthalocyanine pigment is a pigment represented by the general formula (1), X ₁ represents a halogen atom, M ₁ represents Al, Ga or In, Y ₁ represents -OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , -OS (= O) ₂ R ₄ or a hydroxyl group. In each of the compounds contained in the pigment, n is an integer of 1 to 10, and X ₁ may be the same or different from each other. Also, M ₁ is the same metal and Y ₁ is the same group. Provided that the average value of the number of substitution of halogen atoms represented by X ₁ in the pigment is 1 or more and less than 6 and the halogen distribution width is 2 or more.

According to a preferred example, X ₁ is at least one member selected from the group consisting of a bromine atom and a chlorine atom, Y ₁ is _{-OP (= O) R 1 R} 2, -OC (= O) R 3 , or -OS (= O) ₂ R &lt; _{4 &} gt ;. M ₁ is preferably Al.

According to a preferred example, X ₁ is a bromine atom and Y ₁ is -OP (= O) R ₁ R ₂ . R ₁ and R ₂ are preferably a phenyl group or a phenoxy group. M ₁ is preferably Al.

In one embodiment of the present invention, the phthalocyanine pigment is a pigment represented by the general formula (2), X ₂ represents a halogen atom, M ₂ represents Si, Ge or Sn, Y ₂ and Y ₃ represent - OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , -OS (= O) ₂ R ₄ or a hydroxyl group. In each of the compounds contained in the pigment, n is an integer of 1 to 10, and X ₂ may be the same or different from each other. M ₂ is the same metal, Y ₂ is the same group, and Y ₃ is the same group. Y ₂ and Y ₃ may be the same or different from each other. Provided that the average value of the number of substituents of halogen atoms represented by X ₂ in the pigment is 1 or more and less than 6 and the halogen distribution width is 2 or more.

According to a preferred example, X ₂ is at least one member selected from the group consisting of a bromine atom and a chlorine atom, Y ₂ and Y ₃ is _{-OP (= O) R 1 R} 2, -OC (= O) R 3 or - OS (= O) ₂ R ₄ .

According to a preferred example, X ₂ is a bromine atom and Y ₂ and Y ₃ are -OP (═O) R ₁ R ₂ . R ₁ and R ₂ are preferably a phenyl group or a phenoxy group.

<Production method of phthalocyanine pigment>

According to one embodiment, in the phthalocyanine pigment represented by the general formula (1), the compound wherein Y ₁ is a hydroxyl group is obtained by halogenating a phthalocyanine compound represented by the following general formula (3) and then hydrolyzing (4)). On the other hand, according to one embodiment, a compound in which Y ₁ is a substituent group other than a hydroxyl group is a phthalocyanine pigment represented by the general formula (4) as a starting material. An acidic compound represented by a phthalocyanine pigment represented by the general formula _{(4), Z 1 P (} = O) R 1 R 2, Z 2 C (= O) R 3 or _{Z 3 S (= O) 2} R 4 By the reaction, a phthalocyanine pigment having a desired substituent can be obtained. In the acidic compound, Z ₁ to Z _{3 each} represent a halogen atom or a hydroxyl group, and R ₁ to R ₄ each have the same meaning as R ₁ to R ₄ in the general formula (1).

(7)

[Chemical Formula 8]

Wherein X ₁ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₁ is 1 or more and less than 6 and a halogen distribution width is 2 or more. M ₁ represents Al, Ga or In. Y ₄ represents a halogen atom or a hydroxyl group. Y ₅ represents a hydroxyl group.]

According to one embodiment, in the phthalocyanine pigment represented by the general formula (2), the compound wherein Y ₂ and / or Y ₃ is a hydroxyl group can be obtained by halogenating a phthalocyanine compound represented by the following general formula (5) (Formula (6)). On the other hand, a compound in which Y ₂ and / or Y ₃ is a substituent group other than a hydroxyl group, is a phthalocyanine pigment represented by the general formula (6) as a starting material. An acidic compound represented by a phthalocyanine pigment represented by the general formula _{(6), Z 1 P (} = O) R 1 R 2, Z 2 C (= O) R 3 or _{Z 3 S (= O) 2} R 4 By the reaction, a phthalocyanine pigment having a desired substituent can be obtained. The acid in the compound Z ₁ ~ Z ₃ represents a halogen atom or a hydroxyl group, R ₁ ~ R ₄ is an R ₁ ~ R ₄ and accept, respectively in the formula (1).

[Chemical Formula 9]

[Chemical formula 10]

Wherein X ₂ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₂ is 1 or more and less than 6 and a halogen distribution width is 2 or more. M ₂ represents Si, Ge or Sn. Y ₆ and Y ₇ represent a halogen atom or a hydroxyl group. Y ₈ and Y ₉ represent a hydroxyl group.

The halogenation of the phthalocyanine compound represented by the general formula (3) or (5) can be carried out, for example, by the chlorosulfonic acid method described in "The Phthalocyanines Volume II Manufacture and Applications" (CRC Press, Inc., 1983) Melting method and the like. In any of the methods, the average value of the substitution number of the halogen atom and the halogen distribution width can be adjusted by changing the blending ratio of the phthalocyanine compound represented by the general formula (3) or the general formula (5) and the halogenating agent.

As the chlorosulfonic acid method, a method of dissolving a phthalocyanine compound represented by the general formula (3) or (5) in a sulfuric acid-based solvent such as chlorosulfonic acid or sulfuric acid and adding a halogenating agent thereto to halogenate . The reaction at this time is preferably carried out at a temperature of from 20 to 120 캜, preferably from 1 to 10 hours.

Examples of the melting method include aluminum halides such as aluminum chloride and aluminum bromide, as disclosed in, for example, Japanese Patent Application Laid-Open No. S51-64534 (U.S. Patent No. 4,077,974); Titanium halides such as titanium tetrachloride; An alkali metal halide such as sodium chloride or sodium bromide or an alkaline earth metal halide [hereinafter referred to as an alkali (earth) metal halide); There can be mentioned a method of halogenating the phthalocyanine represented by the general formula (3) or the general formula (5) in a melt of one kind or a mixture of two or more kinds of various halogenating agents such as thionyl chloride .

The halogenating agent used for the halogenation means a fluorinating agent, a chlorinating agent, a brominating agent and an iodinating agent. Examples of the fluorinating agent include fluoroxytrifluoromethane, cesium fluoride sulfate, acetyl hypofluorite, N-fluorosulfonamide, diethylaminosulfatrifluoride, N-fluoropyridinium salt and the like. have.

Examples of the chlorinating agent include chlorine (Cl ₂ ), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloro isocyanurate, 2,3,4,5,6,6-hexachloro- Cyclohexadienone, 2,3,4,4,5,6-hexachloro-2,5-cyclohexadieneone, N-chlorotriethylammonium chloride, benzene cerenenyl chloride and the like.

Examples of the brominating agent include bromine (Br ₂ ), N-bromosuccinimide, silver bromide, tetramethylammonium tribromide, trifluoroacetyl hypobromide, dibromoisocyanuric acid, 2,4,4,6- Bromo succinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1, 2-diamino-1,3-thiazole hydrobromide, , 3-dibromo-5,5-dimethylhydantoin, and the like.

Examples of the iodide agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodide, iodine-iodic acid, ethylene iodide chloride, N- And the like.

In one embodiment, the phthalocyanine represented by the general formula (4) or the general formula (6) has properties as a pigment and can be used as it is. Further, in one embodiment, the phthalocyanine represented by the general formula (4) or (6) is a starting material of a desired pigment. In this embodiment, in order to improve the reaction efficiency with the acidic compound, the compound represented by the general formula (4) or the general formula (6) may be prepared by a method such as an acid pasting method, a solvent salt milling method, Is preferably carried out. By making the phthalocyanine represented by the general formula (4) or the general formula (6) finely preliminarily, the phthalocyanine pigment produced by using the phthalocyanine can be easily obtained in a fine state. When such a finely divided phthalocyanine pigment is used as a coloring composition, it becomes easy to obtain high brightness and high contrast.

The reaction of the phthalocyanine represented by the general formula (4) or (6) with the acidic compound can be carried out, for example, by mixing and stirring in an organic solvent. Subsequently, 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,

Butylene glycol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6- hexanetriol, acetylene glycol derivatives, A polyhydric alcohol-based solvent such as an isopropanol,

Pyrrolidinone, epsilon -caprolactam, formamide, N-methylformamide, N, N-dimethylformamide Amide solvents such as acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea or tetramethylurea,

In addition, a lower monoalkyl ether solvent of a polyhydric alcohol such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl)

Polyether type solvents such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether (triglyme)

Sulfolane, dimethylsulfoxide, or a sulfur-based solvent such as 3-sulfolene,

Polyfunctional solvents such as diacetone alcohol and diethanolamine,

A carboxylic acid-based solvent such as acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, or trifluoroacetic acid,

Methane sulfonic acid, or sulfonic acid solvent such as trifluorosulfonic acid,

Aromatic hydrocarbon solvents such as benzene, toluene and xylene.

In one embodiment, a monovalent alcohol-based solvent such as methanol, ethanol, isopropyl alcohol or the like, or a monohydric alcohol solvent such as dimethylsulfoxide, N, N-dimethylformamide, 1-methyl- It is preferable to use aprotic polar solvent such as pyrrolidinone. These organic solvents may be used alone or in combination of two or more.

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

<Minimization of phthalocyanine pigment>

Examples of the method of micronization include common coloring agents such as acid pasting method, solvent salt milling method and the like, and methods known in the art used for micronizing pigments.

The acid paste method is a method in which a pigment is added and dissolved in sulfuric acid, a sulfuric acid solution is dripped into a large amount of water, and the solution is precipitated to obtain a fine colorant. By optimizing the amount of water to be used for precipitation, temperature, and the like, it is possible to obtain pigment particles having a very small primary particle diameter and a narrow distribution width and a sharp particle size distribution.

The solvent salt milling method is a method in which a pigment, a mixture of a water-soluble inorganic salt and a water-soluble organic solvent is heated by a kneader such as a kneader, a two roll mill, a three roll mill, a ball mill, an attritor, Followed by mechanically kneading, and then removing water-soluble inorganic salt and water-soluble organic solvent by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment particles are crushed using the height of the hardness of the inorganic salt at the time of salt milling. By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very small primary particle size, narrow distribution width, and sharp particle size distribution.

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

The water-soluble organic solvent is not particularly limited as long as it acts to wet the pigment and the water-soluble inorganic salt, dissolves in water (miscible), and does not substantially dissolve the inorganic salt used. However, in the case of salt milling, the temperature rises and the solvent is liable to evaporate. Therefore, from the viewpoint of safety, it is preferable that the solvent has a boiling point of not lower than 120 캜. Examples of such water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl 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, and liquid polypropylene glycol. These water-soluble organic solvents are used in an amount of preferably 5 to 1000% by weight, more preferably 50 to 500% by weight based on the total weight of the phthalocyanine pigment (100% by weight).

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

In one embodiment, the phthalocyanine pigment may be used in combination with a phthalocyanine pigment represented by the general formula (1) or (2) and two or more kinds of phthalocyanine pigments other than the phthalocyanine pigment in accordance with the intended use . In this case, the phthalocyanine pigments prepared in each case are preferably mixed with each other. Alternatively, if it is possible to produce at the same time, it is also possible to use a pigment prepared by synthesizing or finely dispersing two or more kinds of phthalocyanine pigments.

However, it is also presumed that the phthalocyanine pigment represented by the general formula (1) is present in the phthalocyanine pigment after the combined use even when used in combination. That is, when X ₁ is a halogen atom, n is an integer of 1 to 10, M ₁ is Al, Ga, or In, and Y ₁ is -OP (= O) R ₁ R _{2 in the} phthalocyanine pigment, A phthalocyanine compound represented by -OC (= O) R ₃ , -OS (= O) ₂ R ₄ or a hydroxyl group satisfies an average value of substitution number of halogen atoms of 1 to 6 and a halogen distribution width of 2 or more. The same applies to the phthalocyanine pigment represented by the general formula (2).

<Coloring composition>

The coloring composition as an embodiment 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 (2). In one embodiment, the coloring composition has a green color tone derived from the phthalocyanine pigment represented by the general formula (1) or the general formula (2) used as a coloring agent. In one embodiment, the coloring composition may further contain, as a colorant, at least one colorant selected from the group consisting of an additional colorant (1) and a colorant (2) for the purpose of chromaticity adjustment or the like so long as the effect of the phthalocyanine pigment represented by the general formula . &Lt; / RTI &gt;

<Colorant>

(Green color)

In one embodiment, the coloring composition may further contain, in order to adjust the chromaticity, a compound represented by the general formula (1) or general formula (2) within a range not deteriorating the effect of the phthalocyanine pigment represented by the general formula (1) A green pigment other than the phthalocyanine pigment represented by the formula (2) may be contained. The green colorant is not particularly limited, but generally includes a green pigment or a green colorant.

As the green pigment, for example, C.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; Zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, etc.; Aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, and the like, but the present invention is not limited thereto. Among these, from the standpoint of obtaining a high contrast ratio and high brightness, it is preferable that C.I. Pigment Green 7, 36, 58.

As the green dye, C.I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. Solvent dyes; C.I. CI Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, Acid dye; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, Direct dyes; C.I. C.I., such as Mordant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, Mordant dyes and the like. As the green pigment, C.I. Pigment Green 7, 36 and 58. It is preferable that at least one selected from the group consisting of Pigment Green 7,

(Yellow pigment)

The coloring composition may further contain a yellow coloring matter to the extent that the effect of the phthalocyanine pigment represented by the general formula (1) or (2) is not impaired to further adjust the chromaticity. The yellow dye is not particularly limited, but generally includes yellow pigment or yellow dye.

As the yellow pigment, an organic or inorganic pigment can be used singly or in combination of two or more. It is preferable to use a pigment having a high coloring property and a high heat resistance, particularly a pigment having a high heat decomposition resistance. do. Commercially available organic pigments can be used, and natural pigments and inorganic pigments can be used together according to the color of a desired filter segment.

Specific examples of yellow organic pigments usable in the above colored composition are shown below. As the yellow pigment, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 , 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188 , 192, 193, 194, 196, 198, 199, 213, 214; A yellow pigment such as a quinophthalone pigment represented by the general formula (7) described in JP-A-2012-226110 can be used. In particular, from the viewpoints of heat resistance, light resistance, and lightness of the filter segment, the yellow colorant is preferably C.I. Pigment Yellow 138, 139, 150, 185 and a quinophthalone pigment represented by the general formula (7).

(7)

(11)

[In the formula (7), R ¹ to R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent. Provided that at least one adjacent pair of R ¹ to R ⁴ groups and / or at least one adjacent pair of R ¹⁰ to R ¹³ are integral to form an aromatic ring which may have a substituent .]

Examples of the halogen atom in the general formula (7) include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, 2-ethylhexyl group, and the like. In addition, examples of the aryl group include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group And the like.

Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, Dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group. Further, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropyloxy group, a 2,2-ditrifluoromethyl group An alkoxyl group having a substituent such as a propoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, or a benzyloxy group.

Examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group and an anthranyl group. Further, examples of the aryl group include a phenyl group such as a p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, An aryl group having a substituent such as a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinone group, .

In one embodiment, the quinophthalone pigment is preferably any one of formulas (7A) to (7C). Here, in R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ , a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, The aryl group has the same meaning as described in the general formula (7).

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the general formulas (7A) to (7C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, An alkoxyl group which may have a substituent, or an aryl group which may have a substituent.]

Further, in one embodiment, the quinophthalone pigment is a pigment in which R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ^{60 in} formulas (7A) to (7C) are a hydrogen atom or a halogen atom Is more preferable. Among them, the structure of the general formula (7B) is particularly preferable.

Examples of the yellow dye include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, , Nitro dyes, quinoline dyes, naphthoquinone dyes, and oxazine dyes.

Thus, specific examples of the yellow dye include C.I. 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 41, 42, 42: 1, 43, 44, 46, 48, 48, 41, 42, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 171, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 192, 199, and the like.

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

Also, C.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, 105, 106, and the like.

Also, C.I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 90, 93, 85, 88, 89, 90, 93, 94, 95, 72, 73, 77, 79, 81, 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,

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

When the green pigment is used in combination with the phthalocyanine pigment represented by the general formula (1) or (2), the coloring matter represented by the green pigment / general formula (1) or the general formula (2) The mass ratio of the phthalocyanine pigment (the total mass when the phthalocyanine pigment represented by the formula (1) or the formula (2) is used in combination) is preferably in the range of 10/90 to 70/30. More preferably in the range of 20/80 to 40/60, and still more preferably in the range of 20/80 to 35/65.

When the yellow pigment is used in combination with the phthalocyanine pigment represented by the general formula (1) or (2), the yellow pigment / phthalocyanine represented by the general formula (1) or (2) The mass ratio of the pigment (the total mass when the phthalocyanine pigment represented by the formula (1) or the formula (2) is used in combination) 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 more preferably in the range of 70/30 to 40/60.

(Refinement of colorant)

The coloring agent used in the coloring composition can be suitably used as a coloring agent for a color filter by finely smecting the coloring agent particles by a salt milling treatment or the like as necessary in order to obtain high brightness and high contrast. The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to enhance dispersibility in the colorant carrier. Further, in order to obtain a filter segment having a high contrast, it is preferable that it is 80 nm or less. In one embodiment, it is more preferably in the range of 20 to 60 nm, and more preferably in the range of 30 to 50 nm.

The salt milling treatment is in agreement with the solvent salt milling method described in &quot; Minification of the phthalocyanine pigment &quot;.

<Binder Resin>

The binder resin may be one which disperses a coloring agent such as a pigment and a dye, particularly a phthalocyanine pigment represented by the general formula (1) or (2). Specific examples of the binder resin include a thermoplastic resin and a thermosetting resin.

(Thermoplastic resin)

Examples of the thermoplastic resin for use in the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, (HDPE, LDPE), polybutadiene, and polyimide resin, and the like can be given as examples of the resin (A), the resin (B), the resin have. Among them, it is preferable to use an acrylic resin.

(Thermosetting resin)

Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic resins, rosin-modified fumaric acid resins, melamine resins, urea resins, cardo resins, have.

The thermosetting resin may be a low molecular compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound and a phenol compound , But is not limited thereto. By including such a thermosetting resin, an effect is obtained that the resin reacts during firing of the filter segments, the cross-linking density of the coating film is increased, the heat resistance is improved, and the pigment agglomeration upon firing the filter segments is suppressed. Of these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

When a color filter is produced using a coloring composition, the binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in a propagation region of 400 to 700 nm in a visible light region .

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

The binder resin is preferably used in an amount of 30 parts by mass or more based on 100 parts by mass of the total mass of the colorant in view of good film formability and various resistance properties. The binder resin preferably has a high colorant concentration and exhibits good color characteristics , It is preferably used in an amount of not more than 500 parts by mass as resin solid content. In one embodiment, the binder resin is used in an amount of preferably 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 development type colored resist material, a vinyl-based alkali-soluble resin prepared using an acid-group-containing ethylenically unsaturated monomer (monomer) from the viewpoint of developability is used as a binder resin Is preferably used. In another embodiment, a photosensitive coloring composition may be constituted for the purpose of improving photosensitivity and improving 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.

Examples of the vinyl-based alkali-soluble resin which can be suitably used as a binder include 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 sulfonic group. Specific examples of the vinyl-based alkali-soluble resin include acrylic resins having an acidic group,? -Olefin / (maleic anhydride) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene / (Maleic anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from a (meth) acrylic resin having an acidic group and a styrene / styrenesulfonic acid copolymer is preferable. Particularly, the (meth) acrylic resin having an acidic group has a high heat resistance and transparency, and therefore is suitably used.

The acidic group in the acidic group-containing ethylenically unsaturated monomer used for preparing the resin is preferably a carboxylic acid group or a hydroxyl group. Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. As examples of the ethylenically unsaturated monomer having a hydroxyl group, there can be mentioned, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxypropyl acrylate, or a caprolactone adduct of these monomers (the number of added moles is preferably 1 to 5), and the like. .

In one embodiment, in the case of constituting a photosensitive coloring composition for a color filter, from the viewpoints of dispersibility, permeability, developability, and heat resistance of the pigment, the binder resin is preferably selected from the group consisting of a colorant adsorber and a carboxyl group , The balance between the aliphatic group and the aromatic group serving as the affinity group for the colorant carrier and the solvent is preferably good. In one embodiment, a resin having an acid value of 20 to 300 mgKOH / g is preferably used as the binder resin from the viewpoints of dispersibility, permeability, developability, and further durability of the pigment. By using a resin having an acid value within the above range, suitable solubility in a developer can be obtained and it becomes easy to form a fine pattern.

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

In another embodiment, when forming a photosensitive coloring composition as an alkali developing type colored resist material 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, It is preferable to use an active energy ray-curable resin having an unsaturated double bond. When the resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, there is a tendency that the stability of the coloring agent in the resist material is improved because no water is formed in the coating film after the resist material is applied. In the case of using the above linear resin having no ethylenically unsaturated double bond in the side chain, in the liquid in which the resin and the colorant are mixed, the colorant is hardly trapped in the resin and has a degree of freedom, so that 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 tends to be trapped in the resin in which the resin and the colorant are mixed. For this reason, in the solvent resistance test, the coloring matters are hardly eluted, and the coloring agent components are hardly aggregated and precipitated. Further, when the film is formed by exposure with an active energy ray, it is presumed that the colorant molecules are fixed by three-dimensionally cross-linking the resin, and the colorant components are hardly aggregated and precipitated even when the solvent is removed in the subsequent developing process.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin into which an ethylenically unsaturated double bond is introduced by the following method (a) or (b).

(Method (a))

As the method (a), for example, a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with at least one other monomer And then reacting the resulting hydroxyl group with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

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

Examples of the unsaturated monobasic acid include (meth) acrylic acid; Crotonic acid; o-, m-, or p-vinylbenzoic acid; And monocarboxylic acids such as haloalkyl, alkoxyl, halogen, nitro, or cyano substituent at the? -Position of (meth) acrylic acid, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, xanthate, and maleic anhydride, and these may be used alone or in combination of two or more. A tricarboxylic acid anhydride such as trimellitic anhydride is used or a tetracarboxylic acid anhydride such as pyromellitic acid anhydride is used to hydrolyze the remaining anhydride groups in order to increase the number of carboxyl groups can do. Further, as the polybasic acid anhydride, it is possible to further increase the ethylenically unsaturated double bond by using tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond.

As a similar method of the method (a), for example, an ethylenically unsaturated monomer having an epoxy group is added to a part of side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers, To introduce an ethylenically unsaturated double bond and a carboxyl group.

(Method (b))

As the method (b), an ethylenically unsaturated monomer having a hydroxyl group is used, and a side chain hydroxyl group of a copolymer obtained by copolymerizing a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is added to an ethylenically unsaturated monomer having an isocyanate group Of the isocyanate group.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4- (Meth) acrylates such as glycerol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and the like. These may be used alone or in combination of two or more. none. Further, polyether mono (meth) acrylate, (poly) gamma -valerolactone, (poly) acrylonitrile, and poly (meth) acrylate obtained by addition polymerization of the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, ), (poly) ester mono (meth) acrylate with addition of (poly) 12-hydroxystearic acid and the like can also be used. From the viewpoint of coating water repellency, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

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

<Organic solvents>

To easily form a filter segment by dissolving a coloring agent sufficiently in a monomer and a resin, and further applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate, an organic solvent is contained in the coloring composition.

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, Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutanol, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-butylbenzene, n-butylbenzene, , o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, Butyrolactone, isobutyl alcohol, and isophorone.

Further, it is possible to use ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tertiary butyl ether, ethylene glycol monobutyl ether, 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, tri Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene 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, Propyleneglycol monomethyl ether propionate, benzyl alcohol, methylisobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, acetic acid Isoamyl acetate, isobutyl acetate, may be mentioned propyl acetate, dibasic acid esters and the like.

These organic solvents may be used singly or in combination of two or more kinds.

Of these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monomethyl ether acetate are preferable from the viewpoint of good dispersibility, permeability, Glycol acetates such as acetate; Alcohols such as benzyl alcohol and diacetone alcohol; Ketones such as cyclohexanone and the like are preferably used.

The organic solvent is preferably used in an amount of 500 to 4000 parts by mass per 100 parts by mass of the total mass of the coloring agent in that the coloring composition can be adjusted to an appropriate viscosity and a desired filter segment of a desired film thickness can be formed Is preferably used. In one embodiment, the organic solvent is used in an amount of 500 to 2000 parts by mass, more preferably 500 to 1000 parts by mass, based on 100 parts by mass of the total mass of the colorant.

&Lt; Production method of colored composition >

In one embodiment, the coloring composition is obtained by mixing a colorant containing a phthalocyanine pigment represented by the general formula (1) or (2) in a colorant carrier containing the binder resin and a solvent as required, It can be finely dispersed by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor together with a dispersing aid such as a pigment derivative. When the solubility of the phthalocyanine pigment represented by the general formula (1) or (2) is high, specifically, the solubility in the organic solvent to be used is high and the solubility is dissipated by stirring, , It is not necessary to prepare them finely dispersed as described above.

The coloring composition may also be produced by mixing phthalocyanine pigments represented by the general formula (1) or (2) and other coloring agents dispersed in a colorant carrier such as a binder resin.

&Lt; Dispersing agent &

When the colorant containing the phthalocyanine pigment represented by the general formula (1) or (2) is dispersed in the colorant carrier, a dispersant aid such as a pigment derivative, a resin type dispersant or a surfactant can be suitably used. The dispersing aid is excellent in dispersion of the coloring agent and has a large effect of preventing re-aggregation of the coloring agent after dispersion. Therefore, when the coloring composition comprising the coloring agent dispersed in the coloring agent carrier using the dispersion aid is used, A filter is obtained.

Examples of the pigment derivative include compounds in which a phthalimide methyl group, which may have a basic substituent, an acidic substituent or a substituent, is introduced into an organic pigment, anthraquinone, acridone or triazine. For example, Japanese Patent Application Laid-Open No. S63-305173, Japanese Patent Publication S57-15620, Japanese Patent Publication S59-40172, Japanese Patent Publication No. S63-17102, Japanese Patent Publication No. H5-9469 These may be used singly or in combination of two or more kinds.

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

The resinous dispersant has a pigment affinity site having a property of adsorbing to a colorant and a site compatible with the colorant carrier, and adsorbs on the colorant to stabilize dispersion of the colorant carrier. Specific examples of the resinous dispersing agent include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, An oil dispersant such as an amide or a salt thereof formed by the reaction of a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic ester, a modified product thereof, a poly (lower alkyleneimine) and a polyester having a free carboxyl group, Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, Compounds, modified polyacrylate compounds, ethylene oxide / propylene oxide addition compounds, phosphoric acid ester compounds And the like, which may be used alone or in combination of two or more, but are not limited thereto.

Commercially available resinous dispersing agents include the following.

101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181 of the Big- 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 et al.

3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500,

EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502,

Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine Techno Co., Ltd.

Examples of the surfactant include the following surfactants.

Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, lauryl sulfuric acid monoethanol Anionic surfactants such as amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester;

Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate;

Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;

Alkyl betaine such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactant such as alkylimidazoline.

These may be used singly or in combination of two or more, but are not limited thereto.

When a resinous 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 45 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant, Mass part.

As an embodiment, the colorant may be subjected to dispersion treatment independently before the dispersion treatment for the colorant carrier such as the binder resin. That is, after the pigment dispersion is prepared by dispersing the pigment, it may be used as a coloring agent.

In one embodiment, the coloring composition may further include 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 this embodiment can be suitably used as a photosensitive coloring composition for a color filter. Further, the coloring composition 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 components described above. Hereinafter, each component will be described.

<Photopolymerization initiator>

The coloring composition may contain a photopolymerization initiator. The blending amount when the photopolymerization initiator is used is preferably from 5 to 200 parts by mass based on 100 parts by mass of the phthalocyanine pigment represented by the general formula (1) or (2), and from 10 to 150 parts by mass Is more preferable.

As the photopolymerization initiator, conventionally known polymerization initiators can be used. Specifically, the following can be mentioned.

2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethylketal, 4- (2-hydroxyethoxy) phenyl- , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- 2-methylpropionyl) benzyl] phenyl] -2-methylpropan-1-one;

Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;

Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;

Other phenylglyoxylic methyl esters and the like.

More specifically, Irgacure 651, Irgacure 184, Darocur-1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, 01, Irgacure OXE-02 (BASF), Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE- Adeka Optomer N1717, Adeka Optomer N1919, Adeka Cruz NCI-831 (ADEKA), and Esacure 1001M (Lamberti).

In addition, triazine derivatives disclosed in Japanese Patent Publication S59-1281, S61-9621 and S60-60104, Japanese Patent Laid-Open Publication S59-1504 and Japanese Patent Publication S61-243807 Organic peroxides described in Japanese Patent Publication No. S43-23684, Japanese Patent Publication No. S44-6413, Japanese Patent Publication No. S47-1604, and diazonium compounds described in USP No. 3567453, USP No. 2848328 , USP No. 2852379 and USP 2940853, organic azide compounds described in the specification of Japanese Patent Publication No. S36-22062, Japanese Patent Publication No. S37-13109, Japanese Patent Publication No. S38-18015, and Japanese Patent Publication No. S45 Quinonediazides described in JP-A-9610, JP-A S55-39162, JP S59-140203 and MACROMOLECULES, Vol. 10, p. 1307 (1977) ) Various onium compounds, including iodonium compounds, and azo compounds described in Japanese Patent Application Laid-Open No. S59-142205.

Further, in Japanese Patent Application Laid-Open Publication H1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of Imaging Science", vol. 30, p. 174 (1986), titanocenes described in Japanese Patent Application Laid-Open No. S61-151197, "COORDINATION CHEMISTRY REVIEW", vol. 84, pp. 85 to 277 (1988) A transition metal complex containing a transition metal such as ruthenium described in Japanese Patent Application Laid-Open No. H1-182701, an aluminate complex described in Japanese Patent Application Laid-Open No. H3-209477, a borate compound described in Japanese Patent Application Laid- 2,4,5-triarylimidazole dimer described in JP-A S55-127550 and JP-A S60-202437, carbon tetrabromide, an organohalogen compound described in JP S59-107344 , Japanese Patent Application Laid-Open No. H5-255347 Sulfonium complexes or oxosulfonium complexes, the amino ketone compounds described in Japanese Patent Application Laid-Open Nos. S54-99185, S63-264560 and H10-29977, Japanese Patent Application Laid-Open No. 2001-264530, Japanese Patent Application Laid-Open Nos. 2001-261761, 2000-80068, 2001-233842, 2004-534797, 2006-342166, 2008-094770, Japan Japanese Patent Application Laid-Open Nos. 2009-40762, 2010-15025, 2010-189279, 2010-189280, 2010-526846, 2010-527338, 2010-527339, USP3558309 (1971), USP4202697 (1980) and oxime ester compounds described in Japanese Patent Application Laid-Open No. 61-24558.

These photopolymerization initiators may be used singly or as a mixture of two or more kinds in an optional ratio as required. In one embodiment, from the viewpoint of patterning sensitivity, it is preferable to use an? -Aminoalkylphenone-based or oxime ester-based compound. For example, a group consisting of Irgacure 907, Irgacure 369, Irgacure 379, Irgacure OXE-01, Irgacure OXE-02 (manufactured by BASF), and Adeka Optomer N1919 May be used.

<Photopolymerizable Monomer>

The photopolymerizable monomer includes a monomer or an oligomer which is cured by ultraviolet rays and / or heat to produce a transparent resin, and these may be used singly or in combination of two or more. More specifically, the photopolymerizable monomer is a compound having at least one photopolymerizable group in the molecule, and its molecular weight is typically 1000 or less.

Examples of the monomer or oligomer that is cured by ultraviolet rays and / or heat to produce a transparent resin include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl ) Isocyanurate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, di (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, methacrylic acid ester and methacrylic acid ester such as trimethylolpropane tetra (meth) acrylate, epoxy acrylate and pentaerythritol tetra But are not limited to, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide and acrylonitrile .

Further, the photopolymerizable monomer may contain an acid group. For example, an esterified product of a polyhydric alcohol with a free hydroxyl group-containing poly (meth) acrylate of (meth) acrylic acid and a dicarboxylic acid; Esters of polyvalent carboxylic acids with monohydroxyalkyl (meth) acrylates, and the like. Specific examples include mono (meth) acrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol penta methacrylate; A free carboxyl group-containing monoesterified product of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid, etc., with hydroxyolycoacrylates or monohydroxy oligomethacrylates; Propane-1,2,3-tricarboxylic acid (tricarbalic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene- Tricarboxylic acids such as tricarboxylic acid and benzene-1,3,5-tricarboxylic acid, and tricarboxylic acids such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Monohydroxy monoacrylates such as hydroxypropylmethacrylate, and hydroxypropylmethacrylate, and free carboxyl group-containing oligoesters with monohydroxymonomethacrylates, but are not limited thereto.

In one embodiment, from the viewpoints of patterning sensitivity and adhesion to a glass substrate, it is preferable to use a multifunctional monomer having a plurality of photopolymerizable groups in one molecule. As the polyfunctional monomer, it is preferable to have 3 to 6 photopolymerizable groups per molecule. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used. For example, Aronix M-402, a trade name of East Asia Synthetic Chemical Co., and A-DPH, Shin-Nakamura Chemical Industry Co., Ltd., may be used.

The content of the photopolymerizable monomer is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the colorant from the viewpoints of photocurability and developability It is used as the amount of the mass part.

<Increase / decrease>

Further, the coloring composition may contain a sensitizer. Examples of the sensitizer include unsaturated ketone derivatives represented by benzophenone derivatives, chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives , Polymethine pigments such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, melocyanine derivatives and oxolin derivatives, Anthraquinone derivatives, triazine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrine derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Pyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine There can be used a compound represented by the following general formula (1): wherein R 1 and R 2 are each independently selected from the group consisting of a halogen atom, a halogen atom, a fluorine atom, a fluorine atom, a halogen atom, But are not limited to these.

More specific examples include "Ogawara no Nobu" (1986, Kodansha), Ogawara Nobu, etc., "Functional dye chemistry" (1981, CMC), Ikemori Chu Saburo, Functional materials &quot; (CMC, 1986). However, the present invention is not limited to these, and other dyes or sensitizers that exhibit absorption for light from ultraviolet to near infrared can be used. These may be used in combination of two or more kinds at an arbitrary ratio as required.

Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthio Oxanone, 1-chloro-4-propoxycitoxone, and the like. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-bis (Diethylamino) benzophenone, and the like. Examples of coumarins include coumarin 1, coumarin 338, coumarin 102, and the like. Examples of ketocoumarines include 3,3'-carbonylbis (7-diethylaminocoumarin) and the like. However, the present invention is not limited to these.

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

<Multifunctional Thiol>

The coloring composition may contain a polyfunctional thiol which acts as a chain transfer agent. The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexane dithiol, decane dithiol, 1,4-butanediol bis-thiophosphate, 1,4-butanediol bis-thioglycolate, ethylene glycol Trimethylolpropane tris (thio) propionate, trimethylolpropane tris (5-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate , Pentaerythritol tetrakisthiopropionate, trimercapto propionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine , 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, and the like.

These polyfunctional thiols may be used singly or as a mixture of two or more kinds in an optional ratio as required.

The content of the polyfunctional thiol is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the mass of the total solid content of the coloring composition (100 mass%). When the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient. When the content of the polyfunctional thiol is more than 30% by mass, the sensitivity is excessively high.

<Amine compound>

In addition, the coloring composition may contain an amine compound having an action of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2- 2-ethylhexyl dimethylamino benzoate, and N, N-dimethyl para-toluidine.

<Leveling agent>

It is preferable to add a leveling agent to the coloring composition in order to improve the leveling property of the composition on the transparent substrate. The leveling agent is preferably a dimethylsiloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., and BYK-333 manufactured by Big Chemie. Specific examples of the 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 may be used in combination. The content of the leveling agent is usually preferably in the range of 0.003 to 0.5% by mass in the total 100% by mass of the coloring composition.

Particularly preferred as the leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophobic group in the molecule. More specifically, it is preferable to have a property that the solubility in water is low while having a hydrophilic group, and when it is added to a coloring composition, its surface tension lowering ability is low. In addition, it is advantageous that the wettability to the glass plate is good even though the surface tension lowering ability is low, and further, it is preferable to use those capable of sufficiently suppressing charging property at an addition amount at which defects of the coating film due to foam generation do not appear . As the leveling agent having such preferable characteristics, 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 the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The bonding form of the dimethylpolysiloxane of the polyalkylene oxide unit may be a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modification in which the terminal of the dimethylpolysiloxane is bonded to the terminal of the dimethylpolysiloxane, Chain block copolymer type. FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2110, FZ-2122, FZ-2130 and FZ- -2207, but are not limited thereto.

It is also possible to add anionic, cationic, nonionic, or amphoteric surfactant to the leveling agent. The surfactants may be used in combination of two or more.

Examples of the anionic surfactant added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, alkyldiphenyl ether disulfonic acid Sodium monostearate, sodium laurylsulfate monoethanolamine, laurylsulfate triethanolamine, ammonium laurylsulfate, stearic acid monoethanolamine, sodium stearate, sodium laurylsulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkylether phosphate ester, etc. .

Examples of the cationic surfactant added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of the nonionic surfactant to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate Polyoxyalkylene alkyl ethers such as polyethylene glycol monolaurate; Alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based or silicone-based surfactants.

<Curing agent, hardening accelerator>

The coloring composition may also contain a curing agent, a curing accelerator and the like, if necessary, to assist curing of the thermosetting resin. As the curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not limited thereto, and any curing agent I can use it. Among them, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably used. Examples of the curing accelerator include amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, Benzylamine, 4-methyl-N, N-dimethylbenzylamine and the like), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride), block isocyanate compounds (e.g., dimethylamine and the like) Bicyclic amidine compounds and salts thereof such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Imidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine Pyran, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine and the like), s-triazine derivatives (for example, 2,4-diamino-6-methacryloyl Oxyethyl-s-triazine, Vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine isocyanuric acid adduct, 2,4-diamino- Triethylamine, isobutylamine, isopropylamine, isobutylamine, isobutylamine, isobutylamine, isobutylamine, isopropylamine, These may be used alone, or two or more of them may be used in combination. The content of the curing accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting resin.

<Other additives>

The coloring composition may contain a storage stabilizer to stabilize the viscosity (time viscosity) of the composition over time. Further, in order to improve the adhesion with the transparent substrate, a adhesion improving agent such as a silane coupling agent may be contained.

Examples of the storage stabilizer include organic acids such as quaternary ammonium chloride, lactic acid and oxalic acid such as benzyltrimethyl chloride and diethylhydroxyamine, and their methyl ethers, t-butyl pyrocatechol, tetraethylphosphine, tetraphenyl Organic phosphine such as phosphine, phosphite, and the like. The storage stabilizer may be used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the colorant.

Examples of the adhesion improver include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilane such as? -Methacryloxypropyltrimethoxysilane (5,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (5,4-epoxycyclohexyl) methyltrimethoxysilane,? - Epoxysilanes such as? - (5,4-epoxycyclohexyl) methyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane and? -Glycidoxypropyltriethoxysilane, N-β (Aminoethyl)? -Aminopropyltrimethoxysilane, N-? (Aminoethyl)? -Aminopropyltriethoxysilane, N-? (Aminoethyl)? -Aminopropylmethyldiethoxysilane,? -Aminopropyltri Aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltriethoxysilane Of it may be mentioned amino silanes, γ- mercaptopropyltrimethoxysilane, γ- mercapto silane coupling agents such as silanes, such as the thio propyl triethoxysilane. The adhesion-improving agent 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 coloring agent in the coloring composition.

Although not particularly limited, in one embodiment, the coloring composition includes a colorant containing a phthalocyanine pigment represented by the general formula (1) or (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 using an ethylenic unsaturated monomer containing an acidic group. In another embodiment, the coloring composition further includes 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, it is particularly preferable to use a vinyl-based alkali-soluble resin obtained by copolymerizing an ethylenic unsaturated monomer containing an acidic group as the binder resin and to use a polyfunctional monomer having a plurality of photopolymerizable groups in one molecule as the photopolymerizable monomer desirable. Here, as the binder resin, it is more preferable to use a copolymer of a (meth) acrylic polymerizable monomer having an acidic group and other polymerizable monomer. According to this embodiment, it is easy to obtain a colored composition having excellent developability, patterning sensitivity, and glass adhesion.

<Removal of Coarse Particles>

The coloring composition can be produced by finely dispersing each component using various dispersion means as described above. In one embodiment, coarse particles of 5 占 퐉 or larger, preferably coarse particles of 1 占 퐉 or larger, more preferably coarse particles of 0.5 占 퐉 or larger, and particles of coarse particles It is preferable to perform dust removal. Here, the coarse particle means a state of a secondary particle aggregated by the primary particle. Therefore, it is preferable that the coloring composition does not contain secondary particles of substantially 0.5 mu m or more. In one embodiment, the particle size of the particles in the coloring composition is preferably less than 0.5 占 퐉, more preferably 0.3 占 퐉 or less.

<Color filter>

A color filter, which is an embodiment of the present invention, comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In addition, the color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

As a substrate such as a transparent substrate constituting the color filter, a glass plate such as soda lime glass, low alkali borosilicate glass, or alkali-free aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethacrylate methyl, or polyethylene terephthalate is used . A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surfaces of the glass plate and the resin plate for liquid crystal driving after paneling.

<Manufacturing Method of Color Filter>

The color filter can be produced by a printing method or a photolithography method using the above colored composition.

Formation of the filter segment by the printing method can be performed only by repeating printing and drying of the coloring composition prepared as the printing ink, so that the method of producing the color filter is low in cost and excellent in mass productivity. Further, by the development of the printing technique, it is possible to perform printing of a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. Further, from the viewpoint of controlling the flowability of the ink on the printing machine, the ink viscosity can also be adjusted by the dispersing agent or the extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the coloring resist material of the solvent developing type or the alkali developing type is applied onto the transparent substrate by a coating method such as a spray coating, a spin coating, a slit coating, To a dry film thickness of 0.2 to 5 占 퐉. The dried film is subjected to ultraviolet exposure through a mask having a predetermined pattern provided in contact or noncontact state with the film. Thereafter, a desired pattern is formed by dipping in a solvent or an alkaline developing solution, or spraying a developing solution by spraying or the like to remove the uncured portions. By repeating the same operation for different colors, a color filter can be manufactured. Further, in order to accelerate the polymerization of the colored resist material, heating may be carried out if necessary. According to the photolithography method, a color filter having a higher degree than the above-mentioned printing method can be produced.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkali developing solution, and organic alkalis such as dimethylbenzylamine and triethanolamine may be used. Further, a defoaming agent, a surfactant, and the like may be added to the developer. Further, in order to increase the ultraviolet exposure sensitivity, the above-mentioned colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol, water-soluble acrylic resin or the like is applied and dried to form a film for preventing polymerization inhibition by oxygen After that, ultraviolet ray exposure may be performed.

The color filter can be produced by an electrodeposition method, a transfer method, an ink jet method, or the like in addition to the above-mentioned method, and the coloring composition can be used in any method. The electrodeposition method is a method of producing a color filter by electrodepositing colloidal particles on a transparent conductive film formed on a substrate to deposit each color filter segment on a transparent conductive film. The transfer method is a method in which filter segments are formed in advance on the surface of a releasable transfer base sheet, and the filter segments are transferred onto a desired substrate.

A black matrix may be formed in advance before the color filter segments are 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, a resin film in which a light shielding agent is dispersed, and the like are used, but the present invention 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. On the color filter, an overcoat film, a transparent conductive film and the like are formed as necessary.

A liquid crystal is injected from an injection port provided in a seal section and then the injection port is sealed, and a polarizing film, a retardation film, and the like, if necessary, To the outside of the substrate, whereby a liquid crystal display panel is manufactured.

The liquid crystal display panel is composed of twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical re- alignment (VA), optical re- Or the like can be used for the liquid crystal display mode in which coloring is performed.

Example

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, &quot; part &quot; and &quot;% &quot; represent &quot; part by mass &quot; and &quot;% by mass &quot;, respectively.

The following examples relate to phthalocyanine pigments. The pigments prepared in the respective Examples were evaluated as follows.

<Evaluation of Pigment>

(Identification (Identification) of Phthalocyanine Pigment)

The phthalocyanine pigment was identified by confirming the match between the molecular ion peak of the mass spectrum obtained by using a time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by Bruker-Daltonics) and the mass number obtained by calculation And the ratio of carbon, hydrogen, and nitrogen obtained by using an element analyzer (2400 CHN elemental analyzer, manufactured by Perkin-Elmer) and the theoretical value.

(Average value of substitution number of halogen atoms)

The average value of the substitution number of the halogen atoms was determined by analyzing the liquid obtained by burning the phthalocyanine pigment by an oxygen combustion flask method and absorbing the combustible in water by an ion chromatograph (ICS-2000 ion chromatography, manufactured by DIONEX) And calculating the average value of substitution numbers of halogen atoms. Specifically, the halogen atom amount and the central metal amount of the phthalocyanine pigment were determined by an ion chromatograph, and the halogen atom equivalent to one equivalent of the central metal was calculated as an average value of the substitution number of the halogen atom.

(Halogen distribution width in pigment)

The halogen distribution width was determined by measuring the signal intensity of the molecular ion peak corresponding to each component in the mass spectrum obtained by using the time-of-flight mass spectrometer (autoflexIII (TOF-MS), manufactured by Bruker-Daltons) And a value obtained by adding each peak value (total peak value) was calculated. The number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted to obtain the halogen distribution width.

(Volume average primary particle diameter (MV))

The volume average primary particle size (MV) was determined by a transmission electron microscope (TEM) "H-7650" manufactured by Hitachi High-Technologies Corporation and the following calculation formula. First, the phthalocyanine pigment was photographed by TEM. As an image obtained, arbitrary 100 phthalocyanine pigments were selected, and the average value of the short axis diameter and the major axis diameter of the primary particles was determined as the particle diameter (d) of the phthalocyanine pigment. Subsequently, the respective phthalocyanine pigments were regarded as spheres having the particle diameters d obtained first, and the volume (V) of each particle was determined. This operation was performed on 100 phthalocyanine pigments, and was calculated from the following formula (1).

Equation (1)

MV =? (V? Ed) /? (V)

&Lt; Preparation of phthalocyanine pigment >

[Example 1]

(Production of phthalocyanine pigment (CP-1)

225 parts of phthalonitrile and 78 parts of aluminum chloride anhydride were mixed and stirred in 1250 parts of n-amyl alcohol in a reaction vessel. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the mixture was heated and refluxed at 136 DEG C for 5 hours. The reaction solution cooled to 30 deg. C as it was stirred 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 of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (see Chemical Formula (8) below).

As a result of elemental analysis on the obtained chloroaluminum phthalocyanine, 66.7% of the measured values (C), 3.0% of H, 3.0% of N (N) and 19.49% of the calculated values (C) ) 19.2%, and the target compound was identified.

[Chemical Formula 15]

Then, in 1500 parts of concentrated sulfuric acid (concentrated sulfuric acid and concentrated sulfuric acid), 100 parts of the chloroaluminum phthalocyanine was added to the reaction vessel under an ice bath (ice bath). Then, 40 parts of 1,3-dibromo-5,5-dimethylhydantoin was slowly added, and the mixture was stirred at 25 占 폚 for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 占 폚, and the resultant precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution and washing with water and drying to obtain 125 parts of phthalocyanine pigment (CP- 1).

A bromine substitution number was calculated with respect to the obtained phthalocyanine pigment (CP-1). As a result, an average of 1.8 was obtained. From the mass spectrum, a peak corresponding to the same molecular weight was identified. The halogen distribution width was 3, and the volume average primary particle diameter was 43 nm.

[Example 2]

(Preparation of phthalocyanine pigment (CP-2)

In the same manner as in Example 1 except that 40 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 80 parts of N-bromosuccinimide in the preparation of the phthalocyanine pigment (CP-1) , 143 parts of phthalocyanine pigment (CP-2) was prepared. As a result of calculating the bromine substitution number for the obtained phthalocyanine pigment (CP-2), an average value of 2.6 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 5, and the volume average primary particle diameter was 47 nm.

[Example 3]

(Production of phthalocyanine pigment (CP-3)

In the preparation of the phthalocyanine pigment (CP-1), 40 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 100 parts of 1,3-dibromo-5,5-dimethylhydantoin 143 parts of a phthalocyanine pigment (CP-3) was produced in the same manner as in Example 1 except for the above. As a result of calculating the bromine substitution number with respect to the resulting phthalocyanine pigment (CP-3), an average of 4.2 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 6, and the volume average primary particle diameter was 38 nm.

[Example 4]

(Preparation of phthalocyanine pigment (CP-4)

In the preparation of the phthalocyanine pigment (CP-1), 40 parts of 1,3-dibromo-5,5-dimethylhydantoin and 120 parts of 1,3-dibromo-5,5-dimethylhydantoin 143 parts of a phthalocyanine pigment (CP-4) was produced in the same manner as in Example 1 except for the above. A bromine substitution number was calculated with respect to the obtained phthalocyanine pigment (CP-4). As a result, an average of 5.7 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified. The halogen distribution width was 7, and the volume average primary particle diameter was 36 nm.

[Example 5]

(Production of phthalocyanine pigment (CP-5)

406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and at 140 DEG C, 100 parts of the same chloroaluminum phthalocyanine as in Example 1 was added. The temperature was raised to 160 DEG C and 20 parts of chlorine was blown. The obtained reaction solution was poured 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 washing and hot water washing, and then dried to obtain crude chlorinated aluminum phthalocyanine 160 parts were obtained. The obtained crude aluminum chlorthalate phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid, and the mixture was stirred at 50 캜 for 3 hours. Subsequently, 7200 parts of water was poured with stirring into the solution, heated to 70 占 폚, filtered, washed with hot water, washed with 1% sodium hydroxide aqueous solution, washed with warm water and dried to prepare 152 parts of phthalocyanine pigment (CP-5). Chlorine-substituted water was calculated for the resulting phthalocyanine pigment (CP-5). As a result, an average of 1.6 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified and the desired compound was identified. The halogen distribution width was 2, and the volume average primary particle diameter was 46 nm.

[Example 6]

(Production of phthalocyanine pigment (CP-6)

168 parts of a phthalocyanine pigment (CP-6) was prepared in the same manner as in Example 5 except that 20 parts of chlorine and 30 parts of chlorine were used in the preparation of the phthalocyanine pigment (CP-5). Chlorine-substituted water was calculated for the obtained phthalocyanine pigment (CP-6), and the average was 2.3, and peaks corresponding to the same molecular weight were identified from the mass spectrum, and the desired compound was identified. The halogen distribution width was 4, and the volume average primary particle diameter was 43 nm.

[Example 7]

(Preparation of phthalocyanine pigment (CP-7)

168 parts of a phthalocyanine pigment (CP-7) was prepared in the same manner as in Example 5, except that 20 parts of chlorine and 45 parts of chlorine were used in the preparation of the phthalocyanine pigment (CP-5). Chlorine-substituted water was calculated for the obtained phthalocyanine pigment (CP-7). As a result, an average of 3.8 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified. The halogen distribution width was 6, and the volume average primary particle diameter was 43 nm.

[Example 8]

(Production of phthalocyanine pigment (CP-8)

The chloroaluminum phthalocyanine represented by the formula (8) was synthesized in the same manner as in the procedure described in Example 1. Subsequently, in the reaction vessel, 1500 parts of the concentrated sulfuric acid was added with 100 parts of the chloroaluminum phthalocyanine in an ice bath. Thereafter, 45 parts of 1,3-dibromo-5,5-dimethylhydantoin and 45 parts of N-chlorosuccinimide were slowly added and the mixture was stirred at 25 ° C for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 占 폚, and the resultant precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution and washing with water and drying to obtain 141 parts of a phthalocyanine pigment (CP- 8). As a result of calculating the bromine and chlorine-substituted water for the obtained phthalocyanine pigment (CP-8), it was found that chlorine was present in an average of 2.4 and bromine was in an average of 2.2 (mean value of the halogen sum was 4.6). From the mass spectrum, And the target compound was identified. The halogen distribution width was 10, and the volume average primary particle diameter was 43 nm.

[Example 9]

(Preparation of phthalocyanine pigment (CP-9)

In the production of the phthalocyanine pigment (CP-1), except that 40 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 120 parts of 1,3-diiodo-5,5-dimethylhydantoin , 135 parts of phthalocyanine pigment (CP-9) was prepared in the same manner as in Example 1. The resulting phthalocyanine pigment (CP-9) was found to have an iodine substitution number of 4.0, and a peak corresponding to the same molecular weight was identified from the mass spectrum to identify the desired compound. The halogen distribution width was 7, and the volume average primary particle diameter was 47 nm.

[Example 10]

(Production of phthalocyanine pigment (CP-10)

225 parts of phthalonitrile and 85 parts of gallium trichloride were mixed and stirred in 1250 parts of n-amyl alcohol in a reaction vessel. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the mixture was heated and refluxed at 136 DEG C for 5 hours. The reaction solution cooled to 30 deg. C as it was stirred 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 of 2000 parts of methanol and 4000 parts of water, and dried to obtain 203 parts of chlorogallium phthalocyanine (see Chemical Formula 9 below).

As a result of elemental analysis on the obtained chlorogallium phthalocyanine, an actual value (C) of 62.4%, (H) of 2.7% and (N) of (N) was obtained for 62.22%, 2.61% ) 18.0%, and the target compound was identified.

[Chemical Formula 16]

Subsequently, in the reaction vessel, 1500 parts of the concentrated sulfuric acid was added with 100 parts of the chlorogallium phthalocyanine in an ice bath. Thereafter, 90 parts of 1,3-dibromo-5,5-dimethylhydantoin was slowly added and the mixture was stirred at 25 占 폚 for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 占 폚, and the resultant precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution and washing with water and drying to obtain 113 parts of phthalocyanine pigment (CP- 10).

As a result of calculating the bromine substitution number with respect to the obtained phthalocyanine pigment (CP-10), an average of 4.1 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 7, and the volume average primary particle size was 42 nm.

[Example 11]

(Preparation of phthalocyanine pigment (CP-11)

225 parts of phthalonitrile and 107 parts of silicon tetrachloride were mixed and stirred in 1250 parts of n-amyl alcohol in a reaction vessel. To this was added 266 parts of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene), and the mixture was heated and refluxed at 136 DEG C for 8 hours. The reaction solution cooled to 30 deg. C as it was stirred 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 of 2000 parts of methanol and 4000 parts of water, and dried to obtain 188 parts of dichlorosilicot phthalocyanine (see Chemical Formula (10) below).

The obtained dichlorosilicone phthalocyanine was subjected to elemental analysis. As a result, the measured values (C), (H) and (N) were 62.6%, 2.5% and 2.5%, respectively, for 62.85%, 2.64% ) 18.2%, and the compound of interest was identified.

[Chemical Formula 17]

Subsequently, in the reaction vessel, 1500 parts of concentrated sulfuric acid was added to 100 parts of the above dichlorosilicic phthalocyanine in an ice bath. Thereafter, 100 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 占 폚 for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 占 폚, and the resultant precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution and washing with water and drying to obtain 161 parts of phthalocyanine pigment (CP- 11).

As a result of calculating the bromine substitution number with respect to the obtained phthalocyanine pigment (CP-11), an average of 3.9 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 6, and the volume average primary particle diameter was 41 nm.

[Example 12]

(Production of phthalocyanine pigment (CP-12)

225 parts of phthalonitrile and 126 parts of tin tetrachloride were mixed and stirred in 1,250 parts of n-amyl alcohol in a reaction vessel. 266 parts of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) was added thereto, and the mixture was heated and refluxed at 136 DEG C for 10 hours. The reaction solution cooled to 30 deg. C as it was stirred 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 of 2000 parts of methanol and 4000 parts of water, and dried to obtain 215 parts of dichloro-tin phthalocyanine (see Chemical Formula (11) below).

As a result of elemental analysis on the obtained dichlorotin phthalocyanine, the measured values (C), (H) and (N) were 54.6%, 2.3% and 2.3% ) &Lt; / RTI &gt; 15.8%, and the target compound was identified.

[Chemical Formula 18]

Then, 406 parts of aluminum bromide, 94 parts of sodium bromide and 10 parts of ferric bromide were heated and melted in a reaction vessel, and 100 parts of the above dichlorotin phthalocyanine was added at 140 占 폚. The temperature was raised to 160 DEG C and 30 parts of bromine was added dropwise. The reaction solution was poured 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 washing and hot water washing, and then dried to give crude tin phthalocyanine 213 parts were obtained. The resulting crude tin phthalocyanine was dissolved in 1900 parts of concentrated sulfuric acid, and the mixture was stirred at 50 캜 for 3 hours. Subsequently, 200 parts of phthalocyanine pigment (CP-12) was prepared by pouring the dissolution liquid into 12,000 parts of water while heating at 70 DEG C, followed by filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing and drying.

As a result of calculating the bromine substitution number with respect to the obtained phthalocyanine pigment (CP-12), an average of 3.2 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 5, and the volume average primary particle size was 39 nm.

[Example 13]

(Production of phthalocyanine pigment (CP-13)

225 parts of phthalonitrile and 107 parts of indium trichloride were mixed and stirred in 1250 parts of n-amyl alcohol in a reaction vessel. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), and the mixture was heated and refluxed at 136 DEG C for 7 hours. The reaction solution cooled to 30 deg. C as it was stirred 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 of 2000 parts of methanol and 4000 parts of water, and dried to obtain 218 parts of chloroindium phthalocyanine (see Chemical Formula 12 below).

(H) and 2.3% (N) were measured for elemental analysis of the obtained chloroindium phthalocyanine, with respect to the calculated values (C) 57.99%, (H) 2.43% and (N) 16.91% ) Was 16.7%, and the target compound was identified.

[Chemical Formula 19]

Subsequently, in a reaction vessel, 406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of chloroindium phthalocyanine was added at 140 deg. The temperature was raised to 160 DEG C and 15 parts of chlorine was blown. The reaction solution was poured 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 washing and hot water washing, and then drying was conducted to prepare crude chlorinated indium phthalocyanine 163 parts were obtained. The resulting crude indium phthalocyanine chloride was dissolved in 1200 parts of concentrated sulfuric acid, and the mixture was stirred at 50 캜 for 3 hours. Subsequently, a dissolution liquid was poured into 7200 parts of water with stirring. The mixture was heated to 70 占 폚, filtered, washed with hot water, washed with 1% aqueous sodium hydroxide solution, washed with warm water and dried to obtain 119 parts of phthalocyanine pigment (CP-13).

Chlorine-substituted water was calculated for the obtained phthalocyanine pigment (CP-13). As a result, a peak corresponding to the same molecular weight was identified from the mass spectrum on an average of 2.9, and the target compound was identified. The halogen distribution width was 5, and the volume average primary particle diameter was 37 nm.

[Example 14]

(Production of phthalocyanine pigment (CP-14)

225 parts of phthalonitrile and 104 parts of germanium tetrachloride were mixed and stirred in 1250 parts of n-amyl alcohol in a reaction vessel. 266 parts of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) was added thereto, and the mixture was heated and refluxed at 136 DEG C for 10 hours. The reaction solution cooled to 30 deg. C as it was stirred 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 of 2000 parts of methanol and 4000 parts of water, and dried to obtain 202 parts of dichloro-Germanium phthalocyanine (see Chemical Formula (13) below).

As a result of elemental analysis on the obtained dichloro-germanium phthalocyanine, the measured values (C), (H) and (N) were 58.4%, 2.4% and 2.4% ) 16.9%, and it was identified that the compound was the target compound.

[Chemical Formula 20]

Subsequently, in a reaction vessel, 1500 parts of concentrated sulfuric acid was added to 100 parts of the above dichloro-Germanium phthalocyanine in an ice bath. Then, 71 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25 DEG C for 5 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 占 폚, and the resultant precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution and washing with water and drying to obtain 112 parts of phthalocyanine pigment (CP- 14).

As a result of calculating the number of substitution of chlorine with respect to the obtained phthalocyanine pigment (CP-14), the average of chlorine was 5.9, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum. The halogen distribution width was 8, and the volume average primary particle size was 43 nm.

The structural formulas of the phthalocyanine pigments obtained in Examples 1 to 14 are shown below. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of substitution numbers of halogen atoms.

[Chemical Formula 21]

[Example 15]

(Production of phthalocyanine pigment (P-1)

1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the phthalocyanine pigment (CP-1) obtained in Example 1, and 40 parts of diphenylphosphinic acid were added to a reaction vessel. After reacting at 85 占 폚 for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water and then dried at 60 DEG C for one day under reduced pressure to obtain 124 parts of phthalocyanine pigment (P-1). A bromine substitution number was calculated with respect to the resulting phthalocyanine pigment (P-1). As a result, an average of 1.7 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified and the desired compound was identified. The halogen distribution width was 3, and the volume average primary particle size was 33 nm.

(Preparation of phthalocyanine pigments (P-2) to (P-24)) [

The procedure of Example 15 was repeated except that the phthalocyanine pigment as the raw material and the acidic compound in the preparation of the phthalocyanine pigment (P-1) were each changed under the conditions described in Table 1, and phthalocyanine pigments (P -2) to (P-24). The average value of the number of substitution of halogen atoms represented by X ₁ or X ₂ , the halogen distribution width and the volume average primary particle diameter are shown in Table 2. From the mass spectrum, peaks corresponding to the same molecular weight were confirmed, . &Lt; / RTI &gt;

The structural formulas of the phthalocyanine pigments obtained in Examples 15 to 38 are shown below. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of substitution numbers of halogen atoms.

[Chemical Formula 22]

(23)

&Lt; EMI ID =

&Lt; Preparation of comparative phthalocyanine pigment >

[Comparative Example 1]

(Production of phthalocyanine pigment (P-25)

1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of chloroaluminum phthalocyanine represented by the formula (8) obtained in Example 1, and 49.5 parts of diphenyl phosphate were added to a reaction vessel. After reacting at 85 占 폚 for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water, and dried at 60 DEG C under reduced pressure for one day to obtain 125 parts of phthalocyanine pigment (P-25). The resulting phthalocyanine pigment does not have a halogen substituent on the phthalocyanine ring. The phthalocyanine pigment thus obtained had a volume average primary particle size of 44 nm.

[Comparative Example 2]

(Preparation of phthalocyanine pigment (P-26)

To the reaction vessel, 100 parts of 4-bromophthalimide, 132 parts of urea, 2.4 parts of ammonium molybdate, 0.8 part of sodium sulfate, and 200 parts of 1-chloronaphthalene were added and stirred. After heating to 150 캜, 16.6 parts of aluminum chloride and 21.2 parts of urea were added and reacted at 250 캜 for 7 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried. To the Erlenmeyer flask, 1000 parts of 98% sulfuric acid was added. The dried product was added thereto, dissolved, and stirred at room temperature for 1 hour. Thereafter, the sulfuric acid solution was poured into 6000 parts of ice water at 3 DEG C, and the precipitated solid was filtrated, washed with water and dried to obtain phthalocyanine having an average value of bromine atom substitution of 4 and a halogen distribution width of 1 70.4 parts of pigment were obtained. Subsequently, to the reaction vessel, the obtained phthalocyanine pigment, 1,000 parts of 1-methyl-2-pyrrolidinone and 24 parts of diphenyl phosphate were added. After reacting at 85 占 폚 for 3 hours, this solution was injected into 8000 parts of water. The reaction product was filtered, washed with 16000 parts of water, and dried at 60 ° C under reduced pressure for one day, to obtain 79 parts of a phthalocyanine pigment (P-26).

As a result of calculating the bromine substitution number with respect to the obtained phthalocyanine pigment (P-26), an average of 4.0 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 1. The volume average primary particle size of the obtained phthalocyanine pigment (P-26) was 53 nm.

[Comparative Example 3]

(Production of phthalocyanine pigment (P-27)

In the production of the phthalocyanine pigment (P-25), the chloroaluminum phthalocyanine represented by the formula (8) used as the starting material was added to the chlorogallium phthalocyanine represented by the formula (9) obtained in Example 10, and 49.5 parts of diphenyl phosphate (P-26) was obtained in the same manner as in Comparative Example 1, except that the amount of the phthalocyanine pigment (P-26) was changed to 52 parts. The resulting phthalocyanine pigment does not have a halogen substituent on the phthalocyanine ring. The volume average primary particle size of the obtained phthalocyanine pigment was 57 nm.

[Comparative Example 4]

(Preparation of phthalocyanine pigment (P-28)

To the reaction vessel, 100 parts of 4-bromophthalimide, 132 parts of urea, 2.4 parts of ammonium molybdate, 0.8 part of sodium sulfate, and 200 parts of 1-chloronaphthalene were added and stirred. After heating to 150 占 폚, 20.7 parts of silicon tetrachloride and 21.2 parts of urea were added and reacted at 250 占 폚 for 7 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried. To the Erlenmeyer flask, 1000 parts of 98% sulfuric acid was added. The dried product was added thereto, dissolved, and stirred at room temperature for 1 hour. Thereafter, the sulfuric acid solution was poured into 6000 parts of ice water at 3 DEG C, and the precipitated solid was filtered off, washed with water and dried to obtain 78.8 parts of a phthalocyanine pigment having an average value of bromine atom substitution numbers of 4 and a halogen distribution width of 1 . Subsequently, to the reaction vessel, the obtained phthalocyanine pigment, 1,000 parts of 1-methyl-2-pyrrolidinone and 55 parts of diphenyl phosphate were added. After reacting at 85 占 폚 for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water and then dried at 60 DEG C for one day under reduced pressure to obtain 108 parts of a phthalocyanine pigment (P-28).

A bromine substitution number was calculated for the obtained phthalocyanine pigment (P-28). As a result, an average of 4.0 was obtained. A peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the desired compound was identified. The halogen distribution width was 1. The volume average primary particle size of the obtained phthalocyanine pigment (P-28) was 55 nm.

[Comparative Example 5]

(Preparation of phthalocyanine pigment (P-29)

To the reaction vessel were added 100 parts of 4-chlorophthalic acid, 132 parts of urea, 2.4 parts of ammonium molybdate, 0.8 parts of sodium sulfate, and 200 parts of 1-chloronaphthalene and stirred. After heating to 150 캜, 20 parts of tin chloride and 21.2 parts of urea were added and reacted at 250 캜 for 7 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried. To the Erlenmeyer flask, 1000 parts of 98% sulfuric acid was added. The dried product was added thereto, dissolved, and stirred at room temperature for 1 hour. Subsequently, the sulfuric acid solution was poured into 6000 parts of ice water at 3 DEG C, and the precipitated solid was filtered off, washed with water and dried to obtain 70.4 parts of a phthalocyanine pigment having an average value of chlorine atom substitution number of 4 and a halogen distribution width of 1 . Subsequently, to the reaction vessel, the obtained phthalocyanine pigment, 1,000 parts of 1-methyl-2-pyrrolidinone and 32 parts of diphenyl phosphate were added. After reacting at 85 占 폚 for 3 hours, this solution was injected into 8000 parts of water. The reaction product was filtered, washed with 16000 parts of water and then dried at 60 DEG C for one day under reduced pressure to obtain 79 parts of a phthalocyanine pigment (P-29).

Chlorine-substituted water was calculated for the resulting phthalocyanine pigment (P-29). As a result, an average of 4.0 was obtained. From the mass spectrum, peaks corresponding to the same molecular weight were identified, and the desired compound was identified. The halogen distribution width was 1. The volume average primary particle size of the obtained phthalocyanine pigment (P-29) was 53 nm.

[Comparative Example 6]

(Production of phthalocyanine pigment (P-30)

1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of chloroindium phthalocyanine represented by the chemical formula (12) obtained in Example 13, and 60 parts of diphenyl phosphate were added to a reaction vessel. After reacting at 85 占 폚 for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water and then dried at 60 DEG C for one day under reduced pressure to obtain 125 parts of phthalocyanine pigment (P-30). The resulting phthalocyanine pigment does not have a halogen substituent on the phthalocyanine ring. The phthalocyanine pigment thus obtained had a volume average primary particle diameter of 56 nm.

[Comparative Example 7]

(Preparation of phthalocyanine pigment (P-31)

1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of dichloro-germanium phthalocyanine represented by the formula (13) obtained in Example 14, and 60 parts of diphenyl phosphate were added to a reaction vessel. After reacting at 85 占 폚 for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water, and dried at 60 DEG C for one day under reduced pressure to obtain 125 parts of phthalocyanine pigment (P-31). The resulting phthalocyanine pigment does not have a halogen substituent on the phthalocyanine ring. The phthalocyanine pigment thus obtained had a volume average primary particle diameter of 56 nm.

The structural formulas of the phthalocyanine pigments obtained in Comparative Examples 1 to 7 are shown below. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of substitution numbers of halogen atoms.

(25)

<Coloring composition>

The following Example relates to a coloring composition (pigment dispersion) using the above-prepared phthalocyanine pigment. The dispersant and binder resin used were produced as follows.

&Lt; Production method of binder resin >

(Preparation of methacrylic resin solution (1)) [

70.0 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and the temperature was raised to 80 ° C. After the inside of the reaction vessel was purged with nitrogen, , 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110, And 0.4 part of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a methacrylic resin solution having a weight average molecular weight (Mw) of 26,000. After cooling the obtained resin solution to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure non-volatile matter. Then, in consideration of the measured value, methacrylic resin solution (1) was prepared by adding propylene glycol monoethyl ether acetate to the resin solution obtained so that the nonvolatile content became 20% by mass.

&Lt; Evaluation of resin &

(Polymerization average molecular weight (Mw) of the resin)

(Mw) in terms of polystyrene measured by using THF in a developing solvent in GPC (Hoso Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation).

<Acid value of resin>

("COM-555" manufactured by Hiranuma Industrial Co., Ltd.) was added to 0.5 to 1.0 part of the resin solution, to which 80 ml of acetone and 10 ml of water were added and stirred to uniformly dissolve, and 0.1 mol / , And the acid value of the resin solution was measured. The acid value per solid fraction of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

&Lt; Preparation of resinous dispersant solution >

A commercially available terpolymer dispersant, EFKA4300 manufactured by BASF, and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a nonvolatile content of 40 mass% to obtain a resinous dispersant solution (1).

&Lt; Preparation of pigment dispersion >

[Example 39]

(Pigment dispersion (GP-1))

The mixture having the following composition was stirred and mixed, and then dispersed for 3 hours by means of zirconia beads having a diameter of 0.5 mm by means of AiGa Mill ("Mini Model M-250 MKII" manufactured by IGA Japan). Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 m to prepare a pigment dispersion (GP-1) having a nonvolatile fraction of 20 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 40 to 62 and Comparative Examples 8 to 14]

(Pigment dispersion bodies (GP-2) to (GP-31))

Pigment dispersions (GP-2) to (GP-31) were prepared in the same manner as in Example 39 except that the phthalocyanine pigment (P-1) was changed to the phthalocyanine pigment shown in Table 3.

&Lt; Evaluation of pigment dispersion >

The following evaluations were carried out on the pigment dispersions (GP-1) to (GP-31) obtained in Examples and Comparative Examples. The results are shown in Table 3.

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

Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a pigment dispersion coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel to each other, the light is transmitted through the polarizing plate, but when the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the coating film of the pigment dispersion, scattering or the like occurs by the colorant particles (phthalocyanine pigment particle), and when a part of the polarizing plane is separated, when the polarizing plate is parallel, When the amount of light is reduced and the polarizing plate is orthogonal, some light is transmitted. The transmitted light was measured as the luminance on the polarizing plate, and the ratio of the luminance when the polarizing plate was parallel and the luminance when the polarizing plate was orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (luminance in parallel) / (luminance in orthogonal)

Therefore, when scattering is caused by the coloring agent in the coating film, the brightness at the time of parallelism decreases and the brightness at the time of orthogonality increases, so that the contrast ratio is lowered.

A color luminance meter (BM-5A, Topcon Co.) was used as the luminance meter, and a polarizing plate (NPF-G1220DUN manufactured by Nitto) was used as the polarizer. In the measurement, a measurement was made with a black mask punched with holes of 1 cm in length and width.

Each of the pigment dispersions was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 1.1 mm using a spin coater, followed by drying at 70 DEG C for 20 minutes, followed by heating at 230 DEG C for 60 minutes. Respectively. The contrast ratio (CR) of the obtained coated film substrate was measured. The coated film substrate was prepared so as 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: very good

○: 6000 or more to less than 9000: Good

?: 3000 or more to less than 6000: practically usable

×: less than 3000: poor

(Evaluation of Heat Resistance of Coating Film)

Each of the pigment dispersions was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 1.1 mm using a spin coater, followed by drying at 70 DEG C for 20 minutes, followed by heating at 230 DEG C for 60 minutes. Respectively. The coated film substrate was prepared so as to have a film thickness of 1.5 μm after heat treatment at 230 ° C. [L * (1), a * (1), b * (1)] was measured using a brown spectrophotometer (OSP-SP100, manufactured by Olympus Optics) The chromaticity [L * (2), a * (2), b * (2)] after heating treatment at 250 ° C for 60 minutes was measured and the color difference ΔE * ab was calculated by the following formula .

Equation (2)

ΔE * ab = [[L * (2) -L * (1)] 2 + [a * (2) -a * (1)] 2 + [b * (2) -b * (1)] 2] ^1/2

Heat resistance was evaluated according to the following criteria.

?: ΔE * ab = 1 or less: very good

?: ΔE * ab = 1 to 3: Good

?:? E * ab = 3 to 5: Practically usable

×: ΔE * ab = 5 or more: poor

(Evaluation of light resistance of coating film)

Each of the pigment dispersions was coated on a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 1.1 mm using a spin coater, followed by drying at 70 DEG C for 20 minutes, followed by heating at 230 DEG C for 60 minutes. Respectively. The coated film substrate was prepared so as to have a film thickness of 1.5 μm after heat treatment at 230 ° C. (COLORED OPTICAL GLASS L38 manufactured by Hoya Co.) was attached to the substrate and the color before and after the irradiation of ultraviolet light for 150 hours using a 470 W / m &lt; 2 &gt; xenon lamp was measured. The color difference? E * ab was determined. The judgment criteria are the same as in the heat resistance evaluation.

(Foreign object evaluation)

The generation of foreign matter was evaluated by coating the pigment dispersion on the transparent substrate so that the dry coating film had a thickness of about 2.0 占 퐉 and heating the coated substrate in an oven at 250 占 폚 for 60 minutes to cool the coating film substrate. The surface was observed using an optical microscope "BX53M / BXFM" manufactured by Olympus Systems. The magnification was 500 times, and the number of foreign objects observable in any five fields of view was measured by transmission illumination.

◎: Less than 3 foreign objects: very good

○: Number of foreign matters is 3 or more, less than 20: Good

△: Number of foreign matter is 21 or more, less than 100: practically usable

X: 100 or more foreign objects: bad

As in Comparative Examples 8, 10, 13, and 14, when the phthalocyanine ring was not substituted with a halogen, the contrast ratio and fastness were both low. In Comparative Examples 9, 11, and 12 in which the halogen substitution number was 4 and the halogen distribution width was 1, all of the foreign substance evaluation results were poor. On the other hand, as in Examples 39 to 62, the average value of the substitution number of the halogen atom and the halogen distribution width are within a specific range because of the excellent contrast ratio, heat resistance, light resistance and foreign matter evaluation result, .

&Lt; Preparation of other finely divided pigment >

(Preparation of finely divided green pigment (PG58-1)

Phthalocyanine-based green pigment C.I. 200 parts of Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Respectively. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain a finely divided green pigment (PG58-1).

(Preparation of finely divided green pigment (PG7-1)) [

Phthalocyanine-based green pigment C.I. 200 parts of Pigment Green 7 ("GreenGNX" manufactured by CLARIANT), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain a finely divided green pigment (PG7-1).

(Preparation of finely divided green pigment (PG36-1)

Phthalocyanine-based green pigment C.I. 200 parts of Pigment Green 36 ("Green 8G" manufactured by CLARIANT), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and dried at 85 ° C overnight to obtain a finely divided green pigment (PG36-1).

(Preparation of finely divided yellow pigment (PY150-1)

Nickel complex system yellow pigment C.I. 200 parts of Pigment Yellow 150 (&quot; E-4GN &quot;, manufactured by RANSESS), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by INOUE KK) and kneaded at 80 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 캜 for one day to obtain a finely divided yellow pigment (PY150-1).

(Preparation of finely divided yellow pigment (PY138-1)

Quinophthalone Yellow Pigment C.I. 200 parts of Pigment Yellow 138 ("Paliotol Yellow L 0962HD" manufactured by BASF), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Subsequently, this kneaded product was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for one day to obtain a finely divided yellow pigment (PY138-1).

(Preparation of finely divided yellow pigment (PY139-1)

Isoindoline yellow pigment C.I. 200 parts of Pigment Yellow 139 ("Paliotol Yellow L 2146HD" manufactured by BASF), 1400 parts of sodium chloride and 360 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Subsequently, this kneaded product was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain a finely divided yellow pigment (PY139-1).

(Preparation of finely divided yellow pigment (PY185-1)

Isoindoline yellow pigment C.I. 200 parts of Pigment Yellow 185 ("Paliotol Yellow L 1155" manufactured by BASF Corporation), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Subsequently, this kneaded product was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain a finely divided yellow pigment (PY185-1).

(Preparation of finely divided yellow pigment (BY-1)

100 parts of the compound (A), 108 parts of tetrachloroformic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180 ° C and reacted for 4 hours. TOF-MS confirmed the formation of the quinophthalone compound represented by the formula (7-1) and disappearance of the compound (A) as the starting material. After cooling to room temperature again, the reaction mixture was poured into 3510 parts of acetone and stirred for 1 hour at room temperature. The product was filtered off, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound represented by the formula (7-1). As a result of mass analysis by TOF-MS, a quinophthalone compound represented by the formula (7-1) was identified.

(26)

Subsequently, 100 parts of the quinophthalone compound represented by the formula (7-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol were added to a 1 gallon stainless steel kneader (manufactured by Inoue KK) and kneaded at 60 DEG C for 8 hours Respectively. Subsequently, this kneaded product was charged into hot water and stirred for 1 hour while heating at about 70 DEG C to form a slurry, followed by filtration and washing to remove sodium chloride and diethylene glycol, followed by drying at 80 DEG C overnight, 98 parts of yellow pigment (BY-1) were obtained. The average primary particle diameter was 31.1 nm. The average primary particle diameter is a volume average primary particle diameter determined by the above-described method.

(27)

(Preparation of a finely divided red pigment (PR254-1)

Diketopyrrolopyrrole pigment C.I. 200 parts of Pigment Red 254 (&quot; B-CF &quot; manufactured by BASF), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by INOUE KK) and kneaded at 80 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain 190 parts of finely divided diketopyrrolopyrrole pigment (PR254-1).

(Preparation of finely divided red pigment (PR177-1)) [

Anthraquinone-based red pigment C.I. 200 parts of Pigment Red 177 ("Chromophthalide A2B" manufactured by BASF), 1400 parts of sodium chloride and 360 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours . Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain a fine red colored pigment (PR177-1) of an anthraquinone system.

(Preparation of finely divided blue pigment (PB15: 6-1)

200 parts of phthalocyanine-based blue pigment CI Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd., specific surface area 60 m ² / g)

, And 360 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by INOUE MFG. CO., LTD.) And kneaded at 80 DEG C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day to obtain a finely divided blue pigment (PB15: 6-1).

(Preparation of finely divided violet pigment (PV23-1)

Dioxetrone-based purple pigment C.I. 200 parts of Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color), 1400 parts of sodium chloride and 360 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 6 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while heating at 80 DEG C to form a slurry. The slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for one day to obtain a finely divided violet pigment (PV23-1).

&Lt; Preparation of other finely dispersed pigment dispersion >

(Preparation of finely divided pigment dispersions (GP-32) to (VP-1)) [

Pigment dispersions (GP-32) to (VP-1) were prepared in the same manner as in Example 39 except that the phthalocyanine pigment (P-1) was changed to the finely divided pigment shown in Table 4.

&Lt; Preparation of Photosensitive Coloring Composition >

[Example 63]

(Green photosensitive coloring composition (GR-1))

The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a filter having a pore diameter of 1 탆 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 M-402 manufactured by East Asia Synthetic Chemical Industry Co., Ltd.): 2.0 parts

Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts

("EAB-F" manufactured by Hodagaya Chemical Co., Ltd.): 0.3 part

Cyclohexanone: 39.0 parts

[Examples 64 to 93, Comparative Examples 15 to 21]

(GR-2) to (GR-38) were obtained in the same manner as in Example 63, except that the details of 50 parts of the total of the pigment dispersions were changed to the components and mass parts shown in Table 5, respectively. &Lt; / RTI &gt;

&Lt; Evaluation of Photosensitive Coloring Composition >

The following evaluations were carried out on the photosensitive coloring compositions obtained in Examples and Comparative Examples. The results are shown in Table 5.

(Evaluation of brightness)

The photosensitive coloring composition was applied to a glass substrate having a thickness of 100 mm x 100 mm and a thickness of 1.1 mm using a spin coater and dried in a clean oven at 70 캜 for 20 minutes. Subsequently, the substrate was cooled to room temperature, and ultraviolet light was exposed through a photomask using an ultra-high pressure mercury lamp. Thereafter, this substrate was spray-developed with a 0.2 mass% aqueous solution of sodium carbonate at 23 캜 for 30 seconds, washed with ion-exchanged water, and dried. Again, heat treatment was performed at 230 캜 for 30 minutes in a clean oven to form a green colored pixel layer in the form of a stripe on the substrate. The color of the colored pixel layer was adjusted so that x = 0.297 and y = 0.570 in the C light source. The lightness (Y) of the obtained colored pixel was measured with a brown spot spectrophotometer ("OSP-SP200" manufactured by Olympus Optics). The evaluation criteria are as follows.

◎: 66.5 or more: very good

○: 65.9 or more and less than 66.5: Good

?: 65.3 or more and less than 65.9: practically usable

×: less than 65.3: poor

(Evaluation of coloring power)

First, a green colored pixel layer was formed in the same manner as in the brightness evaluation. The coloring power of the obtained colored pixel layer was measured by measuring the film thickness of the colored pixel layer when x = 0.297 and y = 0.570 in the C light source, and the tinting strength was evaluated. For measurement, a catalytic stepped system (DeKTaK8 made by ULVAC) was used. The evaluation criteria are as follows.

⊚: less than 1.8 μm: very good

?: 1.8 占 퐉 or more and less than 2.0 占 퐉: Good

[Delta]: 2.0 μm or more and less than 2.2 μm: practically usable

×: 2.2 μm or more: poor

(Evaluation of solvent resistance)

First, a green colored pixel layer was formed in the same manner as in the brightness evaluation. The obtained green colored pixel layer was immersed in N-methyl-2-pyrrolidone (NMP) and methanol (MeOH) for 15 minutes to measure the color difference of the green pixel portion before and after immersion. The measurement method, the calculation method, and the evaluation standard of the color difference were the same as the evaluation of the heat resistance and the light resistance.

When the phthalocyanine ring was not substituted with a halogen, as in Comparative Examples 15, 17, 20, and 21, the solvent resistance was low. In Comparative Examples 16, 18 and 19 in which the halogen substitution number was 4 and the halogen distribution width was 1, all of the solvent resistance was poor. On the other hand, as in Examples 63 to 93, the photosensitive coloring composition comprising a phthalocyanine pigment having an average value of halogen-substituted water of not less than 1 and not more than 6 and a halogen distribution width of not less than 2 has high brightness and coloring power, Results.

&Lt; Fabrication of color filter &

A green photosensitive coloring composition containing the phthalocyanine pigment obtained in the above Examples was used to prepare a color filter. The used red photosensitive coloring composition and blue photosensitive coloring composition 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 with a filter having a pore diameter of 1 탆 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 (Aronix M-402 manufactured by East Asia Synthetic Chemical Industry Co., Ltd.): 2.0 parts

Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts

("EAB-F" manufactured by Hodagaya Chemical Co., Ltd.): 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 diameter of 1 m 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 (Aronix M-402 manufactured by East Asia Synthetic Chemical Industry Co., Ltd.): 2.0 parts

Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts

("EAB-F" manufactured by Hodagaya Chemical Co., Ltd.): 0.3 part

Cyclohexanone: 39.0 parts

[Example 94]

The red photosensitive coloring composition (RR-1) was coated on a glass substrate previously coated with a black matrix by spin coating, and then dried in a clean oven at 70 캜 for 20 minutes. Subsequently, the substrate was cooled to room temperature, and ultraviolet rays were exposed through a photomask using an ultra-high pressure mercury lamp. Thereafter, this substrate was spray-developed with a 0.2 mass% aqueous solution of sodium carbonate at 23 캜 for 30 seconds, washed with ion-exchanged water, and dried. Again, heat treatment was performed at 230 캜 for 30 minutes in a clean oven to form a stripe-shaped colored pixel layer on the substrate.

Subsequently, a green coloring pixel layer was formed in the same manner as the red coloring pixel layer using a green photosensitive coloring composition (GR-13). In the same manner, a blue coloring pixel layer was formed using the blue photosensitive coloring composition (BR-1) to obtain a color filter (CF-1). The film thicknesses of the respective coloring pixel layers were all 2.0 mu m.

The obtained color filters were evaluated for brightness and contrast ratio. The measurement method is the same as in the evaluation of the pigment dispersion. All of the color filters using the green coloring composition according to the embodiment of the present invention have high brightness and excellent contrast ratios. In view of the above, the effect of the phthalocyanine pigment which is an embodiment of the present invention has been 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 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₁ is 1 or more and less than 6 and a halogen distribution width is 2 or more.
M ₁ represents Al, Ga or In.
Y ₁ represents -OP (= O) R ₁ R ₂ , -OC (= O) R ₃ , -OS (= O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, 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 represents a hydrogen atom, 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 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

[In the general formula (2)
X ₂ represents a halogen atom, and n represents an integer of 1 to 10. Provided that an average value of the number of substitution of halogen atoms represented by X ₂ is 1 or more and less than 6 and a halogen distribution width is 2 or more.
M ₂ represents Si, Ge or Sn.
Y ₂ and Y ₃ each independently represent -OP (═O) R ₁ R ₂ , -OC (═O) R ₃ , -OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, 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 represents a hydrogen atom, 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 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
The method according to claim 1,
(1), X ₁ represents a chlorine atom or a bromine atom, Y ₁ represents -OP (= O) R ₁ R ₂ , X ₂ represents a chlorine atom or a bromine atom in the general formula (2) And Y ₂ and Y ₃ are -OP (= O) R ₁ R ₂ .
3. The method according to claim 1 or 2,
(1) wherein X ₁ is a bromine atom, Y ₁ is -OP (═O) (OC ₆ H ₅ ) ₂ , X ₂ in the general formula (2) is a bromine atom, Y ₂ and Y ₃ are -OP (= O) (OC ₆ H ₅ ) ₂ .
A coloring composition comprising a colorant, a binder resin and an organic solvent, wherein the colorant contains the phthalocyanine pigment according to claim 1.
5. The method of claim 4,
Wherein the coloring agent further contains at least one of a green coloring matter and a yellow coloring matter.
6. The method of claim 5,
Wherein the green pigment is at least one selected from the group consisting of CI pigment greens 7, 36 and 58, and the yellow pigment is at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150, 185 and the following general formula (7) And a quinophthalone pigment represented by the formula (1).

[In the formula (7), R ¹ to R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent or an aryl group which may have a substituent. Provided that at least one adjacent pair of R ¹ to R ⁴ groups and / or at least one adjacent pair of R ¹⁰ to R ¹³ are integral to form an aromatic ring which may have a substituent .]
5. The method of claim 4,
Further comprising at least one of a photopolymerizable monomer and a photopolymerization initiator.
A color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment comprises any one of the items of any of claims 4 to 7 A color filter formed by the coloring composition according to claim 1.