JP2019086676A - Color filter coloring composition and color filter - Google Patents

Abstract

To provide a color filter coloring composition which offers superior filterability and can be used to form a coating film that offers high heat resistance, solvent resistance, and contrast ratio (CR), and to provide a high-quality color filter which offers high heat resistance, solvent resistance, and contrast ratio (CR).SOLUTION: The above problem is solved by a color filter coloring composition containing a colorant, binder resin, and organic solvent. The colorant contains a salt-forming compound having a structural unit represented by a specific formula and a structural unit represented by another formula different from that of the structural unit in one molecule.SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition for a color filter used in the manufacture of a color filter used in a color liquid crystal display device, a color image pickup tube device and the like, and a color filter provided with a filter segment formed using the same. is there.

  In recent years, dye-based coloring materials have attracted attention in order to realize high contrast ratio and high brightness that can not be achieved with pigments. However, some dyes have fluorescence emission characteristics (see, for example, Patent Document 1), and thus there is a problem that the contrast ratio is low. Further, the dye generally tends to be inferior in fastness such as heat resistance and light resistance as compared with the pigment, and also tends to be inferior in solubility in an organic solvent suitable as a color filter color product. Therefore, in using a dye, to impart organic solvent solubility, to impart fastness, and to a dye having fluorescence are required techniques for suppressing fluorescence.

  Various documents have been proposed as materials for quenching the fluorescence emitted by the dye (see, for example, Patent Document 2), but these quenching materials are sublimated or decomposed in the heating step at the time of preparation of the color filter substrate. The fluorescence quenching effect could not be exhibited, and a sufficient contrast ratio could not be obtained. Furthermore, to effectively exhibit the effect of the quenching material, it is generally known to accelerate energy transfer by shortening the distance between the fluorescent dye and the quenching material. Salt formation of dyes and quenchers can be considered as a method to make this distance closer, and similar methods have been proposed. Although improvement in solvent resistance is shown in this method, heating at the time of substrate preparation for color filters The heat resistance against sublimation and decomposition in the process has not been solved (see Patent Document 3).

Further, as a means for improving the heat resistance to sublimation, decomposition and the like of the quenching material, a method of incorporating it into a resin has been proposed (see Patent Document 4). This method is effective for improving the heat resistance, but since both the dye and the quenching agent are incorporated in the resin, the distance between them is long, and the quenching effect has not been sufficiently obtained.
When using a dye, it is dissolved in a solvent to form a dye solution, and filter filtration is carried out to remove foreign substances. However, since dissolution at a high concentration is currently required, the dye is not sufficient. It is known that the filter is clogged without being dissolved and the filterability becomes an issue.

JP, 2010-032999, A JP, 2013-101166, A Unexamined-Japanese-Patent No. 2011-215572 JP, 2015-018208, A

  An object of the present invention is to provide a coloring composition for color filters excellent in heat resistance, solvent resistance, contrast ratio (CR) and filterability, and a color filter.

It is a coloring composition for color filters containing a <1> coloring agent, a binder resin, and an organic solvent, Comprising: A coloring agent is a structural unit represented by following General formula (1) in 1 molecule, and the following general formula ( The coloring composition for color filters containing the salt-formation compound which has a structural unit represented by 2).

General formula (1)

[In general formula (1), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. The R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a good alkenyl group or a substituted group may have a substituent, R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R ₅ -or -COO-R _5- , and R ₅ represents an alkylene group. Y < ^- > represents an anionic dye (however, except for anions represented by the following general formula (4) to the following general formula (6)). ]

General formula (2)

[In general formula (2), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. The R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a good alkenyl group or a substituted group may have a substituent, R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R ₅ -or -COO-R _5- , and R ₅ represents an alkylene group. Z ⁻ represents an anion having at least one structure selected from the group consisting of the following general formula (4), the following general formula (5) and the following general formula (6). ]

General formula (4)

[In general formula (4), R _{10 to} R ₂₇ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₄₀₁ , -SO ₃ H or an -SO ₂ CH _3. R ₂₈ and R ₂₉ each independently represent a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₄₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₄₀₁ and R ₄₀₂ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 15 carbon atoms. Each of A _{1 to} A ₄ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M. M represents Cr or Co. n represents an integer of 1 to 5; ]

General formula (5)

[In general formula (5), R _{31 to} R ₃₉ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₅₀₁ , -SO ₃ H or -SO ₂ CH ₃ is represented. R ₄₀ represents a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₅₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₅₀₁ and R ₅₀₂ independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms. Each A ₅ and A ₆ are independently, * - O -, * - O-CO -, * - represents a CO-O-. * Represents a bond with M ₁ . M ₁ represents Cr or Co. n ₁ represents an integer of ₁ to 2; ]

General formula (6)

[In the general formula (6), R ₄₂ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is —OH, —OR ₆₀₁ , —CO— OR ₆₀₂ , -O-COR ₆₀₃ , -CONR ₆₀₄ R ₆₀₅ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, and -CH contained in the saturated hydrocarbon group _2- may be replaced by at least one of -O- and -CO-. R ₄₃ represents a hydrogen atom, -CN or -CONH ₂ . R ₄₄ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom. R _{45 to} R ₄₈ are each independently -R ₆₀₆ , -OR ₆₀₇ , -CO-OR ₆₀₈ , -COR ₆₀₉ , -OCO-OR ₆₁₀ , -O-COR ₆₁₁ , -CN, -NO ₂ , a halogen atom, It represents a _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 612 R 613 , or -NR ₅₂ R _53. R ₄₅ and R ₄₆ , R ₄₆ and R ₄₇ , and R ₄₇ and R ₄₈ may be combined with each other to form a 6 to 7-membered ring containing a benzene ring. R _{601 to} R ₆₁₃ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms And a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted by -OR ₅₁ . R ₅₁ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₅₂ and R ₅₃ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms or a tetrahydrofurfuryl group. R ₅₂ and R ₅₃ may be bonded to each other to form a ring containing a nitrogen atom. Each of A _{7 to} A ₁₀ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M ₂ . M ₂ represents Cr or Co. n ₂ represents an integer of 1 to 5. ]

<2> in the general formula (1) Y ^- is, the color filter colored composition for a xanthene anionic dye.

<3> The coloring composition for color filter as described above, further comprising a structural unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, and a t-butyl group. .

<4> Y in salt-forming compound ^- and Z ^- the weight ratio of ^(Z - / Y ^-) is 0.1 to 0.8, the coloring composition for the color filter.

The coloring composition for the above-mentioned color filters, wherein Z ⁻ in <5> general formula (2) is an anion having at least one structure selected from the group consisting of formula (4-1) and formula (5-1) object.

Formula (4-1)

Formula (5-1)

The coloring composition for color filters as described above, wherein the <6> salt-forming compound further has a structural unit derived from benzyl methacrylate.

<7> The colored composition for color filter as described above, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

<8> A color filter comprising a filter segment formed of the above-mentioned coloring composition for color filter on a substrate.

  According to the present invention, a coloring composition for color filter which can form a coating film excellent in filterability and having high heat resistance, solvent resistance and contrast ratio (CR), and high heat resistance, solvent resistance and contrast It is possible to obtain a high quality color filter having a ratio (CR).

Hereinafter, the present invention will be described in detail.
In the present application, when it is described as “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid” or “(meth) acrylate”, unless otherwise described, Acryloyl and / or methacryloyl ”,“ acrylic and / or methacrylic ”,“ acrylic acid and / or methacrylic acid ”or“ acrylate and / or methacrylate ”.
In addition, “CI” listed in the present specification means a color index (CI).

  The coloring composition for color filters of the present invention comprises a colorant, a binder resin and an organic solvent, and the colorant comprises, in one molecule, a structural unit represented by the general formula (1), and a general formula (2) It is characterized by including a salt-forming compound having a structural unit represented.

<Colorant>
Salt-forming compounds
The coloring composition of the present invention contains, as a coloring agent, a salt forming compound having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) in one molecule.

[Structural unit represented by the general formula (1) and structural unit represented by the following general formula (2)]
General formula (1)

[In general formula (1), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. The R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a good alkenyl group or a substituted group may have a substituent, R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R ₅ -or -COO-R _5- , and R ₅ represents an alkylene group. Y < ^- > represents an anionic dye (however, except for anions represented by the following general formula (4) to the following general formula (6)). ]

General formula (2)

[In general formula (2), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. The R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a good alkenyl group or a substituted group may have a substituent, R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R ₅ -or -COO-R _5- , and R ₅ represents an alkylene group. Z ⁻ represents an anion having at least one structure selected from the group consisting of General Formula (4), General Formula (5), and General Formula (6). ]

General formula (4)

[In general formula (4), R _{10 to} R ₂₇ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₄₀₁ , -SO ₃ H or an -SO ₂ CH _3. R ₂₈ and R ₂₉ each independently represent a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₄₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₄₀₁ and R ₄₀₂ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 15 carbon atoms. Each of A _{1 to} A ₄ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M. M represents Cr or Co. n represents an integer of 1 to 5; ]

General formula (5)

[In general formula (5), R _{31 to} R ₃₉ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₅₀₁ , -SO ₃ H or -SO ₂ CH ₃ is represented. R ₄₀ represents a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₅₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₅₀₁ and R ₅₀₂ independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms. Each A ₅ and A ₆ are independently, * - O -, * - O-CO -, * - represents a CO-O-. * Represents a bond with M ₁ . M ₁ represents Cr or Co. n ₁ represents an integer of ₁ to 2; ]

General formula (6)

[In the general formula (6), R ₄₂ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is —OH, —OR ₆₀₁ , —CO— OR ₆₀₂ , -O-COR ₆₀₃ , -CONR ₆₀₄ R ₆₀₅ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, and -CH contained in the saturated hydrocarbon group _2- may be replaced by at least one of -O- and -CO-. R ₄₃ represents a hydrogen atom, -CN or -CONH ₂ . R ₄₄ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom. R _{45 to} R ₄₈ are each independently -R ₆₀₆ , -OR ₆₀₇ , -CO-OR ₆₀₈ , -COR ₆₀₉ , -OCO-OR ₆₁₀ , -O-COR ₆₁₁ , -CN, -NO ₂ , a halogen atom, It represents a _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 612 R 613 , or -NR ₅₂ R _53. R ₄₅ and R ₄₆ , R ₄₆ and R ₄₇ , and R ₄₇ and R ₄₈ may be combined with each other to form a 6 to 7-membered ring containing a benzene ring. R _{601 to} R ₆₁₃ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms And a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted by -OR ₅₁ . R ₅₁ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₅₂ and R ₅₃ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms or a tetrahydrofurfuryl group. R ₅₂ and R ₅₃ may be bonded to each other to form a ring containing a nitrogen atom. Each of A _{7 to} A ₁₀ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M ₂ . M ₂ represents Cr or Co. n ₂ represents an integer of 1 to 5. ]

Examples of the alkyl group in R ₁ of the general formula (1) and the general formula (2) include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group and an n-hexyl group And a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, as R ₁ , a hydrogen atom or a methyl group is most preferable.

Examples of the alkyl group in R _{2 to} R ₄ in the general formula (1) and the general formula (2) include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl etc., branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2- Ethylhexyl and 1,1,3,3-tetramethylbutyl etc., cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc. and bridged cyclic alkyl groups such as norbornyl, adamantyl and pinanyl etc. may be mentioned. As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group as R _{2 to} R ₄ in the general formula (1) and the general formula (2) include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2 Butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl etc., cycloalkenyl group (2-cyclo) Hexenyl and 3-cyclohexenyl and the like). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group in R _{2 to} R ₄ in the general formula (1) and the general formula (2) include a monocyclic aryl group (such as phenyl), a fused polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, Fluorenyl and naphthoquinolyl etc.) and aromatic heterocyclic hydrocarbon group (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyrane), pyridyl (derived from pyridine) Groups), 9-oxoxanthenyl (a group derived from xanthone) and 9-oxothioxanthenyl (a group derived from thioxanthone) and the like.

When the alkyl group, alkenyl group or aryl group in R _{2 to} R ₄ in the general formula (1) and the general formula (2) has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group and an aryloxy The substituent selected from a group, an alkenyl group, an acyl group, an alkoxycarbonyl group, a carboxyl group, a phenyl group etc. is mentioned. Among them, halogen atoms, hydroxyl groups, alkoxyl groups and phenyl groups are particularly preferable as the substituent.

From the viewpoint of stability, an unsubstituted alkyl group is particularly preferable as R _{2 to} R _{4 in the} general formula (1) and the general formula (2). Also, _two of R _{2 to} R ₄ may be bonded to each other to form a ring.

Examples of the alkylene group and arylene group in Q ₁ of General Formula (1) and General Formula (2) include groups in which one hydrogen atom of the alkyl group and aryl group in R _{1 to} R ₄ described above is removed.

The alkylene group for R ₅ in the general formulas (1) and (2) include one group obtained by removing a hydrogen atom of the alkyl group for R ₁ to R ₄ above.

As Q _{1 in the} general formula (1) and the general formula (2), -CONH-R ₅ -and -COO-R ₅ -are preferable from the viewpoint of polymerizability and availability. Further, R ₅ is more preferably a methylene group, an ethylene group, a propylene group or a butylene group, and particularly preferably an ethylene group.

<Y ⁻ : anionic dye (however, except for anions represented by formulas (4) to (6))>
Y ^- anionic dye (provided that the general formula (4) - (excluding anion represented by 6)) in Examples, can be employed without any known limitation, specifically, a carboxylic acid group in the molecule, sulfone Anionic dyes derived from anionic dyes having an acid group, a phenolic hydroxyl group, a phosphoric acid group, or a metal salt thereof can be mentioned. As an anionic dye, for example, anthraquinone anionic dye, monoazo anionic dye, disazo anionic dye, oxazine anionic dye, aminoketone anionic dye, xanthene anionic dye, quinoline anionic dye, Triphenylmethane-based anionic dyes and the like can be mentioned.

Examples of the dye include various dyes such as oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes and acid mordant dyes. As oil-soluble dyes, C.I. As the basic dyes, those classified as C.I. C. I. Basic dyes, and C.I. I. Acids classified as acid, same direct dyes as C.I. I. Direct classification. Here direct dyes, sulfonic acid group in the structure _{(-SO 3 H, -SO 3 Na} ) has, in the present invention, dyes are those regarded as acid dye directly. Anionic dyes are those having an anion moiety such as a sulfone group in the dye skeleton, and generally correspond to what is called an acid dye.
Below, the specific example of anionic dye is shown by a color index number.

  As a red dye, C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 37, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 171, 172, 173, 175, 176, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.

  Also, C.I. I. Direct Red 1, 2, 2, 2, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 31, 33, 33: 1, 34, 35, 36, 37, 42, 43, 43, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72, 72, 72, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 1 8, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like can also be used.

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

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

  As the orange dye, C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like.

  Also, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114 and the like can also be used.

  As a blue dye, C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34 35, 37, 40, 41, 41: 41, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 1 0, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

  Also, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 124, 128, 129, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213 215,225,226,229,230,231,242,243,244,253,254,260,263 and the like can also be used.

  As a purple dye, C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, etc. Can be mentioned.

  Also, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like can also be used.

  As a green dye, C.I. I. Acid green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95 and the like. Also, C.I. I. Direct greens 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

<Z ⁻ : An anion having at least one structure selected from the group consisting of Formula (4), Formula (5), and Formula (6)>
[Anion Represented by General Formula (4)]
General formula (4)

[In general formula (4), R _{10 to} R ₂₇ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₄₀₁ , -SO ₃ H or an -SO ₂ CH _3. R ₂₈ and R ₂₉ each independently represent a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₄₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₄₀₁ and R ₄₀₂ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 15 carbon atoms. Each of A _{1 to} A ₄ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M. M represents Cr or Co. n represents an integer of 1 to 5; ]

In the general formula (4), the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ₁₀ ~R _27, R ₄₀₁ and R _402, a methyl group, an ethyl group, n- propyl radical, n -Linear alkyl groups such as -butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl; isopropyl, sec-butyl, tert-butyl, 1-methylbutyl, 1 And branched chains such as 1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group Like alkyl groups.

It is preferable that at least one of R _{10 to} R ₂₇ be a nitro group. Having a nitro group tends to increase the spectral density of the compound. In addition, having at least one halogen atom in addition to the nitro group tends to weaken the fluorescence of the compound. Among the halogen atoms, chloro and bromo are preferable.
R ₂₈ and R ₂₉ are preferably each independently hydrogen, a methyl group, -SO ₂ NHR ₄₀₂ , -SO ₃ H or -SO ₂ CH.
The alkoxyalkyl group having 2 to 15 carbon atoms represented by R ₄₀₁ and R ₄₀₂ is a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a 1-ethoxypropyl group, 2-ethoxy Propyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2- Examples include isopropoxy-1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

In the general formula (4), one of R _{10 to} R ₁₈ and R _{19 to} R ₂₇ independently represents a hydrogen atom, a chloro group, SO ₂ NHR ₄₀₁ , -SO ₃ H, and -SO ₂ CH ₃ , R ₂₈ and R ₂₉ each independently represent a hydrogen atom, a methyl group or -SO ₃ H, and R ₄₀₁ represents a hydrogen atom, a C 1-4 monovalent saturated hydrocarbon group, or a C 2-8 carbon atom. An alkoxyalkyl group, a combination in which two of A _{1 to} A ₄ are * -O-, and the rest are identically * -O- or * -O-CO-, M is Cr and n is 1 Is preferred.

  As the anion represented by Formula (4), C.I. I. Anion (formula (4-1)) derived from solvent orange 62, C.I. I. Anion derived from Solvent Orange 41, C.I. I. Anion (formula (4-2)) derived from solvent red 130, C.I. I. The anion (formula (4-3)) etc. which originate in Solvent Yellow 21 are mentioned. Among them, preferably C.I. I. Anion (formula (4-1)) derived from Solvent Orange 62 or C.I. I. It is an anion derived from solvent orange 41, more preferably C.I. I. It is an anion (Formula (4-1)) derived from solvent orange 62.

Formula (4-1)

Formula (4-2)

Formula (4-3)

[Anion Represented by General Formula (5)]
General formula (5)

[In general formula (5), R _{31 to} R ₃₉ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₅₀₁ , -SO ₃ H or -SO ₂ CH ₃ is represented. R ₄₀ represents a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₅₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₅₀₁ and R ₅₀₂ independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms. Each A ₅ and A ₆ are independently, * - O -, * - O-CO -, * - represents a CO-O-. * Represents a bond with M ₁ . M ₁ represents Cr or Co. n ₁ represents an integer of ₁ to 2; ]

In the general formula (5), the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ₃₁ ~R _39, R ₅₀₁ and R _502, a methyl group, an ethyl group, n- propyl radical, n -Linear alkyl groups such as -butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl; isopropyl, sec-butyl, tert-butyl, 1-methylbutyl, 1 And branched chains such as 1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group Like alkyl groups.

It is preferable that at least one of R _{31 to} R _{39 be} each independently a hydrogen atom, a nitro group, a halogen atom, -SO ₂ NHR ₅₀₁ , -SO ₃ H or -SO ₂ CH ₃ . Having a nitro group tends to increase the spectral density of the compound. In addition, having a halogen atom is preferable because the fluorescence emission of the compound tends to be weakened. Among the halogen atoms, chloro and bromo are preferable. R ₅₀₁ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.

R ₄₀ is preferably a methyl group, -SO ₂ NHR ₅₀₂ , -SO ₃ H or -SO ₂ CH.
The alkoxyalkyl group having 2 to 15 carbon atoms represented by R ₅₀₂ is a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a 1-ethoxypropyl group, a 2-ethoxypropyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopropoxy- Examples thereof include 1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

In the general formula (5), one of R _{31 to} R ₃₉ is a nitro group, one is a hydrogen atom or a chloro group, and one is selected from SO ₂ NHR ₅₀₁ , -SO ₃ H, and SO ₂ CH ₃ And the rest is a hydrogen atom, R ₄₀ is a methyl group, or —SO ₃ H, and R ₅₀₁ is a hydrogen atom, a C 1-4 monovalent hydrocarbon group, or a carbon number 2 to 8 alkoxyalkyl groups, one of A _{5 to} A ₆ being * -O-, the remainder being * -O- or * -O-CO-, and M 1 being Cr or Co, n ₁ Is preferably a combination of 1.

  As the anion represented by Formula (5), for example, C.I. I. The anion (formula (5-1)) etc. which originate in Solvent Orange 56 are mentioned, and it is used suitably.

Formula (5-1)

[Anion Represented by General Formula (6)]
General formula (6)

[In the general formula (6), R ₄₂ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is —OH, —OR ₆₀₁ , —CO— OR ₆₀₂ , -O-COR ₆₀₃ , -CONR ₆₀₄ R ₆₀₅ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, and -CH contained in the saturated hydrocarbon group _2- may be replaced by at least one of -O- and -CO-. R ₄₃ represents a hydrogen atom, -CN or -CONH ₂ . R ₄₄ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom. R _{45 to} R ₄₈ are each independently -R ₆₀₆ , -OR ₆₀₇ , -CO-OR ₆₀₈ , -COR ₆₀₉ , -OCO-OR ₆₁₀ , -O-COR ₆₁₁ , -CN, -NO ₂ , a halogen atom, It represents a _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 612 R 613 , or -NR ₅₂ R _53. R ₄₅ and R ₄₆ , R ₄₆ and R ₄₇ , and R ₄₇ and R ₄₈ may be combined with each other to form a 6 to 7-membered ring containing a benzene ring. R _{601 to} R ₆₁₃ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms And a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted by -OR ₅₁ . R ₅₁ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₅₂ and R ₅₃ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms or a tetrahydrofurfuryl group. R ₅₂ and R ₅₃ may be bonded to each other to form a ring containing a nitrogen atom. Each of A _{7 to} A ₁₀ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M ₂ . M ₂ represents Cr or Co. n ₂ represents an integer of 1 to 5. ]

In the general formula (6), examples of the monovalent C 1 to C 12 saturated hydrocarbon group represented by R ₄₂ include methyl, ethyl, n-propyl, n-butyl and n-pentyl groups, Linear saturated hydrocarbon groups such as n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc .; isopropyl group, isobutyl group, sec-Butyl, tert-Butyl, isopentyl, methyl pentyl, ethyl butyl, methyl hexyl, ethyl pentyl, propyl butyl, (methyl ethyl) butyl, (methyl ethyl) (methyl) propyl, methyl Heptyl, ethylhexyl, propylpentyl, (methylethyl) pentyl, butylbutyl, (butyl) (methyl) butyl, (dimethylethyl) (butyl) ) Butyl, dimethylpropyl, dimethylbutyl, (ethyl) (methyl) propyl, dimethylpentyl, (ethyl) (methyl) butyl, dimethylhexyl, (ethyl) (methyl) pentyl, (propyl) Branched saturated hydrocarbon groups such as (methyl) butyl group, (methyl ethyl) (methyl) butyl group, diethyl butyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group And alicyclic saturated hydrocarbon groups such as cyclodecyl group.

In the general formula (6), as the alkyl group having 1 to 4 carbon atoms represented by R ₄₄ , a linear saturated hydrocarbon group having 4 or less carbon atoms among the groups exemplified for R ₄₂ , the carbon number Is a branched saturated hydrocarbon group having 4 or less.

In the general formula (6), the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ₆₀₁ to R _613, R ₅₂ and R _53, the carbon of the respective groups exemplified in R ₄₂ The thing whose number is eight or less can be illustrated. Furthermore, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a 2-methyl propenyl group etc. are mentioned.

Examples of the aralkyl group having 7 to 12 carbon atoms as R _{601 to} R ₆₁₃ in the general formula (6) include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ₆₀₁ to R ₆₁₃ and R _51, a phenyl group, toluyl group, xylyl group, and a naphthyl group. The monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R _51, those wherein exemplified R ₄₂ carbon atoms among the groups is 8 or less can be exemplified.

Examples of the acyl group having 2 to 8 carbon atoms in R ₅₂ and R ₅₃ in the general formula (6) include formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group and the like. Be

In the general formula (6), in R _42, -CH ₂ - As the saturated hydrocarbon group is replaced by -O- or -CO-, for example, acetyl group, oxobutyl group, oxopentyl group, oxo hexyl group Saturated hydrocarbon group containing an oxo group of And an oxo group-containing saturated hydrocarbon group substituted with an aromatic group such as oxo (naphthyl) propyl group; a saturated hydrocarbon group in which one —CH ₂ — is replaced by —CO— and the like; 2- (acetyloxy) acetoxy] ethyl group, 2- (2-ethylhexanoyloxy) ethyl group, 2- [2- (methoxycarbonyl) A group formed by an alkyl group such as ethyl carbonyloxy] ethyl group, an alkylene group, and an ester bond; a group formed by an alkylene group such as a 2-benzoyloxyethyl group, an aromatic ring, and an ester bond; is replaced by the -CO-, 1 single -CH ₂ - - 1 one -CH ₂ of include saturated hydrocarbon group which is replaced by -O-.

In the general formula (6), R ₄₂ is an alkyl group having 1 to 4 carbon atoms; a hydroxyalkyl group having 1 to 4 carbon atoms; a group formed by an alkyl group, an alkylene group and two ester bonds, an alkylene group and R ₄₃ is -CN, R ₄₄ is an alkyl group having 1 to 4 carbon atoms, 3 of R _{45 to} R ₄₈ each being a group formed by an aromatic ring and one ester bond One is a hydrogen atom, and the remaining one is a hydrogen atom or -NR ₅₂ R ₅₃ , and one of R ₅₂ and R ₅₃ constituting this -NR ₅₂ R ₅₃ is a hydrogen atom, and the other has 2 to 4 carbon atoms. Acyl groups, two of A _{11 to} A ₁₄ are * -O-, and the rest are identically * -O- or * -O-CO-, M ₂ is Cr, n ₂ is 1 and A combination of

  As an anion represented by Formula (6), the anion represented by Formula (6-1)-(6-6) is mentioned, for example.

Formula (6-1)

Formula (6-2)

Formula (6-3)

Formula (6-4)

Formula (6-5)

Formula (6-6)

The anion Z ⁻ having at least one structure selected from the group consisting of general formula (4), general formula (5) and general formula (6) is represented by general formula (4) or general formula (5) An anion having the following structure is preferred. Among them, C.I. I. Anion (formula (4-1)) derived from Solvent Orange 62 or C.I. I. The anion (formula (5-1)) derived from solvent orange 56 is particularly preferable.

  The salt forming compound further contains at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, and a t-butyl group, as described in the section of production of a salt forming compound described later. Is preferred. In the heating step in the production of the color filter, the thermally crosslinkable group possessed by the salt forming compound forms a crosslink to form a strong film, thereby preventing the color change of the coating film. Thereby, the heat resistance can be improved, and the solvent resistance is also improved.

Further, Y in the salt formation compound ^- and Z ^- the weight ratio of ^(Z - / Y ^-) is preferably 0.1 to 0.8. More preferably, it is 0.1 to 0.4. This is preferably greater than 0.1 in order to sufficiently exhibit the quenching ability of the piazolone azo dye, and is preferably less than 0.4 from the viewpoint of heat resistance and solvent resistance.

<Production of salt forming compounds>
The salt forming compound of the present invention only needs to have the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in one molecule, and particularly preferably the following A vinyl resin having a cationic group in a side chain containing a structural unit represented by the general formula (3), an anionic dye, and a compound having an anion represented by the above general formulas (4) to (6) It is a salt form of.

[Vinyl-Based Resin Having a Cationic Group in a Side Chain Containing a Structural Unit Represented by General Formula (3)]

General formula (3)

[In general formula (3), R ²¹ represents a hydrogen atom or an alkyl group which may have a substituent. R ²² to R ²⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, which may have an optionally substituted alkenyl group or an optionally substituted aryl group, R ²² Two of R ²⁴ may combine with each other to form a ring. Q ³ are an alkylene group, an arylene group, ^{-CONH-R 25} - or ^{-COO-R 5} - ^{represents, R 25} represents an alkylene group. U ^- represents an anion of an inorganic or organic. ]

The alkyl group in R ²¹ of General Formula (3) and the substituent that it may have is the same as the alkyl group in R ₁ of General Formula (1) above and the substituent that it may have.

The alkyl group, the alkenyl group, the aryl group and the substituent which may be possessed by R ^{22 to} R ²⁴ in the general formula (3) are the alkyl group in R _{2 to} R ₄ in the above general formula (1) and It is synonymous with a good substituent.

Alkylene group and arylene group in Q ³ of the general formula (3) has the same meaning as the alkylene and arylene groups in to Q ₁ the above general formula (1).

The alkylene group in R ²⁵ of General Formula (3) has the same meaning as the alkylene group in R ₅ of General Formula (1) described above.

U of general formula (3) ^- in, the inorganic or organic anion, can be employed without any known limitation. Specifically, hydroxide ions; chloride, bromide, halogens such as iodide ions Ions; carboxylate ions such as formate ions and acetate ions; carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, Furthermore, complex ions such as hexacyanoferrate (III) ion may be mentioned. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded to the resin to form an inner salt.

(Method for producing vinyl-based resin having cationic group in side chain)
In order to obtain a vinyl-based resin having a cationic group in a side chain containing a structural unit represented by the general formula (3), copolymerization of an ethylenically unsaturated monomer having a quaternary ammonium base and another monomer is carried out Method of copolymerizing an ethylenically unsaturated monomer having an amino group with another monomer to obtain a vinyl resin having an amino group, and then reacting it with an onium chlorinating agent to carry out ammonium chloride It may be obtained by

  Hereinafter, specific examples of ethylenically unsaturated monomers that can be used to obtain a vinyl-based resin containing a structural unit represented by General Formula (3) will be shown. In the present specification, when either or both of “acrylic and methacrylic” are indicated, it may be described as “(meth) acrylic”. Similarly, when either or both of "acryloyl and methacryloyl" are indicated, "(meth) acryloyl" may be described.

  Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyl trimethyl ammonium chloride, (meth) acryloyl oxyethyl triethyl ammonium chloride, (meth) acryloyl oxyethyl dimethyl benzyl ammonium chloride, (meth ) Alkyloxy (meth) acrylate quaternary ammonium salt such as acryloyloxyethyl methyl morpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acryloyl amide quaternary ammonium salts such as ammonium chloride; Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl (Meth) acrylic acid ester having dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide is mentioned, Styrenes having dialkylamino group such as dimethylaminostyrene, dimethylaminomethylstyrene etc., diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinyl pyrrolidine, N-vinyl pyrrolidone, N-vinyl carbazole and the like.

  As the onium chlorinating agent, for example, alkyl sulfuric acid such as dimethyl sulfuric acid, diethyl sulfuric acid or dipropyl sulfuric acid, methyl p-toluenesulfonic acid, sulfonic acid ester such as methyl benzenesulfonic acid, methyl chloride, ethyl chloride, propyl chloride or Alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, or octyl chlorobromide, or benzyl chloride or benzyl bromide.

In the reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent, an equimolar or less onium chlorination agent is usually added dropwise to the ethylenically unsaturated monomer solution having an amino group. You can do this by The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly about 30 ° C. or less when ammonium vinyl chloride is to be chlorinated, and the reaction time is about 1 to 4 hours.

  Alternatively, alkoxycarbonylalkyl halides can also be used as onium chlorinating agents.

(Other monomers)
As other ethylenically unsaturated monomers, for example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamide , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

Specific examples of such vinyl monomers include, for example, the following compounds.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octodecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxy) (meth) acrylate (Tox) ethyl, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol (meth) acrylate Monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonyl phenoxy polyethylene glycol, (meth) acrylic Dicyclopentenyl acid, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentene (meth) acrylate Le, (meth) perfluorooctyl acrylate, (meth) acrylate, dicyclopentanyl (meth) acrylic acid tribromophenyl, and (meth) tribromophenyl oxyethyl acrylate.
Among them, it is preferable to use benzyl (meth) acrylate as another monomer.

   Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butylate, vinyl methoxyacetate, and vinyl benzoate. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-Butyl acrylic (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N- dimethyl (meth) Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrenes are styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Styrene, hydroxystyrene protected with a deprotectable group with an acidic substance (such as t-Boc), methyl vinyl benzoate, and α-methyl styrene

  The other monomer preferably contains a thermally crosslinkable functional group. In the heating step in the production of the color filter, the thermally crosslinkable functional group possessed by the resin contained in the coloring composition for color filter forms a crosslink to form a strong coating, thereby preventing the color change of the coating. Thereby, the heat resistance can be improved, and the solvent resistance is also improved.

  The preferred structure of the thermally crosslinkable functional group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic acid anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, and an epoxy. Groups, mercapto groups, isocyanate groups, allyl groups, (meth) acrylic groups and the like. Among them, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acrylic group are preferable from the viewpoint of storage stability in the application of the coloring composition for color filter and reactivity with other materials It is preferable to have a carboxyl group from the viewpoint of alkali developability.

Specific examples of the monomer having the thermally crosslinkable functional group are shown below.
As an ethylenically unsaturated monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, Examples thereof include 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (addition molar number is preferably 1 to 5).

  Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like, and the ethylenically unsaturated group having a carboxylic acid anhydride group Examples of the monomer include maleic anhydride and itaconic anhydride.

  As an ethylenically unsaturated monomer having an oxetanyl group, for example, 3- (acryloyloxy methyl) 3-methyl oxetane, 3- (methacryloyloxy methyl) 3-methyl oxetane, 3- (acryloyl oxymethyl) 3-ethyl Oxetane, 3- (methacryloyloxymethyl) 3-ethyl oxetane, 3- (acryloyloxymethyl) 3-butyl oxetane, 3- (methacryloyloxymethyl) 3-butyl oxetane, 3- (acryloyloxymethyl) 3-hexyl oxetane and 3- (methacryloyloxymethyl) 3-hexyl oxetane and the like can be mentioned.

  Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

  As an ethylenic unsaturated monomer which has an isocyanate group, 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate etc. are mentioned, for example.

  As said isocyanate group, block isocyanate group is also contained and it can use preferably. With a blocked isocyanate group, under ordinary conditions, while the reactivity of the isocyanate group is suppressed by protecting the isocyanate group with another functional group, it can be deprotected by heating to regenerate an active isocyanate group. Indicates an isocyanate block. As a commercial item of the ethylenically unsaturated monomer which has such a block isocyanate group, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Methacrylic acid 2- (0- [1 'methylpropylideneamino] carboxyamino) ethyl (Karenz MOI-BM, manufactured by Showa Denko K. K.) and the like can be mentioned.

To introduce a (meth) acryloyl group as a thermally crosslinkable functional group,
There is a method of reacting a compound having a functional group capable of reacting to the functional group and a (meth) acryloyl group with a functional group possessed by the vinyl resin after obtaining a vinyl resin having a cationic group in a side chain. It can be mentioned. For example, a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group is reacted with a carboxyl group in a vinyl resin having a cationic group in a side chain having a carboxyl group as a thermally crosslinkable functional group ( A vinyl resin having a (meth) acryloyl group can be obtained. Further, by reacting the isocyanate group of the ethylenically unsaturated monomer having an isocyanate group with the hydroxyl group of the vinyl resin having a cationic group in the side chain having a hydroxyl group, a (meth) acryloyl group as a thermally crosslinkable functional group A vinyl resin having a group can be obtained.
The thermally crosslinkable functional group needs to be contained at least one kind in the vinyl resin, and two or more kinds may be contained.

Furthermore, in the case where two or more types of thermally crosslinkable functional groups are contained, the effect of crosslinking is improved when the thermally crosslinkable functional groups are a combination that is more likely to react with each other at the time of heating. For example, the combination of a hydroxyl group and a carboxyl group, or a combination of an oxetanyl group and a carboxyl group not only provides a strong coating film by heat crosslinking, but also an alkali development step in the step of alkali development before heat crosslinking. It is preferable because the developability is improved. Moreover, the combination of a hydroxyl group and a block isocyanate group is also effective and preferable.
Furthermore, a combination of an oxetanyl group and a t-butyl group is more preferable because the t-butyl group becomes a carboxyl group upon heating and reacts with the oxetanyl group. The oxetanyl group and t-butyl group are more hydrophobic than hydroxyl groups and carboxyl groups, and even if they are contained in a vinyl resin having a cationic group in the side chain, the compatibility with other resins is poor. Therefore, it is believed that more can be contained, and as a result, the crosslink density of the coating film can be increased and a stronger coating film can be obtained.

  As a method for obtaining a vinyl resin containing a structural unit represented by the general formula (3) suitable for the present invention, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, living radical polymerization, etc. , Known methods can be used. Among these, free radical polymerization or living radical polymerization is preferable.

  The vinyl resin containing the structural unit represented by the general formula (3) suitable for the present invention may be either a random resin or a block resin, but when the composition for color filter of the present invention is a red composition, It is preferable that it is a random resin.

The amount of ammonium base present in the vinyl-based resin containing the structural unit represented by the general formula (3) is not particularly limited, but the ammonium salt value of the resin is 10 to 200 mg KOH / g Preferably, it is more preferably 20 to 130 mg KOH / g.
By setting it as this range, coexistence with coloring power and temporal stability, such as a foreign material etc., can be achieved.

  In order for the ammonium salt value of the resin to satisfy the above range, the ethylenically unsaturated monomer having a quaternary ammonium base is preferably 4 to 74 based on the total amount of ethylenically unsaturated monomers constituting the resin. It is mass%, More preferably, it is 8-48 mass%.

  The molecular weight of the vinyl resin containing the structural unit represented by the general formula (3) is not particularly limited, but the weight average molecular weight as measured by gel permeation chromatography (GPC) is 1,000 to 500. Is preferable, and 3,000 to 15,000 is more preferable.

  Moreover, it is preferable that the vinyl resin containing the structural unit represented by General formula (3) has the characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, a coating film free from the occurrence of foreign matter can be obtained. In particular, dissolution in propylene glycol monomethyl ether acetate is more preferable.

[Anionic dye]
An anionic dye that forms a salt with a vinyl resin having a cationic group in a side chain containing a structural unit represented by the general formula (3) can give an anion at Y ⁻ of the above general formula (1) It is a dye.
The anionic dye which can be preferably used in the present invention, when used as a coloring composition for color filters, must have heat resistance and solvent resistance of a certain level or more. However, although anionic dyes have good spectral characteristics and are excellent in color developability, they can not be used as coloring compositions for color filters because they have poor heat resistance and solvent resistance, and lack of solubility in organic solvents. There are many pigments. Examples of the anionic group contained in the dye include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and bases thereof, and from the viewpoint of heat resistance and solvent resistance, a sulfonic acid group, a phosphoric acid group, and the like It is preferably a base. The dye having an anionic group (having fluorescence) is not particularly limited as long as it is a dye having at least one anionic group, but C.I. I. Acid red 51 (erythrosine (food red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (food red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), C.I. I. Acid Red 254, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, C.I. I. Acid Violet 9, Edible Blue No. 101 (C. I. Acid Blue 1), Acid Pure Blue (C. I. Acid Blue 3), Lake Blue I (C. I. Acid Blue 5), Lake Blue II (C.I. Blue) Acid Blue 7) Edible Blue No. 1 (C. I. Acid Blue 9), C.I. I. Acid Blue 22, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. Acid Blue 109, C. I. Direct Red 70, C. I. Acid Yellow 186, Same Direct Yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, C C. I. Direct Orange 18, C. I. Direct Red 11, and the like. C. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, C.I. I. Acid Red 254 is more preferable in terms of hue and color developability.
Moreover, heat resistance, light resistance, and solvent resistance can be improved by using sulfonamidation as a sulfonic acid amide compound.

[Compound Having an Anion Represented by General Formulas (4) to (6)]
Compounds having an anion represented by the general formulas (4) to (6) which form a salt with a vinyl resin having a cationic group in a side chain containing a structural unit represented by the general formula (3) have the above general formula It is a compound which can give the anion in Z < ^- > of (2), and it is preferable that it is a metal complex dye.
As such a metal complex dye, for example, C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; I. Solvent blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211 can be mentioned. Among these, from the viewpoint of suppression of fluorescence, C.I. I. Solvent Yellow 21, 79, 81, 82, C.I. I. Solvent orange 41, 54, 56, 62, 99, C.I. I. Solvent Red 8, 118, 122, 127 are preferable, and considering the balance between fluorescence emission suppression and lightness, C.I. I. Solvent oranges 41, 56, 62, 99 are particularly preferred.

  The metal atom of the metal complex dye is chromium (Cr) or cobalt (Co), and chromium (Cr) is more preferable in view of the quenching ability.

  Examples of metal complex dyes include 1: 1 form metal complex dyes in which the bonding ratio of metal atoms to dye molecules is 1: 1, and 1: 2 form metal complex dyes in which the ratio is 1: 2. Preferred are 1: 2 metal complex salt dyes.

  The metal complex dye has a fluorescence quenching ability, and when used in combination with the anionic dye, has an effect of increasing the contrast ratio of the coloring composition. An anionic dye and a metal are reacted by reacting an anionic dye and a metal complex dye with a resin having a cationic group in a side chain represented by the general formula (3) to form a salt form coexisting in the same molecule. The complex dyes are in close proximity and fluorescence quenching is performed more efficiently. As a result, a sufficient amount of fluorescence can be suppressed and a high contrast ratio can be expressed. At the same time, by using it in the form of a salt forming compound, the heat resistance and solvent resistance of the metal complex dye are improved, and sublimation and decomposition in the heating step at the time of producing a color filter are suppressed. Further, by incorporating the anionic dye and the metal complex dye in the same resin molecule, the polarity of the salt forming compound becomes a value close to that of the organic solvent, and the compatibility with other resins is improved. Filterability is good.

<Salt formation>
The salt forming compound of the present invention is obtained by dissolving a resin having a cationic group in a side chain and a metal salt or organic cation salt of an anionic dye and a metal complex dye represented by the general formulas (4) to (6). The aqueous solution is stirred and vibrated, or an aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an anionic dye, and a metal salt or organic cation salt of a metal complex dye represented by formulas (4) to (6) It can be easily obtained by mixing it with an aqueous solution of either under stirring or vibration. An aqueous solution of a resin having a cationic group in a side chain is stirred, to which an aqueous solution of an anionic dye and an aqueous solution of a metal salt or organic cation salt of a metal complex dye represented by General Formulas (4) to (6) are dropped. The method of doing is more preferable.
In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and these are ionically bound, and the ionically bound portion becomes water insoluble and precipitates. On the contrary, since the salt consisting of the counter anion of resin and the counter cation of acid dye is water soluble, it can be removed by washing with water or the like. The resin having a cationic group in the side chain to be used and the anionic dye may each be used alone or in combination of two or more types having different structures. In addition, by changing the pH as necessary, the solubility of the anionic dye and the metal complex dye represented by the general formulas (4) to (6) in water can be adjusted to form a salt.

  The ratio of the resin having a cationic group in the side chain to the anionic dye and the metal salt or organic cation salt of the metal complex dye represented by the general formulas (4) to (6) is the total cationic group of the resin If the molar ratio of the anionic dye and the anion represented by the general formulas (4) to (6) with respect to all the anionic groups is in the range of 10/1 to 1/1, the salt forming compound of the present invention is suitably adjusted. It is more preferable if it is in the range of 2/1 to 1/1.

  In addition, the ratio of the anionic dye to the metal salt or organic cation salt of the metal complex dye, which is a compound having an anion represented by the general formulas (4) to (6), is 20/1 to 1/20 in molar ratio The salt forming compound of the present invention can be suitably adjusted as long as it is in the range of 15/1 to 1/15. That is, the molar ratio of the structural unit represented by the general formula (1) of the salt forming compound in the present invention to the structural unit represented by the following general formula (2) is preferably 15/1 to 1/15. .

<Other colorants>
In the composition of the present invention, an organic pigment or other dye can be used as a colorant other than the salt forming compound. One or more of these may be used in combination.

(Organic pigment)
Examples of blue pigments include C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment blue 15: 6.

  In particular, when a coloring composition is used for a blue filter segment, by using a blue pigment in combination, the spectral spectrum has a high transmittance in the vicinity of 425 to 500 nm having characteristic peaks of many backlights. This is preferable because it is possible to obtain high brightness as a blue filter segment rather than a colorant combining conventional blue pigments and other pigments.

  As a green pigment, for example, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58 can be mentioned. Furthermore, the pigment of Unexamined-Japanese-Patent No. 2016-188993 can be used. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment green 7, 36, 58, a pigment described in JP-A-2016-18993.

  Examples of yellow pigments include C.I. I. Pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 185.

  Examples of purple pigments include C.I. I. Pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 25, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, and more preferably C.I. I. Pigment violet 23.

Examples of red pigments include C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like.
As an orange pigment which works similarly to a red pigment, for example, C.I. I. Orange pigments such as pigment orange 36, 38, 43, 51, 55, 59, 61 can be used. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment red 254, C.I. I. It is particularly preferable to use pigment red 177.

(Fined pigment)
The pigment used in the present invention is preferably used after being micronized, but the method of micronization is not particularly limited. Thus, it is possible to carry out salt milling treatment by the kneader method, which is one of wet grinding.

  The primary particle diameter of the finely divided pigment is preferably 20 nm or more, because the dispersion in the colorant carrier is good. In addition, the thickness is preferably 100 nm or less because a filter segment having a high contrast ratio can be formed. The particularly preferred range is in the range of 25 to 85 nm. The primary particle diameter of the pigment was determined by a method of directly measuring the size of the primary particles from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was defined as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to the cube of the determined particle size to obtain an average volume, and the length of one side of the cube having this average volume is averaged to the first order Let the particle size be.

  Salt milling involves heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader, trimix, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, etc. After mechanical kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used in terms of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass, with respect to 100 parts by mass of the pigment, from both the processing efficiency and the 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 used. However, since the temperature rises during salt milling and the solvent is easily evaporated, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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. It is preferable to use 5-1000 mass parts with respect to 100 mass parts of pigments, and, as for a water-soluble organic solvent, it is most preferable to use 50-500 mass parts.

  When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid at room temperature, preferably water insoluble, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

(Other dyes that can be used together)
Next, dyes that can be used in combination with the colored crude product of the present invention will be described. The dye which can be used in combination is preferably one having an oil-soluble dye, an acid dye or a basic dye.

(Oil-soluble dye)
When an oil-soluble dye is used, a xanthene dye or an anthraquinone dye is preferred from the viewpoint of lightness.
As the xanthene-based oil-soluble dyes, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, CI Solvent Red 44, I. Solvent Red 45, C. I. Solvent Red 46, C. I. Solvent Red 47, C. I. Solvent Red 48, C. I. Solvent Red 49, C. I. Solvent Red 72, C.I. Solven Red 73, C. I. Solvent Red 109, C. I. Solvent Red 140, C. I. Solvent Red 141, C. I. Solvent Red 237, C. I. Solvent Red 246, C. I. Solvent Violet 2 or CI Solvent Violet 10 and the like.

  Among them, Rhodamine-based oil-soluble dyes having high coloring properties, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, CI Solvent CI Solvent Red Red 237, C. I. Solvent Red 246, C. I. Solvent Violet 2 are more preferred.

  As anthraquinone-type oil-soluble dyes, CI Solvent Red 172, 222, CI Solvent Violet 60, etc. may be mentioned.

(Acid dye)
As the triarylmethane acid dyes, C. I. Acid Blue 1, 3, 5, 7, 9, 11, 15, 17, 19, 22, 22, 24, 38, 48, 75, 83, 90, 91, 93 93: 1, 100, 103, 104, 109, 110, 119, 147, 269, 123, 213, C. I. Direct Blue 41, C. I. Acid Violet 17, 19, 21, 23, 25, 38 , 49, 72, Direct Blue 41, and the like.

As the xanthene acid dyes, C.I. I. Acid red 51 (erythrosine (food red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (food red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among them, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388, or Rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among them, C.I. rhodamine acid dye is particularly preferred in that it is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. It is most preferred to use Acid Red 289.

  As the anthraquinone acid dye, CI Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 51, 53, 55, 56, 62, 68, 69, 78, 80 81: 1, 11, 124, 127, 127: 1, 140, 150, 175, 215, 230, 277, 344, C. I. Acid Violet 41, 42, 43, C. I. Acid Green 25, 27 Or direct violet 17 and the like.

As an azo acid dye, for example, CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
C. I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C. I. Acid Violet 11, 56, 58; C. I. Acid Yellow 1, 17, 18, 23, 25, 23, 36, 38, 42, 44, 54, 59, 72, 78, 151; C. I. Acid Brown 2, 4, 13, 248; C. I. Acid Blue 92, 102, 113, 117 and the like.

(Basic dye)
When a basic dye is used, a triarylmethane or xanthene dye is preferred in view of lightness.
As the triarylmethane basic dyes, C.I. C. I. Basic Violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta), C.I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victor Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), etc. may be mentioned. Among them, C.I. I. It is preferable to use basic blue 7, green 4, violet 1 and violet 3.

  As rhodamine-based basic dyes, C.I. Basic Red 1 (rhodamine 6G, 6GCP), 3, 8 (rhodamine G), C.I. I. Basic Violet 10 (rhodamine B) and the like. Among them, C.I. I. Basic Red 1, Violet 10, Violet 11 are preferably used.

  As flavin based basic dyes, C.I. Basic Yellow 1 As an auramine-based basic dye, C.I. Basic Yellow 2, 3 As the safranin-based basic dyes, C.I. Basic Red 2 As the phloxine-based basic dye, C.I. Basic Red 12; Examples of acridine-based basic dyes include C.I. Basic Yellow 5 As the oxazine-based basic dye, C.I. Basic Blue 3 As the thiazine-based basic dye, C.I. Basic Blue 24. Examples of methylene blue basic dyes include C.I. I. Basic Blue 9 (methylene blue FZ, methylene blue B), 25 (basic blue GO), 24 (new methylene blue NX), and the like. Among them, C.I. I. It is preferable to use Basic Yellow 1, Blue 9, Blue 24, and Blue 25.

  Examples of the azo-based basic dye include Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16, Basic Brown 17 and the like.

<Binder resin>
The coloring composition of the present invention contains a binder resin. The binder resin is one in which a coloring agent is dispersed, or one in which a salt-forming compound is dyed and permeated, and examples thereof include thermoplastic resins and thermosetting resins.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, and phenol resin.

  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 range of 400 to 700 nm in the visible light range. Moreover, since the coloring composition for color filters of this invention is a form of alkali development type coloring resist material, it is preferable to use the alkali-soluble vinyl-type resin which copolymerized the acidic group containing ethylenic unsaturated monomer.

  As alkali-soluble resin which copolymerized the acidic group containing ethylenic unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as an alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or An isobutylene / (anhydride) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, in particular an acrylic resin having an acidic group, is preferably used because it has high heat resistance and transparency.

  In order to improve the photosensitivity of an alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenic non-monomer, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. Further, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, since this has the effect of improving the solvent resistance of the resist material.

  As active energy ray curable resin which has an ethylenically unsaturated double bond, resin which introduce | transduced the unsaturated ethylenic double bond by the method of (a)-and (c) shown below, for example is mentioned.

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

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group. In addition, unsaturated ethylenic double bonds can be further increased by using, as the polybasic acid anhydride, ethahydrophthalic anhydride having maleic unsaturated double bonds, or maleic anhydride.

[Method (b)]
As a similar method of method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.
In this method, more hydroxyl groups derived from the unsaturated ethylenic monomer having an epoxy group are generated as compared with the method (a). When the resin having a cationic group in the side chain, which is used when obtaining the salt forming compound of the present invention, contains oxetanyl group or t-butyl group as a thermally crosslinkable functional group, the method is used as a binder resin ( Use of the resin obtained by b) is preferable because it exhibits higher heat resistance.

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

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

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethylisocyanate or 1,1-bis [(meth) acryloyloxy] ethylisocyanate, but are not limited thereto. Alternatively, two or more types can be used in combination.

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

  When using binder resin as a photosensitive composition, it is preferable to use resin of an acid value of 20-300 mgKOH / g from a dispersibility of a pigment and a salt-forming compound, permeability, developability, and a heat resistance viewpoint. If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mg KOH / g, fine patterns may not be left.

  The binder resin is preferably used in an amount of 30% by mass or more based on the total weight of the colorant (100% by mass) because the film forming property and the various resistances are good, and the colorant concentration is high and favorable. It is preferable to use it in an amount of 500% by mass or less because it can exhibit color characteristics.

<Thermosetting compound>
The coloring composition of the present invention can further contain a thermosetting compound in combination with a thermoplastic resin which is a binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts at the time of firing of the filter segment to increase the crosslink density of the coating film, and therefore the heat resistance of the filter segment The effect is improved, pigment aggregation at the time of filter segment firing is suppressed, and the contrast ratio is improved.

  As a thermosetting compound, for example, an epoxy compound and / or a resin, a benzoguanamine compound and / or a resin, a rosin modified maleic acid compound and / or a resin, a rosin modified fumaric acid compound and / or a resin, a melamine compound and / or a resin, Although a urea compound and / or resin, and a phenol compound and / or resin are mentioned, this invention is not limited to this. An epoxy compound and / or resin is preferably used in the color composition for color filters of the present invention.

The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxy Weight of benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensation products, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers of nylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone etc) ) Polycondensates with phenols, phenols and aromatic dimethanols (benzenedimethanol, α, α, α ', α'-benzenedimethanol, biphenyl dimethanol, α, α, α', α'-biphenyl di) Polycondensates with methanol etc.), Polycondensates of phenols with aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl etc), Polycondensates of bisphenols with various aldehydes, Alcohols Glycidyl and so on Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resin, glycidyl ester type epoxy resins, but are not limited to these would normally epoxy compound used. These may be used alone or two or more may be used.

  Commercially available products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (above). Are trade names; Japan Epoxy Resins Co., Ltd., TECHMORE VG3101L (trade names; Mitsui Chemical Co., Ltd.), EPPN-501H, 502H (trade names; Nippon Kayaku Co., Ltd.), JER 1032H60 (trade names) Japan Epoxy Resins Co., Ltd., JER 157S65, 157S70 (trade name; Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), JER 152, JER 154 (the above are products) Name: Japan Epoxy Resins Co., Ltd. , EOCN-102S, EOCN-103S, EOCN-104S, EOCN- 1020 (trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (trade names; manufactured by Daicel Chemical Industries, Ltd.) , Denacol EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (the trade names are manufactured by Nagase ChemteX Co., Ltd.) and the like. Although it is not limited to these.

  It is preferable that it is 0.5-300 mass parts with respect to 100 weight of coloring agents, and, as for the compounding quantity of an epoxy compound, it is more preferable that it is 1.0-50 mass parts. If it is less than 0.5 parts by mass, the heat resistance improvement effect is small, and if it is more than 300 parts by mass, problems may occur when forming filter segments by photolithography.

  Moreover, in order to assist hardening of a thermosetting compound, the coloring composition for color filters of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but the curing agent is not particularly limited thereto, and can react with a thermosetting compound. As long as it is a thing, you may use any hardening | curing agent. 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- The (Eg, 4-phenylimidazole), phosphorus compounds (eg, triphenylphosphine 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. It can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting compounds.

<Organic solvent>
The coloring composition of the present invention contains an organic solvent. The organic solvent makes it easy to disperse and infiltrate the colorant into the colorant carrier and apply it on a substrate such as a glass substrate to a dry film thickness of 0.2 to 5 μm to form a filter segment. Can be .

  As an organic solvent, for example, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methyl formamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, 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 monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, ethyl lactate and propylene glycol monomethyl are preferred because of good dispersion and dissolution of a salt forming compound of a dye having a fluorescence and a salt forming compound of a metal complex dye used in the present invention, a pigment optionally used and other dyes usable in combination. It is preferable to use glycol acetates such as ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and 3-methoxybutanol, and ketones such as cyclohexanone . In particular, it is most preferable to use 3-methoxybutanol from the viewpoint of solubility in a salt forming compound of a dye having a fluorescence used in the present invention or a salt forming compound of a metal complex dye.

  These organic solvents can be used alone or in combination of two or more. When it is set as 2 or more types of mixed solvents, it is preferable that 65-95 mass% of said preferable organic solvents are contained.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the coloring agent because it can adjust the coloring composition to an appropriate viscosity and form a filter segment having an intended uniform film thickness. Is preferred.

<Photopolymerizable monomer>
The coloring composition of the present invention may further be added with a photopolymerizable monomer and / or a photopolymerization initiator and used as a photosensitive coloring composition for a color filter.
The photopolymerizable monomer of the present invention includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin, and these can be used alone or in combination of two or more.

Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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 ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether 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 (Meth) acrylates, ester acrylates, (meth) acrylic esters of methylolated melamine, epoxy (meth) acrylates, urethane acrylates and other various acrylic esters and methacrylic 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, rh (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable monomers can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The compounding amount of the photopolymerizable monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability. .

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

As the photopolymerization initiator, 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 ben Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -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- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O (Acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) oxime ester compounds such as hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone; borate compounds; carbazole compounds; imidazole compounds Or titanocene compounds and the like are used.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required. The content of the photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for color filters of the present invention can contain a sensitizer.
As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-diethylaminobenzophenone and the like.
These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as needed.

   More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

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

<Multifunctional thiol>
The coloring composition for color filters of the present invention can contain a multifunctional thiol which acts as a chain transfer agent.
The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bis thioglycolate, ethylene glycol bis thiopropionate, trimethylol propane tris thio glycolate, trimethylol propane tris thio propionate, trimethylol propane tris (3-mercaptobutyrate), pentaerythritol tetrakis thio glycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapic acid -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination of two or more at any ratio as required.
The content of the multifunctional thiol is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass based on the total solid content of the coloring composition for color filter (100% by mass). . When the content of the polyfunctional thiol is less than 0.1% by mass, the effect of adding the multifunctional thiol is insufficient, and when it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition for color filters of the present invention can contain an antioxidant. In order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition for color filter from being oxidized and yellowed due to a heat process at the time of heat curing or ITO annealing, the antioxidant is the transmittance of the coating film. Can be raised. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

In the present invention, the "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, hindered phenol type or hindered amine type as an antioxidant. And phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylic acid ester, and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used.
Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents. Furthermore, more preferably, hindered phenol antioxidants, hindered amine antioxidants, or phosphorus antioxidants are used.
These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required. The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid weight of the coloring composition for a color filter (100% by mass) because the lightness and sensitivity are good.

<Amine compounds>
In addition, the coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.
As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate.
As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370 etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass based on the total weight of the coloring composition (100% by mass).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

  The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.

  Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene 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 stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

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

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine and the like. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 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-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.

<Method of Producing Colored Composition for Color Filter>
The coloring composition of the present invention contains a coloring agent in a coloring agent carrier and / or solvent such as a binder resin using a dispersing aid, if necessary, a kneader, 2-roll mill, 3-roll mill, ball mill, horizontal sand mill It can be finely dispersed and manufactured using various dispersing means such as a vertical sand mill, an annular type bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
An active energy ray-curable resin having an ethylenically unsaturated double bond may be added at the stage of preparing the colorant dispersion, and the same effect can be obtained even if it is added to the prepared colorant dispersion later. From the viewpoint of the stability of the coloring composition, it is preferable to add at the stage of preparing the photosensitive coloring composition.
When the solubility of coloring agents such as dyes is high, specifically, the solubility in the solvent used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is observed, it is finely dispersed and manufactured as described above. There is no need. In this case, the dispersion aid can be used simply by adding to and mixing with the colorant solution in which the dye or the like is dissolved.

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

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, it may contain a dispersing aid such as a resin-type dispersant, a dye derivative, a surfactant and the like as appropriate. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the coloring composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness and viscosity stability. It becomes good.

[Resin type dispersant]
The resin type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant, and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier Work to stabilize the Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, 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.

  As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer, a tertiary amino group in a side chain, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing 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, manufactured by BIC Chem. Japan. 167, 168, 170, 171, 174, 180, 181, 182, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2095, 2150, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., Japan Lubris SOLSPERSE-3000, 9000, 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 34750, 35100, 36600, 38500, 41000, 41090, 41090, 41090 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 458, 4008, 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 , 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4550, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

Moreover, as a resin type dispersing agent used by this invention, it is also preferable to contain following (S1) or (S2) as a resin type dispersing agent which has a carboxyl group.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride.
(S2) a weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Resin type dispersant which is united.

«Resin type dispersant (S1)»
The resin type dispersant (S1) can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406 and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at an end, and for example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used because the terminal hydroxyl group is preferably plural.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, has a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. Produces

«Resin type dispersant (S2)»
The resin type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, etc. For example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of the reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride can get. Among them, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride Preferably, it is a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

  (S1) and (S2) are differences in whether the introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although molecular weight etc. may differ somewhat depending on various conditions, if the raw material and the reaction conditions are the same, theoretically the same one can be obtained.

[Dye derivative]
Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines, compounds having a basic substituent, an acid substituent, or a phthalimidomethyl group which may have a substituent, for example, 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A 2001-335717, JP-A 2003- No. 128669, JP-A 2004-091497, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986, JP-A 2008-095007, JP-A 2008-195916 Patent Publication No. 4585581, etc. can be used. Al may be used either individually or in combination of two or more.

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

[Surfactant]
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene 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 stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

  When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, the added effect is difficult to be obtained, and when the content is more than 55 parts by mass, the dispersing agent may affect the dispersion due to an excess of the dispersing agent. .

<Removal of coarse particles>
The colored composition of the present invention was coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, a sintered filter, membrane filter, etc. It is preferable to carry out dust removal. Thus, the coloring composition preferably contains substantially no particles of 0.5 μm or more. 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 a filter segment formed using the coloring composition for a color filter of the present invention. Color filters include those comprising a red filter segment, a green filter segment, and a blue filter segment, or those comprising a magenta filter segment, a cyan filter segment, and a yellow filter segment.

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

<Method of manufacturing color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method.
Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as printing ink, it is low-cost as a manufacturing method of a color filter, and excellent in mass productivity. There is. Furthermore, with the development of printing technology, printing of fine patterns having high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, it is important to control the flowability of the ink on the printing press, and the viscosity of the ink can be adjusted by the dispersant and the extender pigment.

  When a filter segment is formed by photolithography, the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. The dry film is applied to a thickness of 0.2 to 5 μm by a method. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the developer is dipped in a solvent or an alkaline developer, or the developer is sprayed to remove an uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

  In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, 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 ultraviolet exposure sensitivity, after applying and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

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

  Before forming the color filter segments on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this invention as needed.

  The color filter is bonded to the opposing substrate using a sealing agent, and liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed, and a polarizing film or retardation film is formed on the outside of the substrate as necessary. By bonding, a liquid crystal display panel is manufactured.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), critical alignment (VA), and optically convensend bend (OCB). Etc. can be used in a liquid crystal display mode in which coloring is performed using a color filter.

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

(Average molecular weight of acrylic resin and acidic resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the acidic resin are THF as the developing solvent by GPC (HLC-8120GPC manufactured by Tosoh Corp.) equipped with an RI detector using a TSK gel column (manufactured by Tosoh Corp.) It is the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion which were measured using these.

(Acid dispersant, and acid value of acrylic resin)
The acid value of the acidic dispersant and the acrylic resin is a value obtained by converting the acid value (mg KOH / g) measured in accordance with the potentiometric titration method of JIS K 0070 into a solid content.

(Average molecular weight of basic resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin were measured using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, using SUPER-AW 3000 as a column, and 30 mM triethylamine and 10 mM LiBr as an eluent. The polystyrene equivalent number average molecular weight (Mn) and the weight average molecular weight (Mw) measured using the N, N-dimethylformamide solution of

(Amine value of basic resin)
The amine value of the vinyl resin type dispersant is a value obtained by converting the total amine value (mg KOH / g) measured in solid content in accordance with the method of ASTM D 2074.

<Manufacture of binder resin>
(Binder resin solution 1)
70.0 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device are attached to a separable four-necked flask, the temperature is raised to 80 ° C., the inside of the reaction vessel is purged with nitrogen, and then a dropping pipe 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 ("Alonix M110" manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and methoxypropyl acetate is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. It added and prepared binder resin solution 1. The weight average molecular weight (Mw) was 26000.

(Binder resin solution 2)
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 parts of azobisisobutyronitrile is added dropwise over 2.5 hours from the dropping tube at a temperature for 2.5 hours. The reaction was done.
Next, the inside of the flask is replaced with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone are added to 17.0 parts of acrylic acid, and the reaction is continued at 120 ° C. for 5 hours. The reaction was terminated when it reached .8, and a resin solution having a weight average molecular weight of about 12,000 was obtained.
Furthermore, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added to make the nonvolatile content to be 20% to prepare binder resin solution 2 .

<Manufacture of metal complex salt dyes>
(Compound having an anion represented by formula (6-1))
After adding 100 parts of water to 5.4 parts of a compound represented by the following formula (d-1), 2.0 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 9.5 parts of 35% aqueous sodium nitrite solution was added, and then 30.0 parts of 35% hydrochloric acid was added little by little and dissolved, and stirred for 2 hours to obtain a suspension containing a diazonium salt. Then, an aqueous solution of 6.3 parts of amidosulfuric acid dissolved in 50 parts of water was slowly added to quench excess sodium nitrite.
Then, 7.1 parts of a compound represented by the following formula (d-2) was suspended in 100 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding a 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of the dropwise addition, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.3 parts of a compound represented by the following formula (d-3).

Formula (d-1)

Formula (d-2)

Formula (d-3)

  10 parts of the compound of the formula (d-3) is dissolved in 100 parts of dimethylformamide and dissolved, and 3.7 parts of ammonium chromium (III) sulfate 12 water and 1.1 parts of sodium acetate are added, followed by heating for 4 and a half hours Refluxed. After cooling to room temperature, the reaction solution is poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration is dried at 60 ° C., and a sodium salt compound having an anion represented by the formula (6-1) I got 12.1 copies.

Formula (6-1)

<Production of Resin Having Cationic Group in Side Chain Represented by General Formula (X)>
(Resin P-1 having a cationic group in the side chain)
In a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 75.1 parts of isopropyl alcohol was charged, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, it was dissolved in 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt of methacrylic acid, and 23.4 parts of methyl ethyl ketone separately After equalizing 7.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), it was charged into a dropping funnel, attached to a four-neck separable flask, and dropped over 2 hours. Two hours after the end of dropping, it was confirmed that the polymerization yield was 98% or more, the weight average molecular weight (Mw) was 7300, and the mixture was cooled to 50 ° C. Thereafter, 14.3 parts of methanol was added to obtain a resin P-1 having a cationic group at a side chain of 40% by mass of the resin component.

(Preparation of Resin P-2 to 7 Having a Cationic Group in the Side Chain)
Hereinafter, resin P-2-7 which has a cationic group in a side chain were obtained like resin P-1 except having changed the monomer into the composition shown in Table 1.

The following monomers were used as monomers in Table 1.
MMA: methyl methacrylate,
n-BMA: n-butyl methacrylate,
2-EHMA: 2-ethylhexyl methacrylate,
HEMA: hydroxyethyl methacrylate,
MAA: methacrylic acid,
OXMA: 3- (methacryloyloxymethyl) 3-ethyl oxetane,
t-BuMA: tert-butyl methacrylate,
BzMA: benzyl methacrylate,
DMC78: Dimethylaminoethyl methyl chloride salt of methacrylic acid

<Production of salt forming compounds>
(Salt-forming compound D-1)
In the following procedure, C.I. I. A salt forming compound (D-1) comprising Acid Blue 40 and a resin (P-1) having a cationic group in the side chain was produced.
After adding resin (P-1) (a resin component is 40 mass%) which has a cationic group to 50 parts of side chains to 2000 parts of water and performing sufficient stirring mixing, it heats at 60 degreeC. Meanwhile, in 100 parts of water, 3.3 parts of C.I. I. Acid Blue 40 and 3.3 parts of C.I. I. An aqueous solution in which the solvent yellow 21 is dissolved is prepared and dropped little by little into the above resin solution. After the dropwise addition, the mixture is stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. In order to confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was judged that a salt forming compound was obtained with the point where bleeding was eliminated as the end point. After cooling to room temperature while stirring, suction filtration and washing with water are used as counter anions of a resin having a cationic group in the side chain and C.I. I. Acid Blue 40 or C.I. I. After removing the salt consisting of Solvent Yellow 21 and the cation, the salt-forming compound remaining on the filter paper is dried by a dryer to remove water, and 24.8 parts of C.I. I. Acid Blue 40 and C.I. I. The salt-forming compound (D-1) whose weight ratio (Z < ^- >) / (Y < ^- >) of the solvent yellow 21 is 1.0 was obtained. The weight concentration of the anionic dye contained in this salt forming compound was 12.4%.

(Salt-forming compound D-2 to 24)
Hereinafter, a salt forming compound in the same manner as the salt forming compound D-1 except that the type and composition of the resin having a cationic group in the side chain, the anionic dye and the pyrazolone azo dye are changed to the contents shown in Table 2 (D-2)-(D-24) It produced.

<Production of salt forming compounds for comparison>
(Salt-forming Compound D-25)
In the following procedure, C.I. I. A salt forming compound (D-25) comprising Acid Blue 40 and a resin (P-1) having a cationic group in the side chain was produced.
After adding resin (P-1) (a resin component is 40 mass%) which has a cationic group to 50 parts of side chains to 2000 parts of water and performing sufficient stirring mixing, it heats at 60 degreeC. Meanwhile, in 100 parts of water, 5.6 parts of C.I. I. An aqueous solution in which Acid Blue 40 is dissolved is prepared, and is dropped little by little into the above resin solution. After the dropwise addition, the mixture is stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. In order to confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was judged that a salt forming compound was obtained with the point where bleeding was eliminated as the end point. After cooling to room temperature while stirring, suction filtration and washing with water are used as counter anions of a resin having a cationic group in the side chain and C.I. I. After removing the salt composed of acid blue 40 counter cation, the salt-forming compound remaining on the filter paper is dried by using a drier to remove water, and 25.0 parts of a salt-forming compound (D-25) is obtained. The The weight concentration of the anionic dye contained in this salt forming compound was 21.8%.

(Salt-forming Compound D-26 to 33)
Hereinafter, a salt forming compound (D-26) in the same manner as the salt forming compound D-25 except that the resin having a cationic group in the side chain and the type and composition of the anionic dye are changed to the contents shown in Table 3 ~ (D-33) It produced.

(Salt-forming compound D-34 of SO 62 and cationic resin)
A resin (P-7) having a cationic group in 50 parts of side chains is added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 8.5 parts of C.I. I. Prepare an aqueous solution in which solvent orange 62 is dissolved, and slowly add it to the above resin solution. After the dropwise addition, the mixture is stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. In order to confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was judged that a salt forming compound was obtained with the point where bleeding was eliminated as the end point. After cooling to room temperature while stirring, suction filtration and washing with water are used as counter anions of a resin having a cationic group in the side chain and C.I. I. Solvent Orange After removing salts composed of 62 pairs of cations, the salt-forming compound remaining on the filter paper is dried by a dryer to remove water, and 26.5 parts of C.I. I. A salt forming compound (D-34) of Solvent Orange 62 and a resin (P-7) having a cationic group in the side chain was obtained. The weight concentration of the anionic dye contained in this salt forming compound was 29.7%.

(A salt forming compound D-35 of BV10 and SO62)
In 100 parts of water, 10.0 parts of C.I. I. An aqueous solution in which Basic Violet 10 is dissolved and 15.0 parts of C.I. I. An aqueous solution in which solvent orange 62 was dissolved was prepared. Thereafter, the two aqueous solutions were mixed at room temperature and stirred for about 1 hour. Thereafter, unreacted C.I. I. Basic Violet 10 and C.I. I. After the solvent orange 62 is removed, the salt-forming compound remaining on the filter paper is dried by a dryer to remove water, and 21.2 parts of C.I. I. Basic Violet 10 and C.I. I. A salt forming compound (D-35) with solvent orange 62 was obtained. The weight concentration of the anionic dye contained in this salt forming compound was 40.0%.

(CI Solvent Yellow 21 Solution S-1)
5.0 parts of C.I. I. After dissolving the solvent yellow 21, the solution was filtered through a 1.0 μm filter to prepare a 5.0% by mass methanol solution (S-1).

(CI Solvent Orange 62 solution S-2)
5.0 parts of C.I. I. After dissolving the solvent orange 62, the solution was filtered through a 1.0 μm filter to prepare a 5.0% by mass methanol solution (S-2).

(CI solvent orange 56 solution S-2)
5.0 parts of C.I. I. After dissolving the solvent orange 56, the solution was filtered through a 1.0 μm filter to prepare a 5.0% by mass methanol solution (S-3).

C. I. Anion Structure of Solvent Yellow 21: General Formula (4-3)

C. I. Anion structure of Solvent Orange 62: General Formula (4-1)

C. I. Anion structure of Solvent Orange 56: General Formula (5-1)

Anion structure represented by the general formula (6-1)

<Production of Colored Composition for Color Filter>
Example 1 Coloring Composition DP-1
12.10 parts of salt-forming compound (D-1), 14.52 parts of binder resin solution 1, and 73.38 parts of cyclohexanone are stirred and mixed for 30 minutes, and the anionic dye in solid content is 10.0 The coloring composition (DP-1) was manufactured so that it might become mass%.

(Examples 2 to 24; coloring composition DP-2 to 24)
Thereafter, the anionic dye in the solid content is 10.0% by mass in the same manner as in Example 1 except that the salt-forming compound, the binder resin solution 1 and the cyclohexanone are changed to those shown in Table 4. Colored compositions (DP-2) to (DP-24) were produced.

(Comparative example 1; coloring composition DP-25)
6.88 parts of salt forming compound (D-25), C.I. I. 30.00 parts of 5 mass% methanol solution (S-1) of solvent yellow 21, 33.10 parts of binder resin solution 1, and 30.02 parts of cyclohexanone are mixed by stirring for 30 minutes to obtain anions in solid content Pigment to 10.0% by mass, and C.I. to anionic dye in solid content. I. The coloring composition (DP-25) was manufactured so that the ratio of the solvent yellow 21 might be 1.0.

(Comparative Examples 2 to 13; Colored Composition DP-26 to 37)
The contents shown in Table 5 below are salt forming compounds, pyrazolone azo dye methanol 5% by mass solution, ratio of pyrazolone azo dye to anionic dye in solid content, types and compositions of binder resin solution 1 and cyclohexanone. Colored compositions (DP-26) to (DP-37) were produced in the same manner as in the colored composition DP-25, except that the anionic dye in the solid content was 10.0% by mass, except for the change. .

(Comparative example 14; coloring composition DP-38)
5.88 parts of the salt forming compound (D-33) of AR 52, 1.52 parts of the salt forming compound (D-34) of SO 62, 38.01 parts of the binder resin solution 1, and 54.59 parts of cyclohexanone The mixture was stirred and mixed for 30 minutes to obtain 10.0% by mass of the anionic dye in the solid content, and C.I. I. The coloring composition (DP-38) was manufactured so that the ratio of the solvent orange 62 would be 0.3.

(Comparative example 15; coloring composition DP-39)
3.75 parts of salt forming compound (D-35) of BV10 and SO62, 56.25 parts of binder resin solution 1, and 40.00 parts of cyclohexanone are mixed by stirring for 30 minutes, and cationic system in solid content The amount of xanthene dye is 10.0% by mass and C.I. I. The coloring composition (DP-38) was manufactured so that the ratio of the solvent orange 62 would be 1.0.

<Evaluation of color composition for color filter>
About the obtained coloring composition (DP-1-39), the test regarding CR, heat resistance, solvent resistance, and filterability was done with the following method. The results are shown in Table 6.

(CR evaluation of coating film)
The obtained colored composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, baked in an oven at 230 ° C. for 30 minutes, and the film thickness of the heat-treated film is the surface shape Three coated substrates were prepared so that the film thickness was about 1.5 μm as measured using a measuring apparatus “Dektak 8 (manufactured by Veeco)”. The film thickness and contrast ratio of each substrate were measured, and the contrast at a film thickness of 1.5 μm was determined by the first-order correlation method from data of three points. The judgment criteria are as follows. Note that ◎ is a very good level, ○ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
:: CR ≧ 17000 or more ○: CR = 15,000 or more, less than 17000 Δ: CR = 12000 or more, less than 15000 ×: CR less than 12000

(Evaluation of heat resistance of coating film)
The obtained colored composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, baked in an oven at 230 ° C. for 30 minutes, and the film thickness of the heat-treated film is the surface shape Three coated substrates were manufactured so that the film thickness was about 2.0 μm as measured using a measuring apparatus “Dektak 8 (manufactured by Veeco)”. The chromaticity ([L * (1), a * (1), b * (1)) at the C light source of the obtained coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. After that, heat at 230 ° C. for 1 hour as a heat resistance test, and measure the chromaticity ([L * (2), a * (2), b * (2)]) at the C light source, according to the following formula The color difference ΔEab * was determined and evaluated according to the following judgment criteria. Note that ◎ is a very good level, ○ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
:: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 C: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of solvent resistance of coating film)
The obtained colored composition is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, baked in an oven at 230 ° C. for 30 minutes, and the film thickness of the heat-treated film is the surface shape Three coated substrates were manufactured so that the film thickness was about 2.0 μm as measured using a measuring apparatus “Dektak 8 (manufactured by Veeco)”. The chromaticity ([L * (1), a * (1), b * (1)) at the C light source of the obtained coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. After that, the coating film obtained as a chemical resistance test is immersed in 1-methyl-2-pyrrolidone for 30 minutes, and after that, the 1-methyl-2-pyrrolidone is washed with pure water, and then the chromaticity at C light source ( [L * (2), a * (2), b * (2)] was measured, and the color difference ΔEab * was determined by the following formula, and evaluated based on the following determination criteria. Note that ◎ is a very good level, ○ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
:: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 C: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of filterability)
10 g of the obtained coloring composition is passed through a filter (φ 0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), and the amount obtained through the filter is measured and evaluated according to the following judgment criteria did.
:: filtration amount is 8.0 g or more O: filtration amount is 5.0 g or more and less than 8.0 g Δ: filtration amount is 3.0 g or more and less than 5.0 g ×: filtration amount is 3.0 g or less

By making the anionic dye and the metal complex dye exist in the same resin molecule by salt formation, the distance between the two dyes becomes close, and the fluorescence quenching ability of the metal complex dye is more effectively exhibited, which is high. The coloring composition of contrast ratio was able to be obtained (Examples 1 to 24). In particular, by having benzyl methacrylate in the cationic resin, the arrangement of the anionic dye and the metal complex dye becomes regular via the benzene ring to exhibit a higher quenching ability and show a very high contrast ratio. (Examples 20 to 24). On the other hand, when the metal complex dye is not present in the same resin and is added as a solution, the distance from the fluorescent anionic dye is increased, and sufficient quenching ability can not be obtained, resulting in a low contrast ratio. (Comparative Examples 1 to 13).
Moreover, heat resistance and solvent resistance became a comparatively favorable result as shown in Examples 1-24 by forming metal salt dyestuff with bad heat resistance and solvent resistance with resin. Among them, when the content of the metal complex dye to the anionic dye is reduced, the solvent resistance shows very good results (Examples 10 to 24). Furthermore, when the metal complex dye is changed to the structure represented by the general formula (4-1) or (5-1), the heat resistance is improved (Examples 14 to 24). On the other hand, in Comparative Examples 1 to 13 in which the metal complex dye was not salted with the resin, good results in both heat resistance and solvent resistance were not obtained.

In a system in which an anionic dye and a metal complex dye are salted with different resins as shown in Comparative Example 14, the improvement effect of the heat resistance and solvent resistance of the metal complex dye by the salt formation can be seen, but the same resin Since the anionic dye and the metal complex dye were not present in the molecule, the quenching ability was not sufficient and showed a low contrast ratio. Further, since the distance between the two dyes is long, there is no interaction between the dye molecules, and the heat resistance and solvent resistance are slightly inferior to those of Example 22 having the same composition.
As shown in Comparative Example 15, in the structure in which the cationic xanthene dye and the metal complex dye are formed directly, since the distance between the two dyes is close, a very high CR is shown, but a high molecular weight molecule like resin The heat resistance and solvent resistance were poor because the salt formation was not so.
In addition, the presence of the anionic dye and the metal complex dye in the same resin greatly improved the solubility in the solvent and the compatibility with the binder resin, and resulted in a colored composition with very good filterability. On the other hand, the filterability shown in the comparative example was poor.

<Production of Photosensitive Colored Composition for Color Filter>
(Example 25; photosensitive coloring composition DR-1)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali-developable resist material (DR-1).
Salt-forming compound (D-1): 12.10 parts Binder resin solution 2: 9.98 parts Trimethylolpropane triacrylate: 0.75 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corp.): 0.15 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.008 parts Cyclohexanone: 21.25 parts Propylene glycol monomethyl ether acetate: 55.76 copies

(Examples 26 to 48; photosensitive coloring composition DR-2 to 24)
(Comparative examples 16 to 30; photosensitive coloring composition DR-25 to 39)
Photosensitive coloring composition DR except that the salt-forming compound, binder resin solution 2, trimethylolpropane triacrylate, photopolymerization initiator, sensitizer, cyclohexanone, and propylene glycol monomethyl ether acetate are changed to the contents shown in Table 7. Photosensitive coloring compositions (DR-2) to (DR-39) were produced in the same manner as -1.

<Evaluation of photosensitive coloring composition for color filter>
About the obtained colored composition (DR-1-39), the test regarding CR, heat resistance, solvent resistance, and filterability was done with the following method. The results are shown in Table 8.

(CR evaluation of coating film)
The obtained photosensitive coloring composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, exposed to ultraviolet light at an exposure dose of 50 mJ / cm ² , and then 0.2 at 23 ° C. Spray development for 30 seconds in a mass% sodium carbonate aqueous solution, and baking for 30 minutes at 230 ° C. in an oven, and the film thickness of the heat-treated film is measured using a surface shape measuring apparatus “Dektak 8 (manufactured by Veeco)” A coated substrate of three photosensitive coloring compositions was prepared to have a thickness of about 1.5 μm. The film thickness and contrast ratio of each substrate were measured, and the contrast at a film thickness of 1.5 μm was determined by the first-order correlation method from data of three points. The judgment criteria are as follows. Note that ◎ is a very good level, ○ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
:: CR ≧ 17000 or more ○: CR = 15,000 or more, less than 17000 Δ: CR = 12000 or more, less than 15000 ×: CR less than 12000

(Evaluation of heat resistance of coating film)
The obtained photosensitive coloring composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, exposed to ultraviolet light at an exposure dose of 50 mJ / cm ² , and then 0.2 at 23 ° C. Spray development for 30 seconds in a mass% sodium carbonate aqueous solution, and baking for 30 minutes at 230 ° C. in an oven, and the film thickness of the heat-treated film is measured using a surface shape measuring apparatus “Dektak 8 (manufactured by Veeco)” A coated substrate of three photosensitive coloring compositions was prepared to have a thickness of about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)) at the C light source of the obtained coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. After that, heat at 230 ° C. for 1 hour as a heat resistance test, and measure the chromaticity ([L * (2), a * (2), b * (2)]) at the C light source, according to the following formula The color difference ΔEab * was determined and evaluated according to the following judgment criteria. Note that ◎ is a very good level, ○ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
:: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 C: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of solvent resistance of coating film)
The obtained photosensitive coloring composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, exposed to ultraviolet light at an exposure dose of 50 mJ / cm ² , and then 0.2 at 23 ° C. Spray development for 30 seconds in a mass% sodium carbonate aqueous solution, and baking for 30 minutes at 230 ° C. in an oven, and the film thickness of the heat-treated film is measured using a surface shape measuring apparatus “Dektak 8 (manufactured by Veeco)” A coated substrate of three photosensitive coloring compositions was prepared to have a thickness of about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)) at the C light source of the obtained coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. After that, the coating film obtained as a chemical resistance test is immersed in 1-methyl-2-pyrrolidone for 30 minutes, and after that, the 1-methyl-2-pyrrolidone is washed with pure water, and then the chromaticity at C light source ( [L * (2), a * (2), b * (2)] was measured, and the color difference ΔEab * was determined by the following formula, and evaluated based on the following determination criteria. Note that ◎ is a very good level, ○ is a good level, Δ is a practical level, and x is a level not suitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
:: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 C: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of filterability)
10 g of the photosensitive coloring composition obtained is passed through a filter (φ 0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), and the amount obtained through the filter is measured, and the following judgment criteria It evaluated by.
:: filtration amount is 8.0 g or more O: filtration amount is 5.0 g or more and less than 8.0 g Δ: filtration amount is 3.0 g or more and less than 5.0 g ×: filtration amount is 3.0 g or less

  Similar results to those of the colored composition were obtained. By making an anionic dye and a metal complex dye coexist in the same resin molecule, a photosensitive coloring composition having high contrast ratio, heat resistance, solvent resistance and filterability could be obtained.

<Manufacture of color filter>
(Preparation of a red photosensitive coloring composition (RR-1))
A mixture of the following composition is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5 The mixture was filtered through a 0 μm filter to prepare a red colored composition (RP-1).
Red pigment (CI pigment red 254) 12.0 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Corp.) 1.0 part Binder resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced the red photosensitive coloring composition (RR-1).
Red colored composition (RP-1) 30.0 parts Red colored composition (D-20) 4.4 parts Binder resin solution 2 2.9 parts Photopolymerizable monomer ("ALONIX M400" manufactured by Toagosei Co., Ltd.) 2.3 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corp.) 1.5 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.3 parts ethylene glycol monomethyl ether acetate 58.6 Department

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture of the following composition is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5 The mixture was filtered through a 0 μm filter to prepare a blue coloring composition (BP-1).
Blue pigment (CI pigment blue 15: 6) 7.2 parts Purple pigment (CI pigment violet 23) 4.8 parts Resin type dispersant (manufactured by BASF, "EFKA 4300") 1.0 part binder resin Solution 1 17.5 parts Propylene glycol monomethyl ether acetate 69.5 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced the blue photosensitive coloring composition (RB-1).
Blue colored composition (BP-1) 34.0 parts Binder resin solution 2 7.6 parts Photopolymerizable monomer ("Alonix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Corporation) Irgacure 907 ") 2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 52.7 parts

(Preparation of green photosensitive coloring composition (RG-1))
A mixture of the following composition is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5 The mixture was filtered through a 0 μm filter to prepare a green coloring composition (GP-1).
Green pigment (CI pigment green 58) 12.0 parts Resin type dispersant ("EFKA 4300" manufactured by BASF Corp.) 1.0 part Binder resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced the green photosensitive coloring composition (RG-1).
Green coloring composition (GP-1) 34.0 parts Binder resin solution 15.2 parts Photopolymerizable monomer ("Alonix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Corp.) Irgacure 907 "2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 45.1 parts

  A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was coated on the substrate to a film thickness of 2.0 μm by a spin coater to form a colored film. The film was irradiated with ultraviolet light of 300 mJ / cm 2 through a photomask using an extra-high pressure mercury lamp. Next, after spray development with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate to remove an unexposed portion, the substrate is washed with ion exchanged water and heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, the blue photosensitive coloring composition (RB-1) of the present invention is used to form a blue filter segment, and then the green photosensitive coloring composition (RG-1) is applied to each to form a blue color. Segments, green segments were formed to obtain color filters.

  By using the photosensitive coloring composition of the present invention, the contrast ratio, heat resistance and solvent resistance of the color filter can be improved and can be suitably used.

Claims (8)

It is a coloring composition for color filters containing a coloring agent, a binder resin, and an organic solvent, and the coloring agent is a structural unit represented by the following general formula (1) in one molecule, and the following general formula (2) The coloring composition for color filters containing the salt-forming compound which has a structural unit represented.
General formula (1)
[In general formula (1), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. The R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a good alkenyl group or a substituted group may have a substituent, R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R ₅ -or -COO-R _5- , and R ₅ represents an alkylene group. Y < ^- > represents an anionic dye (however, except for anions represented by the following general formula (4) to the following general formula (6)). ]

General formula (2)
[In general formula (2), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. The R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an aryl group which may have a good alkenyl group or a substituted group may have a substituent, R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R ₅ -or -COO-R _5- , and R ₅ represents an alkylene group. Z ⁻ represents an anion having at least one structure selected from the group consisting of the following general formula (4), the following general formula (5) and the following general formula (6). ]

General formula (4)
[In general formula (4), R _{10 to} R ₂₇ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₄₀₁ , -SO ₃ H or an -SO ₂ CH _3. R ₂₈ and R ₂₉ each independently represent a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₄₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₄₀₁ and R ₄₀₂ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or an alkoxyalkyl group having 2 to 15 carbon atoms. Each of A _{1 to} A ₄ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M. M represents Cr or Co. n represents an integer of 1 to 5; ]

General formula (5)
[In general formula (5), R _{31 to} R ₃₉ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a halogen atom, -SO ₂ NHR ₅₀₁ , -SO ₃ H or -SO ₂ CH ₃ is represented. R ₄₀ represents a hydrogen atom, a methyl group, an ethyl group, -SO ₂ NHR ₅₀₂ , -SO ₃ H or -SO ₂ CH ₃ . Each of R ₅₀₁ and R ₅₀₂ independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms. Each A ₅ and A ₆ are independently, * - O -, * - O-CO -, * - represents a CO-O-. * Represents a bond with M ₁ . M ₁ represents Cr or Co. n ₁ represents an integer of ₁ to 2; ]

General formula (6)
[In the general formula (6), R ₄₂ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is —OH, —OR ₆₀₁ , —CO— OR ₆₀₂ , -O-COR ₆₀₃ , -CONR ₆₀₄ R ₆₀₅ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, and -CH contained in the saturated hydrocarbon group _2- may be replaced by at least one of -O- and -CO-. R ₄₃ represents a hydrogen atom, -CN or -CONH ₂ . R ₄₄ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom. R _{45 to} R ₄₈ are each independently -R ₆₀₆ , -OR ₆₀₇ , -CO-OR ₆₀₈ , -COR ₆₀₉ , -OCO-OR ₆₁₀ , -O-COR ₆₁₁ , -CN, -NO ₂ , a halogen atom, It represents a _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 612 R 613 , or -NR ₅₂ R _53. R ₄₅ and R ₄₆ , R ₄₆ and R ₄₇ , and R ₄₇ and R ₄₈ may be combined with each other to form a 6 to 7-membered ring containing a benzene ring. R _{601 to} R ₆₁₃ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms And a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted by -OR ₅₁ . R ₅₁ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. R ₅₂ and R ₅₃ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms or a tetrahydrofurfuryl group. R ₅₂ and R ₅₃ may be bonded to each other to form a ring containing a nitrogen atom. Each of A _{7 to} A ₁₀ independently represents * -O-, * -O-CO- or * -CO-O-. * Represents a bond with M ₂ . M ₂ represents Cr or Co. n ₂ represents an integer of 1 to 5. ] Y in the general formula (1) ^- is a color filter for coloring composition according to claim 1 is a xanthene-based anionic dyes. The color filter according to claim 1 or 2, wherein the salt forming compound further has a structural unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, and a t-butyl group. Coloring composition. Y in salt formation compound ^- and Z ^- the weight ratio of ^(Z - / Y ^-) is 0.1 to 0.8, a color filter coloring composition according to any one of claims 1 to 3. Z in the general formula (2) ^- is of the formula (4-1), and an anion having at least one structure selected from the group consisting of the formulas (5-1), any one of claims 1 to 4 The coloring composition for color filters as described in-.
Formula (4-1)

Formula (5-1)
The coloring composition for color filters according to any one of claims 1 to 5, wherein the salt forming compound further has a structural unit derived from benzyl methacrylate. The coloring composition for color filters according to any one of claims 1 to 6, further comprising a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising a filter segment formed of the coloring composition for color filter according to any one of claims 1 to 7 on a substrate.