JP2018163287A - Coloring agent for color filter, coloring composition, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring agent for a color filter and a coloring composition for a color filter which not only have an excellent color characteristic (brightness) and an excellent contrast ratio but also can attain an extremely high dispersion property and storage stability when used as a composition, and to provide a high-quality color filter that uses the coloring composition for a color filter .SOLUTION: The above object is achieved by aluminum phthalocyanine having a specific structure of the present application, a coloring composition using the specific aluminum phthalocyanine, and a color filter.SELECTED DRAWING: Figure 1

Description

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

  Patent Document 1 proposes an aluminum phthalocyanine pigment having a halogen distribution width and an X-ray diffraction pattern different from that of the present application as a colorant. However, the above-mentioned aluminum phthalocyanine pigment has not been able to achieve the recently required high level of dispersibility and storage stability.

International Publication No. 2016/125806

  The problem to be solved by the present invention is not only excellent in color characteristics (brightness) and contrast ratio, but also a color filter capable of achieving very excellent dispersibility and storage stability when formed into a composition. It is to provide a colorant for color, a color composition for color filter, and a high-quality color filter using the same.

  As a result of intensive studies to solve the above problems, the present inventors obtained novel aluminum phthalocyanines, which are excellent in dispersibility and storage stability, and excellent in color characteristics such as brightness and contrast. And found out that the present invention.

  That is, the present invention is represented by the following general formula (1), and the X-ray diffraction pattern by CuKα rays is set to Bragg angles 2θ (± 0.2) = 5.7 °, 24.3 °, 25.2 °. The present invention relates to a color filter colorant containing a phthalocyanine pigment having a peak.

[In General Formula (1), X represents a halogen atom, n represents the average value of the number of halogen atoms substituted, and is 1-15. However, the halogen distribution width of the halogen atom represented by X is 4 or more. Y ₁ represents —OP (═O) (OC ₆ H ₅ ) ₂ . ]

  The present invention also relates to a color filter coloring composition containing a colorant, a binder resin and an organic solvent, wherein the colorant contains the color filter colorant.

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

  In the present invention, the green pigment may be C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. Pigment Green 58, which is at least one selected from the group consisting of C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. It is related with the said coloring composition for color filters which is at least 1 sort (s) chosen from the group which consists of pigment yellow 185.

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

  Furthermore, the present invention provides a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment is the color filter coloring composition. It relates to a color filter formed by the above.

  According to the present invention, not only the color characteristics (brightness) and contrast ratio are excellent, but also when used as a composition, the color filter colorant and the color filter color composition exhibit extremely high dispersibility and storage stability. And a high-quality color filter using the same.

FIG. 1 is an X-ray diffraction pattern of aluminum phthalocyanine (P-1) produced in Example 1 by CuKα rays. FIG. 2 is an X-ray diffraction pattern of aluminum phthalocyanine (P-14) produced in Comparative Example 3 using CuKα rays. FIG. 3 is an X-ray diffraction pattern of the aluminum phthalocyanine (P-15) produced in Comparative Example 4 using CuKα rays.

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

<Phthalocyanine pigment>
The phthalocyanine pigment of the present invention is represented by the following general formula (1) and has a specific X-ray diffraction pattern (black angle 2θ (± 0.2) = 5.7 °, 24.3 °, 25.2 °). And can be suitably used as a color filter colorant, particularly a green colorant, used in a color filter color composition.

[In General Formula (1), X represents a halogen atom, n represents the average value of the number of halogen atoms substituted, and is 1-15. However, the halogen distribution width of the halogen atom represented by X is 4 or more. Y ₁ represents —OP (═O) (OC ₆ H ₅ ) ₂ . ]

  The aluminum phthalocyanine represented by the general formula (1) in the crystal form has properties as a pigment and can be suitably used as a colorant, particularly a green colorant. Here, (± 0.2) at the flag angle 2θ represents any value in the range from 5.1-0.2 to 5.1 + 0.2 in the case of 5.1 °, for example.

  In the general formula (1), examples of “halogen” include fluorine, bromine, chlorine and iodine, bromine and chlorine are preferred, and bromine is particularly preferred. Two or more halogens may be used in combination.

  When the average value of the number of substitutions of the halogen atom represented by X in the general formula (1) is 1 to 15, it is easy to obtain various desired characteristics. The average value of the number of substituents of the halogen atom is preferably 2 to 12 from the viewpoint of fastness, and more preferably 4 to 10 from the viewpoint of hue and fastness. The halogen distribution width is 4 or more, preferably 4 to 9, and more preferably 5 to 8. When the halogen distribution width is 4 or more, association and aggregation of phthalocyanine molecules tend to be remarkably suppressed. Therefore, when the halogen distribution width is within the above range, it greatly contributes to the suppression of the increase in particle size and the decrease in contrast caused by the association and aggregation between molecules, and it becomes easy to obtain various desired characteristics.

  Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigment represented by the general formula (1). In the mass spectrum obtained by mass spectrometry, the halogen distribution width was obtained by integrating the signal intensity (each peak value) of the molecular ion peak corresponding to the molecular weight of aluminum phthalocyanine of each component according to the number of halogen substitutions and each peak value. A value (total peak value) was calculated, and the number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width. Two or more halogen atoms may be used in combination as long as the average number of substitutions and the distribution width are within the above ranges. In this case, it is particularly preferable to use bromine and chlorine in combination.

<Method for producing phthalocyanine pigment>
Then, the manufacturing method of the aluminum phthalocyanine of this invention is demonstrated. The phthalocyanine pigment represented by the general formula (1) of the present invention is a halogenated hydroxyaluminum phthalocyanine (general formula (2) obtained by hydrolyzing an aluminum phthalocyanine represented by the following general formula (2). The desired aluminum phthalocyanine can be obtained by reacting 3)) with diphenyl phosphate.

[In General Formulas (2) and (3), X represents a halogen atom, and n represents an average value of the number of substitutions of halogen atoms, and is 1 to 15. However, the halogen distribution width of the halogen atom represented by X is 4 or more. Y ₂ represents a halogen atom or a hydroxyl group. Y ₃ represents a hydroxyl group. ]

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

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

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

  The halogenating agent used for halogenation means a fluorinating agent, a chlorinating agent, a brominating agent and an iodinating agent. For example, examples of the fluorinating agent include fluoroxytrifluoromethane, cesium fluoride sulfate, acetyl hypofluorite, N-fluorosulfonamide, diethylaminosulfur trifluoride, and N-fluoropyridinium salt.

As chlorinating agents, chlorine (Cl ₂ ), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone 2,3,4,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethylammonium chloride, benzeneselenenyl chloride and the like.

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

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

  In addition, the reaction of the halogenated hydroxyaluminum phthalocyanine represented by the general formula (3) and diphenyl phosphate can be advanced by, for example, mixing and stirring in an organic solvent. Next, the desired aluminum phthalocyanine can be obtained by removing the organic solvent.

Examples of the organic solvent used in the production of aluminum phthalocyanine include the following.
Monohydric alcohol solvents represented by methanol, ethanol, isopropanol, t-butanol,
Ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc. A polyhydric alcohol solvent represented by
1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N Amide solvents such as N, dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea or tetramethylurea,
In addition, lower monoalkyl ether solvents of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether,
Polyether solvents such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether (triglyme);
Sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, or 3-sulfolene,
Polyfunctional solvents such as diacetone alcohol and diethanolamine,
Carboxylic acid solvents such as acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, or trifluoroacetic acid,
Sulfonic acid solvents such as methanesulfonic acid or trifluorosulfonic acid,
Aromatic hydrocarbon solvents such as benzene, toluene and xylene.

  In one embodiment, since the dissolution of diphenyl phosphate is good, monohydric alcohol solvents such as methanol, ethanol, isopropyl alcohol, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone It is preferable to use an aprotic polar solvent such as These organic solvents can be used alone or in admixture of two or more.

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

  As a method for obtaining the above-mentioned aluminum phthalocyanine, for example, it is desirable to change the solvent species, reaction time, or precipitation method when reacting the halogenated hydroxyaluminum phthalocyanine represented by the general formula (3) with diphenyl phosphate. Aluminum phthalocyanine having an X-ray diffraction pattern of In particular, it is important to make the change in the degree of solution supersaturation smaller before and after mixing, and a method in which water is added to the reaction solution to precipitate the pigment is preferably used.

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

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

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

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

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent easily evaporates, those having a high boiling point of 120 ° C. or higher are preferred from the viewpoint of safety. Examples of such a water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid Polypropylene glycol or the like is used. These water-soluble organic solvents are preferably used in the range of 5 to 1000% by weight, more preferably 50 to 500% by weight, based on the total weight of aluminum phthalocyanine (100% by weight).

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

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

<Coloring composition for color filter>
The coloring composition of the present invention contains a colorant, a binder resin, and an organic solvent, and the colorant contains the specific phthalocyanine pigment of the present application represented by the general formula (1) and having a specific X-ray diffraction pattern. It is characterized by that. In one embodiment, the colored composition has a green tint derived from the present specific phthalocyanine pigment used as a colorant. The coloring composition of the present invention may contain an additional dye as a coloring agent within a range that does not impair the effect of the specific phthalocyanine pigment for adjusting the chromaticity.

<Colorant>
(Green pigment)
In one embodiment of the present invention, the coloring composition may further contain a green pigment other than the specific phthalocyanine pigment of the present application within a range not impairing the effects of the present invention in order to further adjust the chromaticity. Although there is no restriction | limiting in particular as a green pigment | dye, Generally, a green pigment or a green dye is mentioned.

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, JP2008- The zinc phthalocyanine pigment described in JP 19383, JP 2007-320986 A, JP 2004-70342 A, and the like, and the aluminum phthalocyanine pigment described in Japanese Patent No. 4893859, etc. can be exemplified. It is not limited. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36, and 58.

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

(Yellow pigment)
In order to further adjust the chromaticity, the colored composition of the present invention may contain a yellow pigment as long as the effects of the present invention are not impaired. Although there is no restriction | limiting in particular as a yellow pigment | dye, Generally, a yellow pigment or a yellow dye is mentioned.

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

  Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,192,193,194,196,198,199,213,214, may be used yellow pigment quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, examples of yellow pigments include C.I. I. It is preferably at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and 185.

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

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

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

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

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

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

  In the case of using a green dye together with the phthalocyanine pigment represented by the general formula (1), from the viewpoint of brightness and hue, the mass ratio of the green dye / the specific phthalocyanine pigment of the present application is in the range of 10/90 to 70/30. preferable. More preferably, it is the range of 20 / 80-40 / 60, More preferably, it is the range of 20 / 80-35 / 65.

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

(Miniaturization of colorant)
The colorant used in the coloring composition of the present invention is suitable as a color filter colorant by obtaining finer colorant particles by a salt milling process or the like as necessary in order to obtain high brightness and high contrast. Can be used for The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to enhance dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 80 nm or less. In one embodiment, it is more preferably in the range of 20 to 60 nm, and further preferably in the range of 30 to 50 nm.

  The salt milling process is synonymous with the solvent salt milling method described above in the section “Refining aluminum phthalocyanine”.

<Binder resin>
The binder resin may be any one that disperses a colorant such as a pigment or a dye, particularly the specific aluminum phthalocyanine of the present application. Specific examples of the binder resin include a thermoplastic resin and a thermosetting resin.

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

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

  The thermosetting resin may be, for example, a low-molecular compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing the filter segment, the cross-linking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. It is done. Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. Remaining by using a tricarboxylic anhydride such as trimellitic anhydride or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, if necessary, such as increasing the number of carboxyl groups An anhydride group can also be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

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

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

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

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

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dissolved in a monomer, a resin, and the like, and further applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, an organic solvent is included.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, Examples include tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, and isophorone.

  Furthermore, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene group Cole monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene group Coal phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Examples thereof include methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

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

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

<Method for producing colored composition>
The coloring composition of the present invention contains a coloring agent containing the specific phthalocyanine pigment of the present application in a coloring agent carrier composed of the binder resin and, if necessary, a solvent, preferably together with a dispersion aid such as a pigment derivative. It can be produced by finely dispersing using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. In addition, when the specific phthalocyanine pigment of the present application is highly soluble, specifically, it is highly soluble in the organic solvent to be used, dissolved by stirring and finely dispersed as described above if no foreign matter is confirmed. And need not be manufactured.

  The colored composition of the present invention can also be produced by mixing pigments, the specific phthalocyanine pigment of the present application, and other colorants separately in a colorant carrier such as a binder resin.

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

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

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

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

The following is mentioned as a commercially available resin-type dispersing agent.
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181 manufactured by Big Chemie Japan 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, Or Lactimon, Lactimon-WS or Bykumen etc.
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Nippon Lubrizol 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.
EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by BASF 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.
Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc.

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

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

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

<Photopolymerization initiator>
The coloring composition of the present invention can contain a photopolymerization initiator. It is preferable that the compounding quantity at the time of using a photoinitiator is 5-200 mass parts with respect to 100 mass parts of phthalocyanine pigments represented with General formula (1), and 10-150 from a photocurable viewpoint. More preferably, it is part by mass.

As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specific examples include the following.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo [2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2 -Acetophenones such as methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other phenylglyoxylic methyl esters.

More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01, IRGACURE OXE-02 (BASF), Adekaoptomer N1717, Adekaoptomer N1919, Adeka Arcles NCI- 831 (ADEKA) and Esacure 1001M (Lamberti).
In addition, triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, JP-A-59-1504 and JP-A-61-243807 Organic peroxides, diazonium compound publications described in JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and USP-3567453, USP-2848328, USP-No. No. 2852379 and USP 2940853, azide compounds described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610 Ortho-quinonediazides, Japanese Patent Publication No. 55-39162, Various onium compounds including iodonium compounds described in JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977), JP-A-59-142205 Of the azo compound.

  Furthermore, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science (J. IMAGE. SCI.)”, Volume 30, 174. (1986), titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85 to 277 (1988). ) And a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, an aluminate complex described in JP-A-3-209477, a borate compound described in JP-A-2-157760, JP 55-127550 A and 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, and JP-A-5-255347 Sulfonium complexes or oxosulfonium complexes, aminoketone compounds described in JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261661 JP, 2000-80068, JP 2001-233842, JP 2004-534797, JP 2006-342166, JP 2008-094770, JP 2009-40762, JP 2010-15025, JP Open 2010-189279, JP 2010-1892 No. 80, JP 2010-526846, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP4202697 (1980), and JP-A-61-2558 An ester compound etc. are mentioned.

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

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

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and epoxy (meth). Acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di Various acrylic esters such as enterythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile The effects of the present invention are not limited to these.

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

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

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

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, teto Benzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran Examples thereof include, but are not limited to, derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes.

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

  Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass parts with respect to 100 mass parts of total mass of the photoinitiator contained in a coloring photosensitive composition, and a photocurable viewpoint. It is more preferable that it is 5-50 mass parts. In one embodiment, it is preferable to use a benzophenone derivative from the viewpoint of patterning sensitivity. For example, trade name “EAB-F” manufactured by Hodogaya Chemical Co., Ltd. can be used.

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

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

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

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

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

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

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

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

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And polyoxyalkylene alkyl ethers such as polyethylene glycol monolaurate; amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaines and alkylimidazolines; and fluorine-based and silicone-based surfactants.

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

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

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

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

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

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

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

  As a base material such as a transparent substrate constituting the color filter, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

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

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

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

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

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

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

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

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

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

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

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

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

      Formula (1) MV = Σ (V · d) / Σ (V)

(X-ray diffraction pattern)
The X-ray diffraction pattern by CuKα rays was measured in the range of black angle 2θ = 3 ° to 35 ° with an X-ray sampling interval of 0.02 ° using a desktop X-ray diffractometer manufactured by Rigaku Corporation.

<Manufacture of phthalocyanine pigments>
[Example 1] (Production of aluminum phthalocyanine (P-1))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine represented by the following chemical formula (4). Elemental analysis was performed on the obtained chloroaluminum phthalocyanine. As a result, the calculated value (C) 66.85%, (H) 2.80%, and (N) 19.49% were compared with the actually measured value (C) 66. 7%, (H) 3.0%, (N) 19.2%, and identified as the target compound.

  Next, in a reaction vessel, 100 parts of the chloroaluminum phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and dried to obtain 165 parts of An aluminum halide phthalocyanine represented by the chemical formula (5) was obtained. The number of bromine substitutions calculated for the obtained aluminum halide phthalocyanine was 8.4 on average. From the mass spectrum, a peak corresponding to the same molecular weight was confirmed and identified as the target compound. The halogen distribution width was 8.

  Subsequently, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 31 parts of diphenyl phosphate were added in a reaction vessel. After reacting at 85 ° C. for 3 hours, 3000 parts of water was poured into this solution and stirred for 3 hours. The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 107 parts of aluminum phthalocyanine (P-1). When the bromine substitution number was calculated for the obtained aluminum phthalocyanine (P-1), it was an average of 8.2, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 8. The obtained aluminum phthalocyanine (P-1) had a volume average primary particle size of 32 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 2] (Production of aluminum phthalocyanine (P-2))
108 parts of halogen in the same manner as in Example 1 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 124 parts of N-bromosuccinimide in the production of aluminum phthalocyanine (P-1). Aluminum fluoride phthalocyanine was obtained. Next, 1000 parts of 1-methyl-2-pyrrolidinone and 100 parts of the above-mentioned aluminum halide phthalocyanine were added in a reaction vessel and reacted at 120 ° C. for 3 hours. Subsequently, 650 parts of water was gradually poured into this solution, and after stirring at 80 ° C. for 3 hours, the reaction product was filtered, washed with 6000 parts of water, dried at 60 ° C. under reduced pressure all day and night, and 114 parts. Of aluminum phthalocyanine (P-2) was obtained. When the bromine substitution number was calculated for the obtained aluminum phthalocyanine (P-2), the average was 4.1, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 7. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-2) was 35 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 3] (Production of aluminum phthalocyanine (P-3))
Example 1 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 25 parts of 1,3-dibromo-5,5-dimethylhydantoin in the production of aluminum phthalocyanine (P-1). In the same manner, 77 parts of aluminum halide phthalocyanine was obtained. Subsequently, 500 parts of propylene glycol monomethyl ether acetate, 50 parts of the above-mentioned aluminum halide phthalocyanine and 59 parts of diphenyl phosphate were added in a reaction vessel, and reacted at 20 ° C. for 4 hours. Subsequently, the reaction product was filtered, washed with 500 parts of methanol and 1500 parts of water, and then dried overnight at 60 ° C. under reduced pressure to obtain 61 parts of aluminum phthalocyanine (P-3). When the number of bromine substitutions was calculated for the obtained aluminum phthalocyanine (P-3), the average was 1.0, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 4. The obtained aluminum phthalocyanine (P-3) had a volume average primary particle size of 32 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 4] (Production of aluminum phthalocyanine (P-4))
Example 1 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 274 parts of 1,3-dibromo-5,5-dimethylhydantoin in the production of aluminum phthalocyanine (P-1). In the same manner as above, 163 parts of aluminum halide phthalocyanine was obtained. Next, 1500 parts of N, N-dimethylacetamide, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 28 parts of diphenyl phosphate were added in a reaction vessel. After reacting at 85 ° C. for 3 hours, 150 parts of water was poured into this solution over 1 hour. Thereafter, 300 parts of N, N-dimethylacetamide was again added to the solution, and the mixture was heated and stirred at 85 ° C. for 1 hour, and 1000 parts of water was added over 2 hours. The reaction product was filtered, washed with 9000 parts of water, and then dried under reduced pressure at 60 ° C. overnight to obtain 106 parts of aluminum phthalocyanine (P-4). When the number of bromine substitutions was calculated for the obtained aluminum phthalocyanine (P-4), the average was 9.9, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 8. The obtained aluminum phthalocyanine (P-4) had a volume average primary particle size of 32 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 5] (Production of aluminum phthalocyanine (P-5))
406 parts of aluminum bromide, 94 parts of sodium bromide and 10 parts of ferric bromide were heated and melted, and 100 parts of the above chloroaluminum phthalocyanine was added at 140 ° C. The temperature was raised to 160 ° C., and 178 parts of bromine was added dropwise. The above reaction mixture is poured into 5000 parts of water, treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing and hot water washing, and then dried to obtain a crude halogenated product. 233 parts of aluminum phthalocyanine were obtained. The obtained crude aluminum halide phthalocyanine was dissolved in 1900 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution is poured into 12000 parts of water while stirring, and heated to 70 ° C. to produce 221 parts of aluminum halide phthalocyanine by filtration, warm water washing, 1% sodium hydroxide aqueous solution washing, warm water washing and drying. did. Subsequently, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 25 parts of diphenyl phosphate were added in a reaction vessel. After reacting at 85 ° C. for 1 hour, 8000 parts of water was poured into this solution and stirred for 3 hours. The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 104 parts of aluminum phthalocyanine (P-5). When the number of bromine substitutions was calculated for the obtained aluminum phthalocyanine (P-5), it was an average of 12.0. From the mass spectrum, peaks corresponding to the same molecular weight were confirmed and identified as the target compound. did. The halogen distribution width was 9. The obtained aluminum phthalocyanine (P-5) had a volume average primary particle size of 30 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 6] (Production of aluminum phthalocyanine (P-6))
In the production of aluminum phthalocyanine (P-1), 100 parts of halogenated in the same manner as in Example 1 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 108 parts of trichloroisocyanuric acid. Aluminum phthalocyanine was obtained. Subsequently, 1500 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 46 parts of diphenyl phosphate were added in a reaction vessel. After reacting at 85 ° C. for 3 hours, 4000 parts of water was poured into this solution over 2 hours. The reaction product was filtered, washed with 9000 parts of water, and then dried under reduced pressure at 60 ° C. overnight to obtain 116 parts of aluminum phthalocyanine (P-6). When the number of chlorine substitutions was calculated for the obtained aluminum phthalocyanine (P-6), the average was 7.8, and the peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 7. The obtained aluminum phthalocyanine (P-6) had a volume average primary particle size of 34 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 7] (Production of aluminum phthalocyanine (P-7))
In the production of aluminum phthalocyanine (P-1), 80 parts of halogenated in the same manner as in Example 1 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 40 parts of trichloroisocyanuric acid. Aluminum phthalocyanine was obtained. Next, 500 parts of 1-methyl-2-pyrrolidinone, 50 parts of the above-mentioned aluminum halide phthalocyanine and 57 parts of diphenyl phosphate were added in a reaction vessel, and reacted at 60 ° C. for 5 hours. Subsequently, 300 parts of water was added to this solution and stirred for 3 hours. The reaction product was filtered, washed with 5000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 61 parts of aluminum phthalocyanine (P-7). When the number of chlorine substitutions was calculated for the obtained aluminum phthalocyanine (P-7), the average was 2.8, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 5. The obtained aluminum phthalocyanine (P-7) had a volume average primary particle size of 38 nm. Moreover, when the X-ray-diffraction pattern by a CuK alpha ray was measured, it had a peak in black 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 8] (Production of aluminum phthalocyanine (P-8))
406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of the above chloroaluminum phthalocyanine was added at 140 ° C. The temperature was raised to 160 ° C. and 99 parts of chlorine was blown in. The above reaction mixture is poured into 5000 parts of water, treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing and hot water washing, and then dried to obtain a crude halogenated product. 167 parts of aluminum phthalocyanine were obtained. The obtained crude aluminum halide phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid and added at 50 ° C. over 3 hours. Next, the solution is poured into 7200 parts of water while stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% aqueous sodium hydroxide, washed with warm water, and dried to produce 159 parts of aluminum halide phthalocyanine. did. Subsequently, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 35 parts of diphenyl phosphate were added in a reaction vessel. After reacting at 85 ° C. for 1 hour, 8000 parts of water was poured into this solution and stirred for 3 hours. The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 110 parts of aluminum phthalocyanine (P-8). When the number of chlorine substitutions was calculated for the obtained aluminum phthalocyanine (P-8), the average was 15.0, and peaks corresponding to the same molecular weight were confirmed from the mass spectrum, and the compound was identified as the target compound. did. The halogen distribution width was 4. The obtained aluminum phthalocyanine (P-8) had a volume average primary particle size of 29 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 9] (Production of aluminum phthalocyanine (P-9))
Example 1 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 199 parts of 1,3-diiodo-5,5-dimethylhydantoin in the production of aluminum phthalocyanine (P-1). In the same manner, 162 parts of aluminum halide phthalocyanine were obtained. Next, 1500 parts of methanol, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 28 parts of diphenyl phosphate were added in a reaction vessel. The reaction was carried out at 85 ° C. for 3 hours. The reaction product was filtered, washed with 9000 parts of water, and then dried at 60 ° C. under reduced pressure for 24 hours to obtain 106 parts of aluminum phthalocyanine (P-9). When the number of iodine substitutions was calculated for the obtained aluminum phthalocyanine (P-9), it was an average of 6.0, and the peak corresponding to the same molecular weight was also confirmed from the mass spectrum and identified as the target compound. did. The halogen distribution width was 5. The obtained aluminum phthalocyanine (P-9) had a volume average primary particle size of 38 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 10] (Production of aluminum phthalocyanine (P-10))
In a reaction vessel, 100 parts of the chloroaluminum phthalocyanine was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 27 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the resulting precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying to obtain 128 parts of halogen. Aluminum fluoride phthalocyanine was obtained. Subsequently, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 36 parts of diphenyl phosphate were added in a reaction vessel. After reacting at 85 ° C. for 3 hours, 3000 parts of water was poured into this solution. The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 110 parts of aluminum phthalocyanine (P-10). When the number of substitutions of chlorine and bromine was calculated for the obtained aluminum phthalocyanine (P-10), the average of chlorine was 2.1 and the average of bromine was 7.9. From the mass spectrum, peaks corresponding to the same molecular weight were obtained. Confirmed and identified as the desired compound. The halogen distribution width was 16. The obtained aluminum phthalocyanine (P-10) had a volume average primary particle size of 30 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

[Example 11] (Production of aluminum phthalocyanine (P-11))
Example 10 except that 199 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 199 parts of 1,3-diiodo-5,5-dimethylhydantoin in the production of aluminum phthalocyanine (P-10). 139 parts of aluminum halide phthalocyanine were produced in the same manner as above. Then, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above-mentioned aluminum halide phthalocyanine, and 29 parts of diphenyl phosphate were added in a reaction vessel and reacted at 85 ° C. for 3 hours. Subsequently, 650 parts of water is gradually poured into this solution, and after stirring at 80 ° C. for 3 hours, the reaction product is filtered, washed with 6000 parts of water, dried at 60 ° C. under reduced pressure all day and night, and 108 parts. Of aluminum phthalocyanine was obtained.
When the number of chlorine and iodine substitutions was calculated for the obtained aluminum phthalocyanine (P-11), the chlorine average was 2.0 and the iodine average was 6.0. From the mass spectrum, peaks corresponding to the same molecular weight were obtained. Confirmed and identified as the desired compound. The halogen distribution width was 12. The obtained aluminum phthalocyanine (P-11) had a volume average primary particle size of 39 nm. Moreover, when the X-ray-diffraction pattern by a CuK (alpha) ray was measured, it had a peak in black angle 2 (theta) = 5.7 degrees, 24.3 degrees, and 25.2 degrees.

<Production of comparative aluminum phthalocyanine>
[Comparative Example 1] (Production of aluminum phthalocyanine (P-12))
In the production of aluminum phthalocyanine (P-1), in the reaction of aluminum halide phthalocyanine represented by chemical formula (5) with diphenyl phosphate, the aluminum halide phthalocyanine represented by chemical formula (5) is represented by chemical formula (4). The same procedure as in Example 1 was performed except that 31 parts of diphenyl phosphate was changed to 67 parts of diphenyl phosphate in the chloroaluminum phthalocyanine represented, and aluminum phthalocyanine (P-12) 128 not substituted with halogen was used. Got a part. The obtained aluminum phthalocyanine had a volume average primary particle size of 38 nm. Further, when an X-ray diffraction pattern by CuKα rays was measured, no peaks were observed at black angles 2θ = 5.7 °, 24.3 °, and 25.2 °.

[Comparative Example 2] (Production of aluminum phthalocyanine (P-13))
To the reaction vessel, 100 parts of 4,5-dibromophthalic acid, 132 parts of urea, 2.4 parts of ammonium molybdate, 0.8 part of sodium sulfate and 200 parts of 1-chloronaphthalene were added and stirred. After heating to 150 ° C., 16.6 parts of aluminum chloride and 21.2 parts of urea were added and reacted at 250 ° C. for 7 hours. After cooling to room temperature, the product was filtered, washed with methanol and dried. Next, 1000 parts of 98% sulfuric acid was added to the Erlenmeyer flask. The dried product was added and dissolved therein, followed by stirring at room temperature for 1 hour. Thereafter, sulfuric acid was poured into 6000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried to obtain an aluminum halide phthalocyanine 70 having an average number of substitutions of bromine atoms of 4 and a halogen distribution width of 1. .4 parts were obtained. Next, 50.0 parts of the obtained aluminum phthalocyanine, 500 parts of 1-methyl-2-pyrrolidinone and 32 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 85 ° C. for 3 hours, this solution was poured into 4000 parts of water. The reaction product was filtered, washed with 8000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 54 parts of aluminum phthalocyanine (P-13). When the bromine substitution number of the obtained aluminum phthalocyanine (P-13) was calculated, the average was 8.0, and the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 1. The obtained aluminum phthalocyanine (P-13) had a volume average primary particle size of 52 nm. The obtained aluminum phthalocyanine had a volume average primary particle size of 38 nm. Further, when an X-ray diffraction pattern by CuKα rays was measured, no peaks were observed at black angles 2θ = 5.7 °, 24.3 °, and 25.2 °.

[Comparative Example 3] (Production of aluminum phthalocyanine (P-14))
In accordance with the method described in Example 10 of International Publication No. 2016/125806, 115 parts of the target aluminum phthalocyanine pigment (P-14) was obtained. When the bromine substitution number was calculated for the obtained aluminum phthalocyanine pigment (P-14), the average was 8.3, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was found to be the target compound. Identified. The halogen distribution width was 8. The obtained aluminum phthalocyanine (P-14) had a volume average primary particle size of 32 nm. Further, when the X-ray diffraction pattern by CuKα ray was measured, peaks were observed at black angles 2θ = 9.3 °, 14.5 °, 15.7 °, 18.3 °, 23.5 ° and 24.1 °. Had.

[Comparative Example 4] (Production of aluminum phthalocyanine (P-15))
According to the method described in Example 12 of International Publication No. 2016/125806, 100 parts of the target aluminum phthalocyanine pigment (P-15) was obtained. When the bromine substitution number was calculated for the obtained aluminum phthalocyanine pigment (P-15), it was 10.1 on average, a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was found to be the target compound. Identified. The halogen distribution width was 7. The obtained aluminum phthalocyanine (P-15) had a volume average primary particle size of 31 nm. Further, when the X-ray diffraction pattern by CuKα ray was measured, it had peaks at black angles 2θ = 14.0 °, 23.9 ° and 27.1 °.

  Table 1 shows the yield, the average value of the number of substitution of halogen atoms represented by X, the halogen distribution width, and the volume average primary particle size in the production of the above aluminum phthalocyanines (P-1 to 15).

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

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

<Binder resin production method>
(Preparation of methacrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a methacrylic resin solution having a weight average molecular weight (Mw) of 26000. After the resin solution was cooled to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Next, in consideration of the measured value, methacrylic resin solution 1 was prepared by adding propylene glycol monoethyl ether acetate to the previously obtained resin solution so that the nonvolatile content was 20% by mass.

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

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

<Manufacture of pigment dispersion>
[Example 12] (Pigment dispersion (GP-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. Thereafter, the obtained mixture was filtered through a filter having a pore size of 5.0 μm to prepare a pigment dispersion (GP-1) having a nonvolatile component of 20% by mass.
Aluminum phthalocyanine (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 13 to 22, Comparative Examples 5 to 8] (Pigment dispersions (GP-2) to (GP-15))
Pigment dispersions (GP-2) to (GP-15) were produced in the same manner as in Example 12, except that aluminum phthalocyanine (P-1) was changed to aluminum phthalocyanine shown in Table 2.

<Evaluation of pigment dispersion>
The following evaluation was performed about the pigment dispersions (GP-1)-(GP-15) obtained by the Example and the comparative example. The results are shown in Table 2.

(Evaluation of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

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

(Evaluation of dispersibility)
The dispersibility of the obtained pigment dispersion was evaluated by the initial viscosity of the dispersion. The measurement measured the viscosity (mPa * s) in 25 degreeC using the E-type viscosity meter ("ELD type viscometer" by the Toki Sangyo company).
◎: Less than 10 mPa · s: Very good ○: 10 mPa · s or more, less than 15 mPa · s: Good Δ: 15 mPa · s or more, less than 20 mPa · s: Defect x: When 20 mPa · s or more: Very bad

(Evaluation of storage stability)
The obtained pigment dispersion was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the colored composition after the aging was measured by the same method as the viscosity measurement and stored at 40 ° C. for 1 week. The change rate of the viscosity before and after the calculation was calculated and evaluated in two stages according to the following criteria.
A: When the viscosity change rate is within ± 20% and no precipitate is formed (good)
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is formed even if the viscosity change rate is within ± 20% (defective)

When the phthalocyanine ring was not substituted with halogen as in Comparative Example 5, the contrast ratio, dispersibility, and storage stability were low. Moreover, as in Comparative Example 6, the number of halogen substitutions was 8, but the halogen distribution width of 1 was also low in contrast ratio, dispersibility, and storage stability. Further, even if the halogen substitution number is 8.3, the halogen distribution width is 8, and the halogen substitution number is 10.1 and the halogen distribution width is 7 as in Comparative Example 7, the X In the case of not having a line diffraction pattern, the dispersibility of the pigment dispersion was extremely poor, and as a result, the contrast ratio and storage stability were also lowered.
On the other hand, the pigment dispersion containing aluminum phthalocyanine having an average halogen substitution number of 1 to 15 and a halogen distribution width of 4 or more in Examples 12 to 22 of the present invention has a high contrast ratio, dispersibility, and storage stability. Excellent results. From these results, in order to achieve both the contrast ratio, dispersibility, and storage stability, the pigment has an average number of halogen substitutions of 1 to 15, a halogen distribution width of 4 or more, and a specific X-ray diffraction pattern of the present application. It turns out that what has is effective.

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

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

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

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

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

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

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

(Production of refined yellow pigment (PY185-1))
Isoindoline yellow pigment C.I. I. 200 parts of Pigment Yellow 185 (BASF “Pariotol Yellow L 1155”), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material was put into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain a fine yellow pigment (PY185-1).

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

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

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

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

<Manufacture of other fine pigment dispersions>
(Manufacture of refined pigment dispersion (GP-16) to (VP-1))
Pigment dispersions (GP-16) to (VP-1) were produced in the same manner as in Example 12 except that aluminum phthalocyanine (P-1) was changed to the finer pigment shown in Table 3.

<Production of photosensitive coloring composition>
[Example 23] (Green photosensitive coloring composition (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
Pigment dispersion (GP-1): 25.4 parts PY138 / Pigment dispersion (YP-2): 24.6 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (“Aronix” manufactured by Toagosei Co., Ltd.) M-402 "): 2.0 parts Photopolymerization initiator (" Irgacure 907 "manufactured by BASF): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 24-39, Comparative Examples 9-12]
The green photosensitive coloring compositions (GR-2) to (GR-2) to (GR-2), respectively, in the same manner as in Example 23 except that the total of 50 parts of the pigment dispersion was changed to the components and parts by mass shown in Table 4, respectively. -21) was obtained.

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the obtained photosensitive coloring composition. The results are shown in Table 4.
(Evaluation of brightness)
The photosensitive coloring composition was apply | coated on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness using the spin coater. Next, the coating film was dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes. In this way, a coated substrate was obtained in which the chromaticity of the substrate was x = 0.297 and y = 0.570 in the C light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.
◎: 66.5 or more: Extremely good ○: 65.9 or more and less than 66.5: Good △: 65.3 or more and less than 65.9: Practical use ×: Less than 65.3: Bad

(Evaluation of dispersibility)
The dispersibility of the obtained photosensitive coloring composition was evaluated by the initial viscosity of the coloring composition. The measurement measured the viscosity (mPa * s) in 25 degreeC using the E-type viscosity meter ("ELD type viscometer" by the Toki Sangyo company).
◎: Less than 10 mPa · s: Very good ○: 10 mPa · s or more, less than 15 mPa · s: Good Δ: 15 mPa · s or more, less than 20 mPa · s: Defect x: When 20 mPa · s or more: Very bad

(Evaluation of storage stability)
About the obtained photosensitive coloring composition, after storing for one week in a 40 degreeC thermostat and making it accelerate | stimulate with time, the viscosity of the coloring composition after time-lapse | temporality is measured by the same method as the said viscosity measurement, and it is 1 at 40 degreeC. The rate of change in viscosity before and after storage for a week was calculated and evaluated in two stages according to the following criteria.
A: When the viscosity change rate is within ± 20% and no precipitate is formed (good)
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is formed even if the viscosity change rate is within ± 20% (defective)

When the phthalocyanine ring was not substituted with halogen as in Comparative Example 9, the brightness, dispersibility, and storage stability were low. In addition, as in Comparative Example 10, the number of halogen substitutions was 8, but the halogen distribution width of 1 also had low brightness, dispersibility, and storage stability. Further, even if the halogen substitution number is 8.3, the halogen distribution width is 8, and the halogen substitution number is 10.1 and the halogen distribution width is 7 as in Comparative Example 11, X When there was no line diffraction pattern, the dispersibility of the pigment dispersion was remarkably poor, and as a result, the brightness and storage stability were also lowered.
On the other hand, in the pigment dispersion containing aluminum phthalocyanine of Examples 23 to 39 of the present invention, the brightness, dispersibility, and storage stability were excellent. From this result, in order to achieve both brightness, dispersibility, and storage stability, the average value of the halogen substitution number as the pigment is 1 to 15, the halogen distribution width is 4 or more, and the specific X-ray diffraction pattern of the present application is used. It turns out that what it has is effective. Moreover, even when the aluminum phthalocyanine of the present invention was used in combination with other green pigments and yellow pigments, good results were obtained.

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

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

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

[Example 40]
The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, a heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate. Next, the green photosensitive coloring composition (GR-1) of this invention was used, and the green coloring pixel layer was formed like the red coloring pixel layer. Further, similarly, a blue colored pixel layer was formed using the blue photosensitive coloring composition (BR-1) to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

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

Claims (6)

A phthalocyanine pigment represented by the following general formula (1) and having an X-ray diffraction pattern by CuKα rays having peaks at Bragg angles 2θ (± 0.2) = 5.7 °, 24.3 °, 25.2 ° Colorant for color filter containing

[In General Formula (1), X represents a halogen atom, n represents the average value of the number of halogen atoms substituted, and is 1-15. However, the halogen distribution width of the halogen atom represented by X is 4 or more. Y ₁ represents —OP (═O) (OC ₆ H ₅ ) ₂ . ]   A color composition for a color filter containing a colorant, a binder resin and an organic solvent, wherein the colorant contains the colorant for a color filter according to claim 1.   The coloring composition for a color filter according to claim 2, wherein the colorant further contains at least one of a green pigment and a yellow pigment.   The green pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. Pigment Green 58, which is at least one selected from the group consisting of C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. The coloring composition for a color filter according to claim 2 or 3, which is at least one selected from the group consisting of CI Pigment Yellow 185.   Furthermore, the coloring composition for color filters as described in any one of Claims 2-4 containing at least one of a photopolymerizable monomer and a photoinitiator.   6. A color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment is according to any one of claims 2-5. A color filter formed from a coloring composition for a color filter.