JP2018091916A - Coloring composition for color filters, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for color filter having excellent dispersibility, contrast, and brightness, and a color filter prepared therewith.SOLUTION: The problem is solved by: a coloring composition for color filters containing a colorant [A], a dye derivative [B], a binder resin, and an organic solvent, the dye derivative [B] being a phthalocyanine compound having a specific substituent represented by general formula (1) or (2) and a specific substitution number; and a color filter prepared therewith.SELECTED DRAWING: None

Description

  The present invention includes a color filter coloring composition used for producing a color filter used in a color liquid crystal display device, a color imaging device, an organic EL display device, and the like, and a filter segment formed using the same. The present invention relates to a color filter.

  In the color filter composition, generally, the pigment particles are subjected to a micronization treatment, and by creating a pigment dispersion in which the micronized pigment is close to the primary particles to the limit, light scattering by the pigment is suppressed, High contrast can be achieved. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  However, in the pigment dispersion containing the pigment subjected to the refinement treatment, the specific surface area of the pigment is remarkably increased, and thus there is a problem that the dispersion state of the refined pigment in the pigment dispersion cannot be maintained.

  In order to solve such problems, various dye derivatives have been developed. For example, Patent Document 1 proposes a color filter pigment composition characterized by containing a copper phthalocyanine sulfamoyl compound and a blue organic pigment.

  Patent Document 2 proposes a coloring composition for a color filter characterized by containing a dye derivative containing a phthalocyanine pigment residue and a phthalocyanine pigment.

  However, since the dye derivatives in these patent documents do not contain a halogen atom and do not have a halogen distribution width, dispersibility, contrast, and brightness are insufficient.

JP 2009-79199 A JP 2013-181104 A

  The objective of this invention is providing the coloring composition for color filters excellent in the dispersibility, contrast, and brightness, and a color filter using the same.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention.

  That is, the present invention provides a color composition for a color filter comprising a colorant [A], a pigment derivative [B] containing a compound represented by the following general formula (1) or the following general formula (2), a binder resin and an organic solvent. Related to things.

General formula (1)

[In General Formula (1), X ₁ represents a halogen atom, S ₁ represents a sulfonic acid group, an amine salt, a quaternary ammonium salt or a metal salt thereof, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitutions of the group represented by S ₁ is 1 ~ 2. M ₁ represents Al, Ga, or In. Y ₁ represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

General formula (2)

[In General Formula (2), X ₂ represents a halogen atom, S ₂ represents a sulfonic acid group, an amine salt thereof, a quaternary ammonium salt or a metal salt, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitution of the halogen atom represented by X ₂ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitution of the group represented by S ₂ is 1 to 2. M ₂ represents Si or Sn. Y ₂ and Y ₃ represent —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

  In the present invention, the colorant [A] is a compound represented by the following general formula (3) ', C.I. I. Pigment green 58, C.I. I. Pigment green 7 and C.I. I. The present invention relates to the coloring composition for a color filter, which is at least one selected from the group consisting of CI Pigment Green 36.

General formula (3) '

[In General Formula (3) ′, X ₃ ^′ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X ₃ ^′ is 6 to 15, and the halogen distribution width is 4 or more. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. ]

  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, this invention relates to the color filter which comprises the filter segment formed from the said coloring composition for color filters on a base material.

  According to the present invention, by using the specific phthalocyanine derivative and a colorant in combination, it is possible to provide a color filter coloring composition having good dispersibility, contrast, and brightness. Moreover, the color filter excellent in the brightness and contrast can be obtained by using the coloring composition for color filters of this invention.

  The present invention is a color composition for a color filter containing a colorant [A], a pigment derivative [B], a binder resin and an organic solvent, and the pigment derivative [B] is represented by the following general formula (1) or the following general formula. It contains the compound represented by (2).

[In General Formula (1), X ₁ represents a halogen atom, S ₁ represents a sulfonic acid group, an amine salt, a quaternary ammonium salt or a metal salt thereof, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitutions of the group represented by S ₁ is 1 ~ 2. M ₁ represents Al, Ga, or In. Y ₁ represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

General formula (2)

[In General Formula (2), X ₂ represents a halogen atom, S ₂ represents a sulfonic acid group, an amine salt thereof, a quaternary ammonium salt or a metal salt, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitution of the halogen atom represented by X ₂ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitution of the group represented by S ₂ is 1 to 2. M ₂ represents Si or Sn. Y ₂ and Y ₃ represent —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

  Hereinafter, each component which comprises the coloring composition for color filters of this invention is explained in full 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. “CI” represents a color index (CI).

<Colorant [A]>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. Hereinafter, typical pigments that can be used in the present invention are listed, but the present invention is not limited thereto. Two or more colorants may be used in combination.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,269,270,272,273,274,276,277,278,279,280,2 1, 282, 283, 284, 285, 286, 287, diketopyrrolopyrrole pigment described in JP-T-2011-523433, azo described in JP-A-2011-173971, or JP-A-2012-229344 Compounds and the like. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. In addition to xanthene acid dyes such as Acid Red 52, 87, 92, 289, and 338, these salt-forming compounds are exemplified.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment orange 38, 43, 71, or 73.

  Examples of yellow pigments that can be used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220,221 include quinophthalone pigments described in Japanese Patent No. 4993026. Also, yellow dyes such as quinoline, azo, disazo, and methine can be used.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859. Blue dyes such as triarylmethane dyes and xanthene dyes can also be used.

  Examples of the green pigment that can be used in the present invention include C.I. I. In addition to CI Pigment Green 7, 10, 36, 37, 58, zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, and the like, the general formula (3) Or the phthalocyanine pigment etc. which are represented by General formula (4) are mentioned.

[In General Formula (3), X ₃ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substituted halogen atoms represented by X ₃ is a 6 to 15, halogen distribution width is 4 or more. M ₃ represents Al, Ga, or In. Y ₄ represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

General formula (4)

[In General Formula (4), X ₄ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of halogen atoms represented by X ₄ is 6 to 15, and the halogen distribution width is 4 or more. M ₄ represents Si or Sn. Y ₅ and Y ₆ represent —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

Below, the substituent in general formula (3) and (4) is demonstrated.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine, with bromine and chlorine being preferred. Two or more halogen atoms may be used in combination.

When the average value of the number of substitutions of halogen atoms represented by X ₃ in the general formula (3) or X ₄ in the general formula (4) is 6 to 15, it is easy to obtain various desired characteristics. . The average value of the number of substituents of the halogen atom is preferably 7 to 15 from the viewpoint of fastness, and more preferably 8 to 15 from the viewpoint of hue and fastness. The halogen distribution width is 4 or more, preferably 4 to 9, and more preferably 5 to 8. When the halogen distribution width is 4 or more, association and aggregation of phthalocyanine molecules tend to be remarkably suppressed. Therefore, when the halogen distribution width is within the above range, it greatly contributes to the suppression of the increase in particle size and the decrease in contrast caused by the association and aggregation between molecules, and it becomes easy to obtain various desired characteristics.

  Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigments represented by the general formulas (3) and (4). 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 types of 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.

Examples of the alkyl group in R _{1 to} R ₄ in the general formulas (3) and (4) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, and n-to. Examples include linear or branched alkyl groups such as a xyl group, n-octyl group, stearyl group, and 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and 2-butoxy. Ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl Groups and the like.

Examples of the aryl group in R _{1 to} R ₄ in the general formulas (3) and (4) include monocyclic aromatic hydrocarbon groups such as phenyl group and p-tolyl group, and condensed aromatic carbon groups such as naphthyl group and anthryl group. Examples thereof include a hydrogen group, and a monocyclic aromatic hydrocarbon group is preferable. Moreover, a C6-C12 aryl group is preferable. Examples of the substituent of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryl group having a substituent, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, Examples include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Examples of the alkoxy group in R ₁ and R ₂ in the general formulas (3) and (4) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, and neopentyloxy. Straight chain or branched alkoxy groups such as a group, 2,3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc. 1-6 alkoxy groups are preferred. Examples of the substituent of the alkoxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxy groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkoxy group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples include ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

As the aryloxy group in R ₁ and R ₂ of the general formulas (3) and (4), an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group, a naphthaloxy group, an an An aryloxy group consisting of a condensed aromatic hydrocarbon group such as a thryloxy group can be mentioned, and an aryloxy group consisting of a monocyclic aromatic hydrocarbon group is preferred. Moreover, a C6-C12 aryloxy group is preferable. Examples of the substituent of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxy groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryloxy group having a substituent, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. Can be mentioned.

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

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

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

Y _{4 to} Y ₆ in the general formulas (3) and (4) are each independently preferably —OP (═O) R ₁ R ₂ .

  The colorant [A] is preferably an organic pigment, and is preferably a blue pigment or a green pigment, more preferably a green pigment, in view of the color characteristics of the dye derivative [B]. As the green pigment, a halogenated phthalocyanine compound is preferable, a compound represented by the general formula (3), a compound represented by the general formula (4), C.I. I. Pigment green 58, C.I. I. Pigment green 7, and C.I. I. More preferably, it is at least one selected from the group consisting of CI Pigment Green 36, and a compound represented by the general formula (3) ', C.I. I. Pigment green 58, C.I. I. Pigment green 7, and C.I. I. Particularly preferred is at least one selected from the group consisting of CI Pigment Green 36.

General formula (3) '

[In general formula (3) ′,
X ₃ ′ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of substitutions of halogen atoms represented by X ₃ ′ is 6 to 15, and the halogen distribution width is 4 or more.
R ₁ and R ₂ each independently represents an aryl group which may have a substituent or an aryloxy group which may have a substituent. ]

  The substituent in General formula (3) 'is synonymous with the substituent in General formula (3).

<Miniaturization of pigment>
When the colorant of the present invention is an organic pigment, it is preferable to use the pigment after making it fine. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult, and when the thickness is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using 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, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, 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, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. 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 organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Dye derivative>
[Dye derivative [B]]
Next, the pigment derivative [B] will be described. The pigment derivative [B] includes a phthalocyanine compound represented by the following general formula (1) or (2). Since the pigment derivative [B], which is a constituent requirement of the present invention, is extremely excellent in dispersibility, the scattering of the colorant particles can be reduced, and the viscosity of the colored composition can be kept stable. The dye derivative [B] can control the color tone of the dye derivative by the substituents represented by Y ₁ and Y ₂ in the general formulas (1) and (2). Therefore, when these pigment derivatives [B] are used for the colored composition, a colored composition having higher contrast and excellent viscosity stability and brightness can be obtained.

[In General Formula (1), X ₁ represents a halogen atom, S ₁ represents a sulfonic acid group, an amine salt, a quaternary ammonium salt or a metal salt thereof, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitutions of the group represented by S ₁ is 1 ~ 2. M ₁ represents Al, Ga, or In. Y ₁ represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

General formula (2)

[In General Formula (2), X ₂ represents a halogen atom, S ₂ represents a sulfonic acid group, an amine salt thereof, a quaternary ammonium salt or a metal salt, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitution of the halogen atom represented by X ₂ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitution of the group represented by S ₂ is 1 to 2. M ₂ represents Si or Sn. Y ₂ and Y ₃ represent —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. Represents an aryloxy group which may have a group; R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

Below, the substituent in general formula (1) and (2) is demonstrated.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine, with bromine and chlorine being preferred. Two or more halogen atoms may be used in combination.

When the average value of the number of substitutions of halogen atoms represented by X ₁ in the general formula (1) or X ₂ in the general formula (2) is 6 to 15, it is easy to obtain various desired characteristics. . The average value of the number of substituents of the halogen atom is preferably 7 to 15 from the viewpoint of fastness, and more preferably 8 to 15 from the viewpoint of hue and fastness. The halogen distribution width is 4 or more, preferably 4 to 9, and more preferably 5 to 8. When the halogen distribution width is 4 or more, association and aggregation of phthalocyanine molecules tend to be remarkably suppressed. Therefore, when the halogen distribution width is within the above range, it greatly contributes to the suppression of the increase in particle size and the decrease in contrast caused by the association and aggregation between molecules, and it becomes easy to obtain various desired characteristics.

  Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigments represented by the general formulas (1) and (2). In the mass spectrum obtained by mass spectrometry, the halogen distribution width was obtained by integrating the signal intensity (each peak value) of the molecular ion peak corresponding to the molecular weight of 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 types of 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.

The number of substituents of the sulfonic acid group, its amine salt, its quaternary ammonium salt or metal salt represented by S ₁ in the general formula (1) or S ₂ in the general formula (2), that is, m is 1 or 2. In some cases, it is easy to obtain a colored composition excellent in all of dispersibility, contrast, and brightness. Of these, a sulfonic acid group, its amine salt or metal salt is preferred.

Examples of the alkyl group in R _{1 to} R ₄ in the general formulas (1) and (2) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, and n-to. Examples include linear or branched alkyl groups such as a xyl group, n-octyl group, stearyl group, and 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and 2-butoxy. Examples include an ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

Examples of the aryl group in R _{1 to} R ₄ in the general formulas (1) and (2) include monocyclic aromatic hydrocarbon groups such as a phenyl group and a p-tolyl group, and condensed aromatic carbon groups such as a naphthyl group and an anthryl group. Examples thereof include a hydrogen group, and a monocyclic aromatic hydrocarbon group is preferable. Moreover, a C6-C12 aryl group is preferable. Examples of the substituent of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryl group having a substituent, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, Examples include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

As the alkoxy group in R ₁ and R ₂ of the general formulas (1) and (2), methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy Straight chain or branched alkoxy groups such as a group, 2,3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, etc. 1-6 alkoxy groups are preferred. Examples of the substituent of the alkoxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxy groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkoxy group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples include ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

As the aryloxy group in R ₁ and R ₂ of the general formulas (1) and (2), an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group, a naphthaloxy group, an An aryloxy group consisting of a condensed aromatic hydrocarbon group such as a thryloxy group can be mentioned, and an aryloxy group consisting of a monocyclic aromatic hydrocarbon group is preferred. Moreover, a C6-C12 aryloxy group is preferable. Examples of the substituent of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxy groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryloxy group having a substituent, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. Can be mentioned.

Examples of the cycloalkyl group represented by R ₃ in the general formulas (1) and (2) include monocyclic aliphatic hydrocarbons such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, and a 4-tert-butylcyclohexyl group. And condensed aliphatic hydrocarbon groups such as a bornyl group and an adamantyl group. Moreover, a C5-C12 cycloalkyl group is preferable. Examples of the substituent of the cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxy groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group in R ₃ and R ₄ in the general formulas (1) and (2) include aliphatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, and aromatic heterocyclic groups. A cyclic group is mentioned. Moreover, a C4-C12 heterocyclic group is preferable and a C5-C13 heterocyclic group is preferable. Examples of the substituent of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxy groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

In one embodiment, in the dye derivative [B] represented by the general formula (1) and the general formula (2), S ₁ and S ₂ are each independently a sulfonic acid group, an amine salt or a metal salt thereof. Preferably, Y _{1 to} Y ₃ are each independently —OP (═O) R ₁ R ₂ or —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are Each independently is preferably an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, and R ₄ represents a substituent. It is preferably an aryl group which may have. Furthermore, from the viewpoints of dispersibility and color characteristics, at least one of R ₁ and R ₂ may be an aryl group that may have a substituent or an aryloxy group that may have a substituent. preferable. More preferably, R ₁ and R ₂ are both aryl groups or aryloxy groups. Particularly preferably, R ₁ and R ₂ are both phenyl groups or phenoxy groups.

The _Y 1 to Y ₃ in the general formula (1) and (2), each independently, -OP (= _O) R 1 _{R 2,} is preferably.

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

  The mass ratio of the colorant [A] and the pigment derivative [B] is preferably in the range of [A]: [B] = 60: 40 to 99: 1, and [A]: [B] = 70. Is more preferably in the range of 30 to 97: 3. That is, when the ratio of the pigment derivative [B] is too small with respect to the colorant [A], the ratio tends to be low contrast and high viscosity, and the ratio of the pigment derivative [B] to the colorant [A]. When the amount is too large, not only low contrast and high viscosity but also heat resistance tends to deteriorate.

[Other pigment derivatives]
The colored composition of the present invention may contain a dye derivative other than the dye derivative [B]. Examples of the dye derivative other than the dye derivative [B] include compounds in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine. For example, JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717. JP, 128-128669, JP 2004-091497, JP 2007-156395, JP 2008-094773, JP 2008-094986, JP 2008-095007. , Japanese Patent Application Laid-Open No. 2008-195916, Japanese Patent No. 4585781 and the like. Those are available, or in combination of two or more kinds.

<Binder resin>
The binder resin used in the coloring composition of the present invention is one that disperses, dyes, or penetrates a colorant, and includes a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 7,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

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

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

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

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

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

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

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

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

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

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin. Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto 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, it is preferable to contain an organic solvent. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 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, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  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.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed. The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, 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, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like. These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<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 (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

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

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the colored composition from being oxidized and yellowing due to a thermal process during thermal curing or ITO annealing. be able to. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants. These antioxidants can be used singly or in combination of two or more at any ratio as required. When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

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

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

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

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

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. 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- Til-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 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with 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. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-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 weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant [A] in a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, It can be produced by finely dispersing using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, the pigment derivative [B] may be simultaneously dispersed in the colorant carrier, or may be mixed separately in the colorant carrier. When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good. The dye derivative is as described above.

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

  Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferred Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000 manufactured by Lubrizol Japan, 000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 manufactured by BASF 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4 60, 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. .

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

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

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

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

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

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

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

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

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

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

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

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

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

(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.

(Mean value of number of substituents _{S 1} or _{S 2)}
The average value of the number of substitutions of S ₁ or S _{2 is} the same as the average value of the number of substitutions of halogen atoms. The liquid obtained by burning the pigment by the oxygen combustion flask method and absorbing the combustion product in water is ion The amount of sulfur was determined as a sulfate ion amount by analyzing with a graph (ICS-2000 ion chromatography, manufactured by DIONEX), and converted to an average value of the number of substitutions of S ₁ or S ₂ .

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

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

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

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

<Phthalocyanine pigment and pigment production method>
Hereinafter, a method for producing a phthalocyanine pigment will be described. In the structural formula, the number of substituents bonded to the phthalocyanine ring is an average value of the number of substitutions.

[Production Example 1] (Production of phthalocyanine pigment (a-0))
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 a phthalocyanine pigment (a-0). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (a-0)

[Production Example 2] (Production of phthalocyanine pigment (a-1))
50 parts of phthalocyanine pigment (a-0) was dissolved in 500 parts of 98% sulfuric acid and stirred at 80 ° C. for 6 hours. After allowing to cool to room temperature, the reaction solution was poured into 5000 parts of stirred ice water, the precipitate was filtered off, washed with water, and dried to obtain 52 parts of a phthalocyanine pigment (a-1). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (a-1)

[Production Example 3] (Production of phthalocyanine pigment (a-2))
50 parts of phthalocyanine pigment (a-0) was dissolved in 500 parts of 98% sulfuric acid and stirred at 120 ° C. for 6 hours. After allowing to cool to room temperature, this reaction solution was poured into 5000 parts of stirred ice water, the precipitate was filtered off, washed with water, and dried to obtain 55 parts of a phthalocyanine pigment (a-2). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (a-2)

[Production Example 4] (Production of phthalocyanine pigment (a-3))
In a reaction vessel, 30 parts of the phthalocyanine pigment (a-1) was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 44.4 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the formed precipitate was filtered, followed by post-treatment in the order of 1% sodium hydroxide aqueous solution washing, water washing, drying, and 51 parts of A phthalocyanine pigment (a-3) was obtained. About the obtained phthalocyanine pigment (a-3), the average number of bromine substituents is 6.0, and the average number of sulfonic acid substituents is 1.0, which corresponds to the same molecular weight from mass spectrometry by TOF-MS. To identify the target compound.

Phthalocyanine pigment (a-3)

[Production Examples 5 to 10] (Production of phthalocyanine pigments (a-4) to (a-9)))
The same operations as in Production Example 4 were performed except that the halogenating agent and the addition amount used in Production Example 4 were changed to the conditions described in Table 1, respectively, and the following phthalocyanine pigments (a-4) to (a-9) )

[Production Example 11] (Production of phthalocyanine pigment (a-10)))
In a reaction vessel, 30 parts of the phthalocyanine pigment (a-2) was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 65.8 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the formed precipitate was filtered, followed by post-treatment in the order of 1% sodium hydroxide aqueous solution washing, water washing, drying, and 55 parts of A phthalocyanine pigment (a-10) was obtained. The obtained phthalocyanine pigment (a-10) had an average number of bromine substituents of 10.1 and an average number of sulfonic acid substituents of 2.0. A peak corresponding to the same molecular weight was also confirmed from mass spectrometry by TOF-MS, and the target compound was identified.

Phthalocyanine pigment (a-10)

[Production Example 12] (Production of phthalocyanine pigment (b-0))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 85 parts of gallium trichloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 203 parts of a phthalocyanine pigment (b-0). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (b-0)

[Production Example 13] (Production of phthalocyanine pigment (b-1))
50 parts of phthalocyanine pigment (b-0) was dissolved in 500 parts of 98% sulfuric acid and stirred at 100 ° C. for 6 hours. After allowing to cool to room temperature, this reaction solution was poured into 5000 parts of stirred ice water, the precipitate was filtered off, washed with water, and dried to obtain 52 parts of a phthalocyanine pigment (b-1). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (b-1)

[Production Example 14] (Production of phthalocyanine pigment (b-2))
In a reaction vessel, 30 parts of the phthalocyanine pigment (b-1) was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 69.5 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the formed precipitate was filtered, followed by post-treatment in the order of 1% sodium hydroxide aqueous solution washing, water washing, drying, and 51 parts of A phthalocyanine pigment (b-2) was obtained. With respect to the obtained phthalocyanine pigment (b-2), the average bromine substitution number was 9.9, the average sulfonic acid substitution number was 1.0, and the halogen distribution width was 6. A peak corresponding to the same molecular weight was also confirmed from mass spectrometry by TOF-MS, and the target compound was identified.

Phthalocyanine pigment (b-2)

[Production Example 15] (Production of phthalocyanine pigment (c-0))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 107 parts of indium trichloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 7 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 218 parts of a phthalocyanine pigment (c-0).

Phthalocyanine pigment (c-0)

[Production Example 16] (Production of phthalocyanine pigment (c-1))
50 parts of phthalocyanine pigment (c-0) was dissolved in 500 parts of 98% sulfuric acid and stirred at 100 ° C. for 6 hours. After allowing to cool to room temperature, the reaction solution was poured into 5000 parts of stirred ice water, the precipitate was filtered off, washed with water, and dried to obtain 52 parts of a phthalocyanine pigment (c-1). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (c-1)

[Production Example 17] (Production of phthalocyanine pigment (c-2))
In a reaction vessel, 30 parts of the phthalocyanine pigment (c-1) was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 65.1 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the formed precipitate was filtered, followed by post-treatment in the order of 1% sodium hydroxide aqueous solution washing, water washing, drying, and 51 parts of A phthalocyanine pigment (c-2) was obtained. When the bromine substitution number was calculated for the obtained phthalocyanine pigment (c-2), the average was 9.9, the halogen distribution width was 6, and the peaks corresponding to the same molecular weight were confirmed from the mass analysis by TOF-MS. And identified as the target compound.

Phthalocyanine pigment (c-2)

[Production Example 18] (Production of phthalocyanine pigment (d-0))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 107 parts of silicon tetrachloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 8 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 188 parts of a phthalocyanine pigment (d-0). The compound was identified by mass spectrometry using TOF-MS.

[Production Example 19] (Production of phthalocyanine pigment (d-1))
50 parts of phthalocyanine pigment (d-0) was dissolved in 500 parts of 98% sulfuric acid and stirred at 100 ° C. for 6 hours. After allowing to cool to room temperature, this reaction solution was poured into 5000 parts of stirred ice water, the precipitate was filtered off, washed with water, and dried to obtain 55 parts of a phthalocyanine pigment (d-1). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (d-1)

[Production Example 20] (Production of phthalocyanine pigment (d-2))
In a reaction vessel, 30 parts of the phthalocyanine pigment (d-1) was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 72.1 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the formed precipitate was filtered, followed by post-treatment in the order of 1% sodium hydroxide aqueous solution washing, water washing, drying, and 53 parts of A phthalocyanine pigment (d-2) was obtained. The number of bromine substitutions calculated for the obtained phthalocyanine pigment (d-2) was 9.9 on average, the halogen distribution width was 6, and peaks corresponding to the same molecular weight were confirmed from mass analysis by TOF-MS. And identified as the target compound.

Phthalocyanine pigment (d-2)

[Production Example 21] (Production of phthalocyanine pigment (e-0))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 126 parts of tin tetrachloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 10 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 215 parts of a phthalocyanine pigment. The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (e-0)

[Production Example 22] (Production of phthalocyanine pigment (e-1))
50 parts of phthalocyanine pigment (e-0) was dissolved in 500 parts of 98% sulfuric acid and stirred at 100 ° C. for 6 hours. After allowing to cool to room temperature, the reaction solution was poured into 5000 parts of stirred ice water, the precipitate was filtered off, washed with water, and dried to obtain 53 parts of a phthalocyanine pigment (e-1). The compound was identified by mass spectrometry using TOF-MS.

Phthalocyanine pigment (e-1)

[Production Example 23] (Production of phthalocyanine pigment (e-2))
In a reaction vessel, 30 parts of the phthalocyanine pigment (e-1) was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 63 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the produced precipitate was filtered, followed by post-treatment in the order of washing with 1% aqueous sodium hydroxide and washing with water, and drying to obtain 55 parts of phthalocyanine. A pigment (e-2) was obtained. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (e-2), the average was 9.9, the halogen distribution width was 6, and peaks corresponding to the same molecular weight were confirmed from mass analysis by TOF-MS. And identified as the target compound.

Phthalocyanine pigment (e-2)

Below, it shows about the obtained phthalocyanine pigment.

[Production Example 24] (Production of phthalocyanine pigment (PC-1))
In a reaction vessel, 100 parts of N-methylpyrrolidone, 10 parts of phthalocyanine pigment (a-3) and 3.9 parts of diphenyl phosphate were added and heated to 90 ° C. for reaction for 3 hours. After cooling this to room temperature, it was poured into 1000 parts of water to precipitate the product. The product was filtered, washed with 10,000 parts of water, and then dried to obtain 11.2 parts of a phthalocyanine pigment (PC-1). A peak corresponding to the same molecular weight was also confirmed from mass spectrometry by TOF-MS, and the target compound was identified. The obtained phthalocyanine pigment (PC-1) has a volume average primary particle diameter of 50 nm, an average halogen atom substitution number of 6.1, and an average sulfonic acid group substitution number of 1.0. The halogen distribution width was 5.

Phthalocyanine pigment (PC-1)

[Production Examples 25 to 40] (Production of phthalocyanine pigments (PC-2) to (PC-17))
The same operations as in Production Example 24 were performed except that the raw material phthalocyanine pigment and acidic compound were changed to the conditions described in Table 2, and phthalocyanine pigments (PC-2) to (PC-17) were obtained, respectively. Moreover, the peak corresponding to the molecular weight of each phthalocyanine pigment was confirmed by TOF-MS to identify the target compound.

[Production Example 41] (Production of phthalocyanine pigment (PC-18))
500 parts (water content: 85.0%) of a phthalocyanine pigment (PC-3) water paste was added to 3750 parts of water, stirred and redispersed, and then adjusted to pH 8.0 to 9.0 using 26% aqueous ammonia. It was adjusted. Next, after adding 40 parts of 5% aluminum chloride aqueous solution and stirring for 1 hour, the precipitate was filtered and washed with water to obtain a water-containing cake of aluminum salt of phthalocyanine pigment (PC-3). The obtained water-containing cake was dried at 80 ° C. to obtain 81 parts of the desired phthalocyanine pigment (PC-18). The volume average primary particle diameter of the obtained phthalocyanine pigment (PC-18) is 49 nm, the average value of the halogen atom substitution number is 10.1, and the average value of the sulfonic acid group substitution number is 1.0. The halogen distribution width was 6.

[Production Example 42] (Production of phthalocyanine pigment (PC-19))
500 parts (water content: 85.0%) of an aqueous paste of phthalocyanine pigment (PC-3) was added to 3750 parts of water, stirred and redispersed, and then pH 8.0 to 9.9 using a 25% aqueous sodium hydroxide solution. Adjusted to zero. Next, 14.8 parts of octadecylamine acetate was added and stirred at 80 to 90 ° C. for 1 hour, followed by filtration. The filtrate was washed with water until it did not contain salt to obtain a water-containing cake of octadecylamine salt of phthalocyanine pigment (PC-3). The obtained water-containing cake was dried at 80 ° C. to obtain 83 parts of the desired phthalocyanine pigment (PC-19). The volume average primary particle diameter of the obtained phthalocyanine pigment (PC-19) is 49 nm, the average value of the halogen atom substitution number is 10.1, and the average value of the sulfonic acid group substitution number is 1.0. The halogen distribution width was 6.

  Hereinafter, structural formulas of the phthalocyanine pigments obtained in Production Examples 25 to 40 are shown. In the structural formula, the number of substituents bonded to the phthalocyanine ring is an average value of the number of substitutions.

[Comparative Production Example 1] (Production of phthalocyanine pigment (B-1))
50 parts of phthalocyanine pigment (a-0) was dissolved in 500 parts of 102% sulfuric acid and stirred at 120 ° C. for 8 hours. After allowing to cool to room temperature, 41.2 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, and the mixture was stirred at 25 ° C. for 6 hours. Next, this reaction solution was poured into 5000 parts of cold water at 3 ° C., and the formed precipitate was filtered, followed by post-treatment in the order of washing with 1% aqueous sodium hydroxide and washing with water, drying, and 101 parts of crude product. A phthalocyanine pigment was obtained. Next, 100 parts of N-methylpyrrolidone, 10 parts of the crude phthalocyanine pigment and 2.4 parts of diphenyl phosphate were added to the reaction vessel, and the mixture was heated to 90 ° C. and reacted for 3 hours. After cooling this to room temperature, it was poured into 1000 parts of water to precipitate the product. The product was filtered, washed with 10,000 parts of water, and then dried to obtain 11.2 parts of a phthalocyanine pigment (B-1). A peak corresponding to the same molecular weight was also confirmed from mass spectrometry by TOF-MS, and the target compound was identified. The average value of the number of halogen substituents of the obtained phthalocyanine pigment (B-1) was 8.0, the average value of the number of sulfonic acid substituents was 3.0, and the halogen distribution width was 6.

Phthalocyanine pigment (B-1)

[Comparative Production Example 2] (Production of phthalocyanine pigment (B-2))
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 100 ° C. 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. The average value of the number of substitution of bromine atoms was 8.0, the halogen distribution width was 1, and the sulfonic acid group As a result, 75.4 parts of a phthalocyanine pigment having an average number of substitutions of 1.1 was 1.1. Subsequently, the obtained phthalocyanine pigment, 1000 parts of N-methylpyrrolidone, and 15 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 85 ° C. for 3 hours, this solution was poured into 8000 parts of water. The reaction product was filtered, washed with 16000 parts of water, and then dried overnight at 60 ° C. under reduced pressure to obtain 90 parts of a phthalocyanine pigment (B-2). A peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the target compound was identified. The average value of the number of bromine atoms substituted in the obtained phthalocyanine pigment (B-2) is 8.0, the average value of the number of substituted sulfonic acid groups is 1.1, and the halogen distribution width is 1. there were.

Phthalocyanine pigment (B-2)

A list of the obtained phthalocyanine pigments is shown below.

<Method for Producing Colorant [A]>
(Production of colorant (A-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGENGREENA110” 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. for a whole day and night to obtain a colorant (A-1).

(Production of colorant (A-2))
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. for a whole day and night to obtain a colorant (A-2).

(Production of colorant (A-3))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Green 8G” manufactured by CLARIANT), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded material was put into 8000 parts of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for a whole day and night to obtain a colorant (A-3).

(Production of colorant (A-4))
In a reaction vessel, 30 parts of the phthalocyanine pigment (a-0) described in “Preparation Example 1” was added to 750 parts of 98% sulfuric acid in an ice bath. Thereafter, 82.3 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this reaction solution was poured into 3000 parts of cold water at 3 ° C., and the produced precipitate was filtered, followed by post-treatment in the order of 1% sodium hydroxide aqueous solution washing and water washing, and dried to 55.5 parts. A crude brominated phthalocyanine pigment was obtained. Subsequently, 100 parts of N-methylpyrrolidone, 10 parts of the crude brominated phthalocyanine pigment and 2.8 parts of diphenyl phosphate were added to the reaction vessel, and the mixture was heated to 90 ° C. and reacted for 3 hours. After cooling this to room temperature, it was poured into 1000 parts of water to precipitate the product. The product was filtered, washed with 10,000 parts of water, and then dried to obtain 12.0 parts of a colorant (A-4). The average value of the halogen substitution number of the obtained colorant (A-4) was 10.0 on average, the halogen distribution width was 7, and a peak corresponding to the same molecular weight was confirmed also from mass spectrometry by TOF-MS, The target compound was identified.

Colorant (A-4)

<Manufacture of coloring composition>
About the pigment created above, the pigment dispersion which is one aspect | mode of a coloring composition was manufactured.

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

[Example 1]
(Coloring composition (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. Then, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a colored composition (GP-1) having a nonvolatile component of 20% by mass.
Colorant (A-1): 10.4 parts Dye derivative (PC-3): 0.6 parts Acrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts Resin type dispersant Solution 1: 5.0 parts

[Examples 2 to 25, Comparative Examples 1 to 8]
(Coloring compositions (GP-2) to (GP-33))
Coloring compositions (GP-2) to (GP-33) were prepared in the same manner as in Example 1 except that the coloring agent (A-1) and the pigment derivative (PC-3) were changed to the conditions shown in Table 3. Produced.

<Evaluation of coloring composition>
The following evaluation was performed about the colored composition (GP-2)-(GP-33) obtained by the Example and the comparative example. The results are shown in Table 3.

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

The coloring composition (GP-1 to 33) was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm, respectively, using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 230 ° C. for 60 minutes A coated substrate was prepared by heating and cooling for a minute. 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 and less than 9000: Good Δ: 3000 or more and less than 6000: Practical

(Evaluation of initial viscosity)
The initial viscosity of the coloring composition was measured at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).

(Evaluation of storage stability)
The obtained colored composition was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the colored composition after 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.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.

  As shown in Table 3, when the pigment derivative B-1 was used as in Comparative Examples 1, 3, 5, and 7, the contrast, initial viscosity, and storage stability were all low. This is because the dye derivative B-1 has three sulfonic acid groups, and the dye derivatives B-1 are strongly associated with each other via the sulfonic acid group, thereby inhibiting the adsorption to the colorant [A]. It is guessed. Similarly, in the case of using the pigment derivative B-2 as in Comparative Examples 2, 4, 6, and 8, the brightness, contrast, initial viscosity, and storage stability were all poorly evaluated. This is presumably because the pigment derivative B-2 has a halogen distribution width of 1, and thus the pigment derivatives B-2 are strongly aggregated and the adsorption to the colorant [A] is inhibited. On the other hand, when the pigment derivatives PC-1 to PC-19 described in the claims were used as in Examples 1 to 25, the evaluation results of contrast, initial viscosity, and storage stability were superior to the comparative examples. . This is because the dye derivatives PC-1 to PC-19 described in Claims have a halogen distribution width of 4 or more and the number of sulfonic acid groups is 2 or less, so that association / aggregation between the dye derivatives is weak, This is presumably because the adsorption to the colorant [A] was remarkably improved.

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

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

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

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

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

<Manufacture of fine pigment dispersion>
A pigment dispersion was produced for the fine pigment.

(Production of PY138 / Pigment Dispersion (YP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0 micrometer filter and produced the pigment dispersion (YP-1) whose non-volatile component is 20 mass%.
Refined yellow pigment (PY138-1): 11.0 parts Acrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts Resin-type dispersant solution 1: 5.0 parts

(PR254 / Pigment dispersion (RP-1))
A PR254 / pigment dispersion (RP-1) was produced in the same manner as in the production of YP-1, except that the refined yellow pigment (PY138-1) was changed to PR254-1.

(PR177 / Pigment dispersion (RP-2))
A PR177 / pigment dispersion (RP-2) was produced in the same manner as in the production of YP-1, except that the refined yellow pigment (PY138-1) was changed to PR177-1.

(PB15: 6, pigment dispersion (BP-1))
PB15: 6 • Pigment dispersion (BP-1) was produced in the same manner as in the production of YP-1, except that the fine yellow pigment (PY138-1) was changed to PB15: 6-1.

(PV23 / Pigment Dispersion (VP-1))
A PV23 / pigment dispersion (VP-1) was produced in the same manner as in the production of YP-1, except that the refined yellow pigment (PY138-1) was changed to PV23-1.

<Production of photosensitive coloring composition>
[Example 26]
(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): 35.0 parts Pigment dispersion (YP-1): 15.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts Dipentaerythritol hexaacrylate Photopolymerization initiator (" IRGACURE 907 "manufactured by BASF): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.): 0 .3 parts cyclohexanone: 39.0 parts

[Examples 27 to 50, Comparative Examples 9 to 16]
(Green photosensitive coloring composition (GR-2) to (GR-33))
A green photosensitive coloring composition (GR-2) was prepared in the same manner as in Example 26, except that the total of 50 parts of the coloring composition and the pigment dispersion was changed to the types and parts by mass shown in Table 4, respectively. To 33).

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the obtained photosensitive coloring composition (GR-1)-(GR-33). The results are shown in Table 4.

(Evaluation of brightness)
The green photosensitive coloring composition (GR-1 to 33) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven. Subsequently, after cooling this board | substrate to room temperature, it exposed to the ultraviolet light through the photomask using the ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, heat treatment is performed at 230 ° C. for 30 minutes in a clean oven to form a glass substrate having a stripe-shaped green pixel layer on the substrate such that x = 0.297 and y = 0.570 with a C light source. did. The brightness (Y) of the obtained glass substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.
A: 66.5 or more: Extremely good ○: 65.9 or more and less than 66.5: Good Δ: 65.3 or more and less than 65.9: Practical use ×: Less than 65.3: Poor

(Evaluation of contrast ratio (CR) of coating film)
Contrast measurement was performed using the substrate used in the brightness evaluation.
A: 9000 or more: extremely good B: 6000 or more and less than 9000: good Δ: 3000 or more and less than 6000: practical use ×: less than 3000: poor

(Evaluation of initial viscosity)
The viscosity of the photosensitive coloring composition was determined by measuring the initial viscosity at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.).

(Evaluation of storage stability)
The obtained photosensitive coloring composition was stored in a thermostat at 40 ° C. for 1 week and accelerated over time, and then the viscosity of the photosensitive coloring composition after the aging was measured by the same method as in the above viscosity measurement. 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.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.

  As shown in Table 4, when the pigment derivative B-1 was used as in Comparative Examples 9, 11, 13, and 15, the brightness, contrast, initial viscosity, and storage stability were all low. This is because the dye derivative B-1 has three sulfonic acid groups, and the dye derivatives B-1 are strongly associated with each other via the sulfonic acid group, thereby inhibiting the adsorption to the colorant [A]. It is guessed. Similarly, when the pigment derivative B-2 was used as in Comparative Examples 10, 12, 14, and 16, the brightness, contrast, initial viscosity, and storage stability were all poorly evaluated. This is presumably because the pigment derivative B-2 has a halogen distribution width of 1, and thus the pigment derivatives B-2 are strongly aggregated and the adsorption to the colorant [A] is inhibited. On the other hand, when the pigment derivatives PC-1 to PC-19 described in the claims were used as in Examples 26 to 50, the evaluation results of brightness, contrast, initial viscosity, and storage stability were all superior to those of the comparative examples. ing. This is because the dye derivatives PC-1 to PC-19 described in Claims have a halogen distribution width of 4 or more and the number of sulfonic acid groups is 2 or less, so that association / aggregation between the dye derivatives is weak, This is presumably because the adsorption to the colorant [A] was remarkably improved.

<Production of color filter>
(Red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore diameter of 1 μm to prepare a red photosensitive coloring composition (RR-1).
PR254 pigment dispersion (RP-1): 30.0 parts PR177 / pigment dispersion (RP-2): 20.0 parts Acrylic 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 Acrylic 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 parts cyclohexanone: 39.0 parts

  The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix had been formed in advance by spin coating, and then dried at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed with a 0.2 mass% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and dried. Further, a heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate. Next, using the green photosensitive coloring composition (GR-27) of the present invention, a green coloring pixel layer is formed in the same manner as the red coloring pixel layer, and further the blue photosensitive coloring composition (BR-1) is formed. A blue colored pixel layer was formed using it to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the pigment derivative (PC-1 to PC-19) according to the present invention had high brightness and excellent contrast ratio.

Claims (4)

A coloring composition for a color filter comprising a coloring agent [A], a pigment derivative [B] containing a compound represented by the following general formula (1) or the following general formula (2), a binder resin and an organic solvent.
General formula (1)

[In General Formula (1), X ₁ represents a halogen atom, S ₁ represents a sulfonic acid group, an amine salt, a quaternary ammonium salt or a metal salt thereof, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitutions of the group represented by S ₁ is 1 ~ 2. M ₁ represents Al, Ga, or In. Y ₁ represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

General formula (2)

[In General Formula (2), X ₂ represents a halogen atom, S ₂ represents a sulfonic acid group, an amine salt thereof, a quaternary ammonium salt or a metal salt, and m + n represents an integer of 1 to 16. . However, the average value of the number of substitution of the halogen atom represented by X ₂ is 6 to 15, the halogen distribution width is 4 or more, and the average value of the number of substitution of the group represented by S ₂ is 1 to 2. M ₂ represents Si or Sn. Y ₂ and Y ₃ represent —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ or a hydroxyl group. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ₄ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ] The colorant [A] is a compound represented by the following general formula (3) ′, C.I. I. Pigment green 58, C.I. I. Pigment green 7 and C.I. I. The coloring composition for a color filter according to claim 1, which is at least one selected from the group consisting of CI Pigment Green 36.
General formula (3) '

[In General Formula (3) ′, X ₃ ^′ represents a halogen atom, and n represents an integer of 4 to 16. However, the average value of the number of halogen atoms represented by X ₃ ^′ is 6 to 15, and the halogen distribution width is 4 or more. R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. ]   Furthermore, the coloring composition for color filters of Claim 1 or 2 containing at least one of a photopolymerizable monomer and a photoinitiator.   The color filter which comprises the filter segment formed from the coloring composition for color filters as described in any one of Claims 1-3 on a base material.