JP6160831B2 - Coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like due to their thinness, and recently they have been rapidly spread to television applications. For television applications, it is required to further improve the performance such as brightness and contrast, and further improvement of the transmittance and enhancement of the contrast are desired for the color filter which is a member of the color liquid crystal display device. ing.

  As a method for producing the color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or by forming a transparent electrode of a predetermined pattern in advance, and using a pigment-containing resin dissolved and dispersed in a solvent by voltage application Electrodeposition method for ionization and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, and coloring composition for color filter in which colorant such as pigment is dispersed in photoresist material The pigment dispersion method is known, and recently, the pigment dispersion method has become mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal due to light scattering by the pigment particles, resulting in a decrease in brightness and contrast of the color liquid crystal display device. There is a problem that it is easy.

In order to solve the above problems, for example, Patent Document 1 proposes the use of a xanthene dye having a specific structure. However, the proposed xanthene dyes have many problems as coloring compositions for color filters and are difficult to put into practical use. In order to supplement the heat resistance and organic solvent solubility of this xanthene dye, studies on improving the xanthene dye are widely conducted. For example, Patent Document 2 succeeds in significantly improving heat resistance by using a xanthene dye in the form of a dye multimer, but the colorant purity is low because of the form of the dye multimer. Therefore, the coloring composition for color filters is insufficiently colored and is difficult to put into practical use. In addition, the solubility of the dye multimer in the organic solvent is remarkably improved, but there is also a problem that the voltage holding ratio is remarkably lowered because the dye multimer is easily oozed into the liquid crystal.
Therefore, in order to improve heat resistance, organic solvent solubility, and voltage holding ratio while maintaining coloring power, studies have been made to introduce a polymerizable unsaturated group into the coloring portion of the xanthene dye. (Patent Document 3) However, in this examination content, the voltage holding ratio and coloring power are greatly improved as compared with Patent Document 2, but the contrast ratio is very low due to the fluorescence and the light resistance is also poor. Practical application as a coloring composition for color filters is still difficult.

JP 2008-242311 A JP 2012-32754 A JP 2013-178478 A

  An object of the present invention is to provide a coloring composition for a color filter excellent in light resistance, contrast ratio, heat resistance and voltage holding ratio, and a color filter in which no foreign matter is generated on the coating film.

  As a result of intensive studies to solve the above problems, the present inventors have found that the coloring composition for color filters containing the specific xanthene dye (general formula (1)) has excellent light resistance and contrast. It has been found that it has a ratio, a voltage holding ratio, and heat resistance, and the present invention has been made based on this finding.

  That is, the present invention is a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is a xanthene dye represented by the following general formula (1). The present invention relates to a color filter coloring composition.

General formula (1)
[R ¹ and R ^{2 in} General Formula (1) each independently represent a hydrogen atom, an aryl group which may have a substituent, or an alkyl group which may have a substituent. R ¹ and R ² may be linked to form a cyclic structure. A represents a divalent linking group, and B represents an oxygen atom or a nitrogen atom having a hydrogen atom or a substituent. R ^{3 to} R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms. Or a phenyl group which may have a substituent. R ^{7 to} R ⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a chlorine atom. p and q each independently represent an integer of 1 to 3, and r represents an integer of 1 to 4.
Anion ⁻ represents an organic or inorganic anion. ]

  In addition, the present invention relates to the coloring composition for a color filter, wherein in the formula (1), A is an alkylene group which may have a substituent, and B is an oxygen atom.

In addition, the present invention relates to the coloring composition for a color filter, wherein, in the formula (1), Anion ⁻ is a fluorine group-containing boron anion.

In the present invention, the xanthene dye is
In the acryloyl group of the acryloyl group-containing compound obtained by esterification reaction between the carboxyl group of the compound represented by the general formula (2) and the hydroxyl group of the compound having a hydroxyl group and an acryloyl group,
The present invention relates to a coloring composition for a color filter, which is a xanthene dye obtained by Michael addition reaction of an amino group of a primary amine compound or a secondary amine compound.

General formula (2)

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the color filter coloring composition.

  In the present invention, by using a coloring composition for a color filter containing the xanthene dye specific to the present application (represented by the general formula (1)), excellent light resistance, contrast ratio, heat resistance, voltage holding Rate can be obtained.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, or “(meth) acrylate”, unless otherwise specified, It shall represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid" or "acrylate and / or methacrylate". Further, “CI” in this specification means a color index (CI).

<Colorant>
The colored composition for a color filter of the present invention has excellent heat resistance, contrast ratio, voltage holding ratio, and light resistance by including the xanthene dye represented by the general formula (1). It is also preferable to use a pigment or dye in combination.

[Xanthene Dye Represented by General Formula (1)]
The xanthene dye of the present invention is a compound represented by the general formula (1).

General formula (1)
[R ¹ and R ^{2 in} General Formula (1) each independently represent a hydrogen atom, an aryl group which may have a substituent, or an alkyl group which may have a substituent. R ¹ and R ² may be linked to form a cyclic structure. A represents a divalent linking group, and B represents an oxygen atom, or a nitrogen atom having a hydrogen atom or a substituent. R ^{3 to} R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms. Or a phenyl group which may have a substituent. R ^{7 to} R ⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a chlorine atom. p and q each independently represent an integer of 1 to 3, and when p and q are integers of 2 or more, a plurality of p and q may be the same or different. R represents an integer of 1 to 4, and when r is an integer of 2 or more, a plurality of r may be the same or different. Anion ⁻ represents an organic or inorganic anion. ]

The aryl group in R ¹ and R ² includes a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentaenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tannaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, and a heptaenyl group. Group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group Group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexyl group Phenyl group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.

  These aryl groups may have a substituent. In this case, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an aryl group.

As the alkyl group in R ¹ and R ² , for example, an alkyl group having about 1 to 20 carbon atoms can be used. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, Examples include a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group.

  These alkyl groups may have a substituent. In this case, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an aryl group.

R ¹ and R ² may be linked to form a cyclic structure. When a ring is formed, a heterocyclic compound containing a nitrogen group is formed. Examples of the heterocyclic ring containing a nitrogen group include an aziridine ring, azetidine ring, azeto ring, pyrrole ring, pyrrolidine ring, piperidine ring, pyridine ring, hexamethyleneimine ring, azepine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole. Ring, thiazine ring, imidazoline ring, pyrazine ring, morpholine ring, indole ring, isoindole ring, benzoimidazole ring, purine ring, carbazole ring and the like. From the viewpoints of contrast ratio, light resistance, voltage holding ratio, and heat resistance, a morpholine ring and a pyridine ring are preferable.

Examples of the alkyl group having 1 to 8 carbon atoms in R ^{3 to} R ⁶ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl group, A tertiary amyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, and the like can be given. Especially, a C1-C6 alkyl group is preferable and a C1-C4 alkyl group is preferable.
Examples of the cycloalkyl group having 3 to 8 carbon atoms in R ^{3 to} R ⁶ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, a cycloalkyl group having 5 to 7 carbon atoms is preferable, and a cyclohexyl group is more preferable.

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, and the phenyl group in R ^{3 to} R ⁶ may have a substituent. Examples of the substituent include a halogen atom, —R ¹⁰ , —OH, —OR ¹⁰ , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁰ , —SO ₃ R ¹⁰ —SO. Preferred examples include ₂ NHR ¹¹ , —SO ₂ NR ¹¹ R ¹² , —SO ₃ − and the like.

Wherein, R ¹⁰ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —. May be. R ¹¹ and R ¹² each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms (preferably 3 to 8 carbon atoms), or -G. Or a heterocyclic group having 2 to 10 carbon atoms formed by bonding of R ¹¹ and R ¹² to each other. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -G, -CH = CH ₂ or -CH = CHR ¹⁰ , and the alkyl group and cycloalkyl The methylene group contained in the group may be substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —, and the hydrogen atom contained in the heterocyclic group is substituted with —R ¹⁰ , —OH or —G. May be. M represents a sodium atom or a potassium atom. G represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. However, the hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is —OH, —R ¹⁰ , —OR ¹⁰ , —NO ₂ , —CH═CH ₂ , —CH═CHR ¹⁰ or a halogen atom. May be substituted.

The saturated hydrocarbon group for R ¹⁰ may be linear, branched, or cyclic as long as it has 1 to 10 carbon atoms, and may have a bridged structure. Specific examples include nonyl group, decanyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecanyl group, in addition to the same alkyl group as R ^{3 to} R ⁶ . Examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group.
Specific examples of —CO ₂ R ¹⁰ which is a substituent of the alkyl group, cycloalkyl group and phenyl group in R ^{3 to} R ⁶ include methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxy Examples thereof include a carbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Specific examples of —SO ₃ R ¹⁰ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group.

Specific examples of the heterocyclic group formed by combining R ¹¹ and R ¹² with each other include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline, carbazole, phenanthridine, acridine, phenothiazine and the like. .

  Specific examples of the aromatic hydrocarbon group for G include a phenyl group, a naphthyl group, and an azulenyl group. Specific examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group, an oxazolyl group, an isoxazol group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, and a pyrimidyl group. it can.

Examples of the alkyl group having 1 to 8 carbon atoms in R ^{7 to} R ⁹ include the same ones as described above. p and q represent an integer of 1 to 3, and when p and q are integers of 2 or more, a plurality of p and q may be the same or different. Moreover, r shows the integer of 1-4, and when r is an integer greater than or equal to 2, several r may be same or different.

The divalent linking group in the general formula (1) represents an alkylene group which may have a substituent or an arylene group which may have a substituent. The alkylene group includes a linear or cyclic group. . The linear alkylene group is preferably an alkylene group having 1 to 18 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. The cyclic alkylene group is preferably a cyclic alkylene group having 3 to 7 carbon atoms, and more preferably a cyclopropylene group or a cyclohexylene group. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracene group, and a phenylene group is preferable.
Examples of the substituent include an alkyl group. This alkyl group may have a substituent, and the substituent is preferably a hydroxyl group, a carboxyl group, an alkoxy group, or a (meth) acryloyl group.

The xanthene dye represented by the general formula (1) of the present invention is a compound having a “carboxyl group” of the compound represented by the general formula (3) and a hydroxyl group and an acryloyl group represented by the general formula (4). To give a general formula (5) as an intermediate. For esterification, a known method can be applied. Furthermore, the intermediate represented by the general formula (5) thus obtained and the amine compound represented by the general formula (6) are Michael-added, whereby the xanthene dye represented by the general formula (1) is obtained. Can be obtained. (Reaction Scheme 1) A known method can be applied to the Michaelization reaction.
R ^{1 to} R ⁹ , A, B, Anion ⁻ , p, q, and r in the general formulas (3) to (6) are the same as those in the general formula (1).

(Reaction Scheme 1)

General formula (3)
[R ^{3 to} R ⁶ in General Formula (3) are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted carbon atom. The cycloalkyl group of number 3-8, or the phenyl group which may have a substituent is shown. R ^{7 to} R ⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a chlorine atom. p and q represent an integer of 1 to 3, and when p and q are integers of 2 or more, a plurality of p and q may be the same or different. Moreover, r shows the integer of 1-4, and when r is an integer greater than or equal to 2, several r may be same or different. Anion ⁻ represents an organic or inorganic anion. ]

[Compound having a hydroxyl group and an acryloyl group]
The compound having a hydroxyl group and an acryloyl group is a compound represented by the general formula (4).

General formula (4)
[A in the general formula (4) represents a divalent linking group, and B represents an oxygen atom, or a hydrogen atom or a nitrogen atom having a substituent. ]

  Specific examples of the compound having a hydroxyl group and an acryloyl group include, for example, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxy-n-butyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-n-butyl acrylate. , 3-hydroxy-n-butyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, glycerin monoacrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, 2-hydroxy-3- Examples include phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, and lactone-modified acrylate having a hydroxyl group at the terminal. That.

General formula (5)
[A in the general formula (5) represents a divalent linking group, and B represents an oxygen atom, or a hydrogen atom or a nitrogen atom having a substituent. R ^{3 to} R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms. Or a phenyl group which may have a substituent. R ^{7 to} R ⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a chlorine atom.
p and q represent an integer of 1 to 3, and when p and q are integers of 2 or more, a plurality of p and q may be the same or different. Moreover, r shows the integer of 1-4, and when r is an integer greater than or equal to 2, several r may be same or different.
Anion ⁻ represents an organic or inorganic anion. ]

[Amine compound]
Next, the intermediate acryloyl group represented by the general formula (5) is subjected to Michael addition reaction of the primary amine compound or the secondary amine compound represented by the general formula (6) of the present invention. A xanthene dye represented by the following general formula (1) can be obtained. A well-known method can be applied to the Michael addition reaction.

General formula (6)
[R ₁ and R _{2 in} General Formula (6) each independently represent a hydrogen atom, an aryl group which may have a substituent, or an alkyl group which may have a substituent. R ₁ and R ₂ may each independently form a cyclic structure by linking a hydrogen atom, an aryl group which may have a substituent, or a substituent. ]

  Representative examples of the primary amine compound in the present invention include methylamine, ethylamine, propylamine, butylamine, 2-ethylhexylamine, allylamine, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, cyclohexylamine, Examples include benzylamine and aniline. Among these, ethylamine, propylamine, butylamine, 3-methoxypropylamine, 3-ethoxypropylamine, cyclohexylamine and the like are preferable.

  Representative examples of secondary amine compounds in the present invention include dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, diallylamine, di (3-methoxypropyl) amine, diphenylamine, pyrrolidine, piperidine, pyrrole. , Pyrroline, indole, indoline, morpholine and the like. Among these, diethylamine, dipropylamine, dibutylamine, pyrrolidine, piperidine, morpholine and the like are preferable.

[Anion ^-]
Next, Anion ⁻ in the formula (1) will be described. Anion ⁻ is not particularly limited, and examples thereof include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methide anion.

  Examples of the halogen ion include fluoride ion, chloride ion, bromide ion, and iodide ion.

Examples of the boron anion include inorganic boron anions such as BF ₄ −;
(CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ −, (CF ₃ ) BF ³ −, (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF _{chromatography, (C 2 F 5) BF} 3-, (C 2 F 5) 2 BF 2-, (CF 3) (C 2 F 5) 2 BF -, (C 6 F 5) 4 B -, [( CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ²⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (nC ₃ F ₇ ) ₃ B ^{(CN) -, (n-} C 4 F 9) 3 B (CN) -, (n-C4 F9) 2 B (CN) 2 -, (n-C 6 F 1 3) 3 B (CN) -, (CHF ₂ ) ₃ B (CN) ⁻ , (CHF ₂ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B (CN) ₂ ⁻ , (n-C ₃ F ₇ CH ₂ ) ₂ B (CN) ₂ ⁻ , (C ₆ H ₅ ) ₃ B (CN) ⁻ , tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) Borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ G In addition to organic boron anions such as s (pentafluorophenyl), phenyl] borate and tridecahydride-7,8-dicarbaoundeborate, JP-A-10-195119, JP-A 2010-094807, JP-A 2006 Examples include boron anions described in JP-A Nos. 243594, 2002-341533, and 08-015521.

Examples of the phosphate anion include inorganic phosphate anions such as HPO ₄ ^{2 −} , PO ₄ ^{3 −} and PF ₆ ⁻ ;
(C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (n− C ₃ F ₇ ) ₂ PF ₄ ⁻ , (n-C ₃ F ₇ ) ₃ PF ₃ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (n-C ₄ F ₉ ) ₂ PF ₄ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , octyl Examples thereof include organic phosphate anions such as phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion.

Examples of the carboxylate anion include, for example, CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ^{− and the} like described in JP 2009-265641 A and JP 2008-096680 A Mention may be made of acid anions.

Examples of sulfate anions include sulfate anions and sulfite anions.
Examples of the organic sulfonate anion include alkyl sulfonate anions such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid; benzenesulfonic acid, benzenedisulfonic acid ion, p-toluenesulfonic acid, p -Arylsulfonic acid anions such as trifluoromethylsulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid ion, and 2- (meth) acryloyloxy-1,1,2,2-tetrafluoroethanesulfone Acid, 2- (4-vinylphenyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid, International Publication No. 11/037195 pamphlet, Japanese Patent No. 3736221 specification, Japanese Patent Laid-Open No. 2011-070172 Mentioning the organic sulfonate anions described It can be.

Examples of the nitrogen anion include [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , and [(CF ₃ SO ₂ ). ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ SO ₂ )] −, [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ⁻ , [(FSO ₂ ) N (CF ₃ CF ^{_{2 CF 2 SO 2)] -}} , [(FSO 2) N (CF 3 CF 2 CF 2 CF 2 SO 2)] -, [(FSO 2) N {(CF 3) 2 CFCF 2 SO 2}] -, In addition to [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like, JP 2011-133844 A, Examples thereof include nitrogen anions described in JP 2011-116803 A and JP 2010-090341 A.

Examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ⁻ , and (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ⁻ , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ⁻ , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ⁻ , (FSO ₂ ) ₃ C ^{— and the} like, JP 2011-145540 A, US Pat. No. 5,554,664, JP 2005-309408 A Examples thereof include a methide anion described in JP-A-2004-085657, JP-A-2010-505787, and the like.

  The coloring agent may be a lake pigment of xanthene dye represented by the general formula (1). Lake pigment refers to a soluble dye made into an insoluble pigment by a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and katanol. , Tamol, Complex heteropolyacids (phosphotungstic acid, phosphomolybdic acid, phosphotungsten / molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungsten molybdate, phosphotungsten) Acid, phosphomolybdic acid) and the like. The present colorant as a lake pigment is obtained, for example, by an esterification reaction between a compound represented by the above formula (3) and a compound having a hydroxyl group and a (meth) acryloyl group represented by the above formula (4). Further, an intermediate compound (represented by general formula (5)) and a compound (represented by general formula (1)) obtained by Michael addition reaction with an amine compound represented by general formula (5). It can be produced by rake formation with a precipitant.

<Other colorants that can be used in combination>
The colorant can be used in combination with a pigment or another dye.
When used in combination with other colorants, it is preferable to use organic pigments in order to adjust the hue and improve resistance. When the salt-forming compound of the present invention and the organic pigment are used in combination, the use ratio of the salt-forming compound of the present invention and the organic pigment is 1 to 80 parts by weight of the salt-forming compound of the present invention with respect to 100 parts by weight of the organic pigment. Preferably there is. More preferably, it is 5 to 60 parts by weight. When the addition amount of the salt-forming compound of the present invention is within this range, a composition excellent in hue and reproducible chromaticity region can also be obtained.

  As the pigment used in combination, the following are used for each color filter segment.

[Pigment forming red filter segment]
As the red pigment forming the red filter segment, the red pigment or red dye described below can be used in combination.
Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP-T-2011-523433, or JP2013-161025A Although the naphthol azo pigment etc. which are described in gazette are mentioned, It is not limited to these in particular. Among these, C.I. I. Pigment Red 177, 242, 254, and 269 are preferably used.

  In order to form a red filter segment, a yellow or orange pigment may be used in combination. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026 is used, but is not particularly limited thereto. . Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73 or the like is used.

  These pigments can be used alone or in admixture of two or more at any ratio as required.

[Pigment forming blue filter segment]
Examples of the pigment forming the blue filter segment include blue pigments such as C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination, but are not particularly limited thereto.
Among these, from the viewpoint of brightness and contrast ratio, C.I. I. Pigment Blue 15: 1, 15: 6 is particularly desirable.

[Pigment forming green filter segment]
Examples of the pigment forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58, zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, etc. Although the aluminum phthalocyanine pigment of description is mentioned, it is not specifically limited to these.
Among these, C.I. I. It is preferable to use pigment green 36 or 58.
In addition, a yellow pigment can be used in combination with the green coloring composition in order to adjust the hue. Among them, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 and the quinophthalone pigment described in Japanese Patent No. 4993026 can be used in combination. In particular, it is not limited to these.
Among these, C.I. I. Pigment Yellow 138, 150 or the like is preferably used.

  In the coloring composition for a color filter of the present invention, the concentration of the coloring agent with respect to all the non-volatile components is preferably 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 90% by weight, the concentration of the colorant carrier such as a binder resin is lowered, and the color composition May become unstable.

(Miniaturization of pigment)
The pigment that can be used in the present invention is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As illustrated, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed.

  The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

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

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight 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 to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

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

[dye]
Next, dyes that can be used in combination with the salt-forming compound of the present invention will be described. Examples of the dyes that can be used in combination include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Oil-soluble dyes, acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes, and the like. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes.

(Oil-soluble dye)
When an oil-soluble dye is used, a xanthene dye or an anthraquinone dye is preferable from the viewpoint of lightness.
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. 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. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, or C.
I. Solvent violet 10 etc. are mentioned.

  Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

  Examples of anthraquinone oil-soluble dyes include CI Solvent Red 172, 222, CI Solvent Violet 60, and the like.

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

Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, 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 these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

  As an 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, CI Acid Violet 41, 42, 43, CI Acid Green 25, 27 Or direct violet 17 and the like.

Examples of azo acid dyes include 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;
CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
CI Acid Violet 11, 56, 58;
CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
CI Acid Brown 2, 4, 13, 248;
CI Acid Blue 92, 102, 113, 117 and the like.

(Basic dye)
When a basic dye is used, a triarylmethane dye or a xanthene dye is preferable from the viewpoint of lightness.

  Examples of the triarylmethane basic dye include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like. Among them, C.I. I. It is preferable to use Basic Blue 7, Green 4, Green 1, and Violet 3.

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

Examples of flavin basic dyes include C.I. I. Basic Yellow 1,
Examples of auramine basic dyes include C.I. I. Basic Yellow 2, 3,
Examples of the safranine basic dye include C.I. I. Basic Red 2,
Phloxine basic dyes include C.I. I. Basic Red 12,
Examples of the acridine basic dye include C.I. I. Basic Yellow 5,
Examples of the oxazine-based basic dye include C.I. I. Basic Blue 3,
Examples of thiazine-based basic dyes include C.I. 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. Basic Yellow 1, Blue 9, Blue 24 and Blue 25 are preferably used.

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

(Metal complex dyes)
Since the metal complex dye exhibits a fluorescence quenching effect with respect to a dye having fluorescence, it can be suitably used in the present invention.
Examples of the metal complex dye include 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, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 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; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211 is exemplified. Among these, from the viewpoint of fluorescence quenching, 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 preferred. These metal complex dyes may be used alone or in combination of two or more.

<Binder resin>
Binder resins are those that disperse colorants, particularly salt-forming compounds and pigments, or those that dye and permeate salt-forming compounds, and include thermoplastic resins. In the present invention, the colorant is composed of the salt-forming compound or the salt-forming compound and a pigment.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type color resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

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

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

  The molecular weight of the binder resin used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 5,000 to 100,000. More preferably, it is 7,000-50,000. It is preferable that the converted weight average molecular weight of the binder resin is 5,000 to 100,000, because film loss is unlikely to occur during development, and the non-pixel portion is liable to be easily removed during development. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

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

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances will be insufficient, and if it is more than 500 parts by weight, the concentration of the colorant will be low and color characteristics may not be exhibited.

<Thermosetting compound>
In the present invention, it is preferable to further include a thermosetting compound in combination with the 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 the filter segment to increase the crosslinking density of the coating film, so that the heat resistance of the filter segment is increased. This improves the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio.

  Examples of thermosetting compounds include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, and phenol compounds and / or resins, but the present invention is not limited thereto. In the coloring composition for a color filter of the present invention, an epoxy compound and / or a resin are preferably used.

The epoxy compound may be a low molecular 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 Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Polyphenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimene) Methanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, alcohols Etc. glycidylated 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 in combination of two or more.

  As a commercial item, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more) Is a trade name; manufactured by Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name) ; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (Product Name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (Product Name; Nippon Kayaku Co., Ltd.), JER152, JER154 Name: Japan Epoxy Resin Co., Ltd. , EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above are 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 above are trade names; manufactured by Nagase ChemteX Corporation) However, it is not limited to these.

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving heat resistance is small. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment 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 | curing agent, the hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting compounds.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 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- Methylformamide, 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, since the salt-forming compound used in the present invention and the optional pigment are well dispersed and dissolved, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and 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.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. In the case of using two or more kinds of mixed solvents, it is preferable that the above-mentioned preferable organic solvent is contained in an amount of 65 to 95% by weight.

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

<Dispersion>
When the coloring composition of the present invention further contains a pigment in a colorant carrier composed of a salt-forming compound, the binder resin and a solvent, it is preferably combined with a dispersing aid such as a dye derivative or a resin-type dispersant. It can be produced by finely dispersing using various dispersing means such as a present roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other colorants and the like separately dispersed in a colorant carrier.

《Dispersing aid》
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound is also expected to play a role as a pigment dispersion aid.

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

  The blending amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably from the viewpoint of improving the dispersibility of the additive pigment, based on the total amount of the additive pigment (100% by weight). 3% by weight or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

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

   Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Nippon Lubrizol Co., Ltd. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). It is. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Photopolymerizable monomer>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

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

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

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

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds An imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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

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

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

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

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

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

Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

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

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

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

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

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

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

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

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

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

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

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having 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 and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

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

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

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

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

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

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

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”.

  Moreover, the measuring method of the average primary particle diameter of a pigment, the weight average molecular weight (Mw) of a resin, and a number average molecular weight (Mn) is as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Resin weight average molecular weight (Mw), number average molecular weight (Mn))
Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

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

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of binder resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 1.33 of 2,2′-azobisisobutyronitrile Part of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, after cooling to room temperature, 6.5 parts of 2-methacryloyloxyl ethyl isocyanate, A mixture of 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100 mol% of glycidyl group), and 120 ° C. Then, the reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(Blue refined pigment (P-1): PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “Lionol Blue ES”) 100 parts, 800 parts of ground salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. did. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Purple refined pigment (P-2): PV23)
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts purple refinement | purification pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Red fine pigment (P-3): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Yellow fine pigment (P-4): PY150)
Nickel complex yellow pigment C.I. I. 100 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 95 parts of yellow refined pigments (P-4). The average primary particle diameter of the obtained pigment was 39.2 nm.

(Green refined pigment (P-5): PG36)
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refined pigment (P-5). The average primary particle diameter of the obtained pigment was 32.6 nm.

(Red fine pigment (P-6): PR177)
Anthraquinone red pigment C.I. I. 120 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-6). The average primary particle diameter of the obtained pigment was 38.9 nm.

<Method for producing pigment paste>
(Preparation of pigment paste PP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (PP-1) was produced by filtration using a filter.
Finer pigment (P-1): 10.0 parts Binder resin solution 1: 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts Resin-type dispersant: 15.0 parts (Ajinomoto Fine (20% PGMAc solution of “Ajisper PB821” manufactured by Techno)

(Preparation of pigment paste PP-2 to 6)
Pigment pastes (PP-2 to 6) were obtained in the same manner as the pigment paste (PP-1), except that the type of fine pigment described in Table 1 was changed.

<Method for producing Anion ⁻ used for salt exchange>
The xanthene dye of the present invention has a structure represented by the general formula (1). The present inventors have found that various physical properties such as heat resistance are changed by different types of Anion ^{− in} the general formula (1). In particular, the fluorine-containing boron anion exhibits the most excellent resistances in the present invention. In order to make anion ⁻ on the fluorine-containing boron anion, it is necessary to change the counter to a fluorine-containing boron anion by salt exchange. Here, the manufacturing method of the counter used for salt exchange by this invention is shown.

(Method for producing resin 1 having an anionic group)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 20.0 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12.5 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 3.0 parts of methacrylic acid, 2 -16.5 parts of hydroxyethyl methacrylate, 6.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were made uniform and charged into a dropping funnel. It was attached to a separable flask and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 3390, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a resin component having 47% by weight of an anionic group was obtained.

(Production of fluorine group-containing boron anion (FBA-2): production method of sodium tetrakis (pentafluorophenyl) borate)
Hereinafter, fluorine group-containing boron anions were synthesized with reference to JP2011-201803A.
A reaction vessel purged with deaerated nitrogen is charged with 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran, and cooled to 18 ° C. in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged into a dropping funnel and added dropwise so that the internal temperature does not exceed 25 ° C. After completion of dropping, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. Thereafter, 2.4 parts of boron trifluoride diethyl ether complex is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. The reaction is continued at 65 ° C. for 12 hours after completion of the dropwise addition.
This solution is added to 50 parts of a saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the resulting ethyl acetate layer is added to the previously separated organic layer. added. The organic layer was removed, and the residue was washed twice with hexane, and the residue was dried under reduced pressure to give 5.8 parts of the target product, sodium tetrakis (pentafluorophenyl) borate, yield 40% (purity 98 % Or more). The product (FBA-2) was identified by ¹⁹ F-NMR. In addition, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

(Method for producing imido acid anion G-1)
To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube was added 3.58 g (1.1 equivalents) of trifluoromethanesulfonamide, 5.53 g (2 equivalents) of potassium carbonate, and 60 ml of acetonitrile. Then, 3.53 g of pentafluorobenzenesulfonyl chloride was added in portions, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, 400 ml of acetonitrile was added and stirred well, and then the filtrate obtained by suction filtration was concentrated to obtain 7.30 g of product. ¹ H, ¹³ C—N MR spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the target compound (G-1).

<Method for Producing Xanthene Dye Represented by General Formula (1)>
Here, a method for synthesizing the xanthene dye represented by the general formula (1) will be described. According to the above reaction scheme 1, xanthene compounds (Xa1 to 18) represented by the general formula (1) in the present invention were respectively synthesized.

[Synthesis of Xanthene Dye Xa1]
For the xanthene dye Xa1, first, the intermediate CC1 was synthesized, and then the xanthene dye Xa1 as the target product was synthesized in the next step.

(Synthesis of Intermediate CC1 (Acryloyl Group-Containing Compound))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 10.0 parts of Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd .: Rhodamine B) and 2.4 parts of 2-hydroxyethyl acrylate were dissolved in 80 ml of dichloromethane, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide was dissolved. 4.4 parts of hydrochloride and 0.5 part of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water and dried under reduced pressure, and then purified on a silica gel column to obtain Intermediate CC1. The yield was 61.6%.

(Michael addition reaction between an acryloyl group-containing compound and a primary or secondary amine compound)
Next, 10.0 parts of the intermediate CC1, 2.2 parts of 2-ethylhexylamine, and 0.1 parts of p-methoxyphenol were dissolved in 100 ml of methanol and stirred at 50 ° C. for 6 hours. The obtained methanol solution was distilled off under reduced pressure using an evaporator, 100.0 parts of water was added to the obtained solid, and the mixture was stirred at room temperature for 1 hour and filtered to obtain a solid (xanthene dye Xa1). Got. The yield was 93.2%.

[Synthesis of Xanthene Dye Xa2-18]
It has the structure shown in Table 3 in the same manner as the xanthene dye Xa1 except that the type and weight part of the compound having a hydroxyl group and an acryloyl group in the synthesis method of the xanthene dye intermediate CC1 are changed to the contents shown in Table 2. Intermediates (CC1 to 6) of various xanthene dyes were produced.
Further, the structures shown in Tables 5 to 7 are the same as those of Xa1 except that the intermediate CC1 and 2-ethylhexylamine in the method for synthesizing the xanthene dye Xa1 are changed to the contents shown in Table 4 (type and polymerization part). Various xanthene-based pigments (Xa2-18) having

[Synthesis of Xanthene Dye Xa19]
A xanthene dye Xa19 having a fluorine group-containing boron anion (FBA-2) as a counter was synthesized by performing a salt exchange reaction between the synthesized xanthene dye Xa1 and a fluorine group-containing boron anion (FBA-2).

300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone are mixed with 10 parts of a xanthene dye (Xa1), and 9.9 parts of fluorine group-containing boron anion (FBA-2) is dissolved in 1000 parts of water in advance. Mix the solution in drops. Then, it stirred for 240 minutes at 60 degreeC, and fully reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The extracted salt-forming compound was dried with a drier to obtain xanthene dye Xa19 having 17.4 parts of fluorine group-containing boron anion (FBA-2) as a counter. By this synthesis, the counter anion of Xa1 was salt-exchanged from Cl ⁻ to B (C ₆ F ₅ ) ₄ ⁻ .

[Synthesis of Xanthene Dye Xa20-44]
The xanthene dye Xa19, except that the xanthene dye Xa1, the fluorine group-containing boron anion (FBA-2) type and parts by weight are changed to the xanthene dyes shown in Table 8 and Anion ⁻ type and parts by weight. In the same manner, xanthene dyes Xa20 to 44 having various compounds as counters were synthesized.

[Synthesis of Xanthene Dye Xa45]
Basic violet 10 (18 parts by mass), anhydrous chloroform (170 parts by mass), camphorsulfonic acid (1.0 parts by mass), 4- (N, N-dimethylamino) pyridine (1.4 parts by mass), 2-hydroxy Ethyl methacrylate (18 parts by mass) was added and stirred for about 30 minutes. Then, after slowly adding a solution prepared by adding anhydrous chloroform (47 parts by mass) to 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (10.5 parts by mass) and slowly adding it to room temperature. And stirred for about 2 hours. After performing the liquid separation operation twice with 1N hydrochloric acid aqueous solution (150 parts by mass), the organic layer was washed twice with 10% saline (150 parts by mass). Next, 43 parts by mass of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off to obtain 20.2 parts by mass (yield 87%) of the compound represented by the following formula. The resulting compound was designated as xanthene dye (Xa45).

Xanthene dye (Xa45)

[Synthesis of Xanthene Dye Xa46]
A 500 mL Erlenmeyer flask containing a stirrer was charged with the compound (Xa45) (20 parts by mass) and bis (trifluoromethanesulfonyl) imidolithium (14.5 parts by mass), chloroform (130 parts by mass), ion-exchanged water ( 100 parts by mass) was added and stirred at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water (200 parts by mass). The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 26.2 parts by mass (yield 91%) of the compound represented by the following formula (A2). By 1 H-NMR (solvent: deuterated chloroform) measurement, it was confirmed to be the target compound. The obtained compound was designated as xanthene dye (Xa46).

Xanthene dye (Xa46)

<Method for producing dye paste>
[Example 1]
(Preparation of dye paste DP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (DP-1) was produced by filtration using a filter.
Salt-forming compound (Xa-1): 10.0 parts Binder resin solution 1: 50.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts

[Examples 2-44, Comparative Examples 1-2]
(Preparation of dye paste (DP-2 to DP-46))
Dye pastes DP-2 to DP-46 were prepared in the same manner as the dye paste DP-1, except that the types of salt-forming compounds shown in Table 9 were changed.

<Evaluation of dye paste>
About the obtained coloring composition (DP-1 to 46), the test regarding contrast ratio was done by the following method. The results of the test are shown in Table 9 below.

(Method for evaluating contrast ratio of coating film)
The film thickness after heat treatment at 230 ° C. of the dye paste (DP-1 to 46) on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater is changed to about 1. Three coated substrates were prepared so as to be around 5 μm. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after coating, respectively, and the film thickness and contrast ratio were measured, and the contrast at a film thickness of 1.5 μm was determined from the three-point data by the primary correlation method. It was. X is a difficult level to use.
◎: CR ≧ 2000 or more ○: CR = 1000 or more, less than 2000 Δ: CR = 500 or more, less than 1000 ×: CR = 500 or less

The coloring composition (DP-1 to 44) containing the xanthene pigment specific to the present application as the dye paste gave very good results in terms of the contrast ratio.
However, since a very large fluorescence was observed in the coloring composition (DP-45 to 46) containing a xanthene dye not having a specific structure as the coloring agent, the contrast ratio was greatly inferior to that of the examples, and the heat resistance was high. The results were inferior to those of the examples.
Further, the coloring composition (DP-19 to 36) containing the specific cationic dye containing fluorine-containing boron anion in the counter is a resist material (DP- containing a cationic dye not containing fluorine-containing boron anion in the counter). 1 to 18 and 37 to 44), the contrast ratio was good.

<Method for producing colored composition>
(Preparation of colored composition (DB-1))
Next, when the pigment paste (PP-3) and the dye paste (DP-1) are dried, the chromaticity of the coating film is x = 0 in the microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). .661, y = 0.323 was adjusted at a blending ratio, and the mixture was stirred and mixed with a disper for 1 hour to obtain a colored composition (DB-1).

(Preparation of colored composition (DB-2 to 46))
Next, colored compositions (DB-2 to 46) were produced in the same manner as the colored composition DB-1, except that the types of pigment paste and dye paste shown in Table 10 were changed.

<Evaluation of coloring composition>
About the obtained coloring composition (DB-1-46), the test regarding heat resistance, light resistance, and contrast ratio was done with the following method. The results of the test are shown in Table 10 below.

(Method for evaluating heat resistance of coating film)
The coloring composition (DB-1 to 46) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was heat-treated at 220 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 2.0 Δ: ΔEab * is 2.0 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Light resistance evaluation of coating film)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

(Method for evaluating contrast ratio of coating film)
The film thickness after heat treatment at 230 ° C. of the colored composition (DB-1 to 46) on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater and changing the number of revolutions is about 1 Three coated substrates were prepared so as to have a thickness of about 5 μm. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after coating, respectively, and the film thickness and contrast ratio were measured, and the contrast at a film thickness of 1.5 μm was determined from the three-point data by the primary correlation method. It was. X is a difficult level to use.
◎: CR ≧ 10000 or more ○: CR = 5000 or more, less than 10000 Δ: CR = 3000 or more, less than 5000 ×: CR = less than 3000

The colored composition (DB-1 to 44) containing the xanthene dye specific to the present application as the colorant gave very good results in terms of contrast ratio, light resistance and heat resistance.
However, the coloring composition (DB-45 to 46) containing a xanthene dye that is not a specific structure of the present application as a coloring agent was greatly inferior in contrast ratio and light resistance as compared with Examples, because very large fluorescence was observed. Also, the heat resistance was inferior to the examples.
Further, the coloring composition (DB-19 to 36) containing a specific cationic dye containing fluorine-containing boron anion in the counter is a resist material (DB-) containing a cationic dye not containing fluorine-containing boron anion in the counter. 1-18 and 37-44), heat resistance and contrast ratio were good.

<Production of photosensitive coloring composition (resist material)>
[Example 89]
(Resist material (R-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 developing resist material (R-1).
Coloring composition (DB-1): 60.0 parts Binder resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

[Examples 90 to 132, Comparative Examples 5 to 6]
(Resist material (R-2 to 46))
Hereinafter, alkali-developable resist materials (R-2 to 46) were produced in the same manner as in Example 89 except that the colored composition (DB-1) was changed to the colored composition shown in Table 11.

<Evaluation of photosensitive coloring composition (resist material)>
With respect to the obtained resist materials (R-1 to 46), tests on heat resistance, light resistance, contrast ratio, and voltage holding ratio were performed by the following methods. The test results are shown in Table 11 below.

(Evaluation of heat resistance of coating film)
The obtained resist material (R-1 to 46) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater and then dried at 70 ° C. for 20 minutes to obtain an ultrahigh pressure mercury lamp. Was exposed to ultraviolet light at an integrated light quantity of 150 mJ / cm ² and developed with an alkaline developer at 23 ° C. Subsequently, the coating-film board | substrate was produced by heating and standing to cool at 220 degreeC for 30 minutes. The prepared coated substrate was heat-treated at 220 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 2.0 Δ: ΔEab * is 2.0 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Light resistance evaluation of coating film)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

(Evaluation of contrast ratio)
Using the obtained resist material (R-1 to 46) on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness, using a spin coater, the number of rotations was changed, and the film thickness after heat treatment at 230 ° C. It is applied to three substrates so as to be about 1.5 μm, then dried at 70 ° C. for 20 minutes, and is exposed to ultraviolet light with an integrated light quantity of 150 mJ / cm ² using an ultrahigh pressure mercury lamp, Development was performed with an alkaline developer to obtain a coated substrate. Subsequently, after heating at 220 ° C. for 30 minutes and allowing to cool, the film thickness and contrast ratio of each of the obtained coating film substrates were measured, and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. X is a difficult level to use.
◎: CR ≧ 10000 or more ○: CR = 5000 or more, less than 10000 Δ: CR = 3000 or more, less than 5000 ×: CR = less than 3000

(Voltage holding ratio measurement method)
Each resist material was applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the film thickness of the dry film was 1.8 μm, exposed at an exposure dose of 50 mJ / cm ² , and then resisted at 23 ° C. Spray development was performed with a 2 wt% sodium carbonate aqueous solution for 30 seconds, and baking was performed at 230 ° C. in an oven to obtain a coated substrate of each resist material. After removing 0.05 g of the resist coating film from the obtained coated substrate, it was immersed in 1.5 g of liquid crystal (MLC-2041 manufactured by Merck & Co., Inc.), aged in a 120 ° C. oven for 60 minutes, and at 4000 rpm. After centrifugation for 15 minutes, a supernatant liquid was collected to prepare a resist extraction liquid crystal sample liquid.
On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are placed facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap is 9 μm. did. A resist-extracted liquid crystal sample solution is injected into the small cell between the cell gaps, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V ₁ ] after 16.67 msec has elapsed after the voltage release, Measured with Toyo Technica VHR-1S. The measurement was repeated 5 times, and the measured cell voltages were averaged. And the voltage holding rate (%) was calculated | required from the following formula using the obtained cell voltage. X is a level that is difficult to use. Δ is a level that is not difficult to use but needs improvement.

Voltage holding ratio (%) = ([V ₁ ] / 5) × 1 0 0
The evaluation criteria for the voltage holding ratio (%) are as follows.
◎: 95% or more ○: 90% or more and less than 95% △: 85% or more and less than 90% ×: less than 85%

The resist material (R-1 to 44) containing the xanthene dye specific to the present application as a colorant gave very good results in terms of contrast ratio, voltage holding ratio, light resistance, and heat resistance. (Examples 89 to 132)
However, the resist material (R-45 to 46) containing a xanthene dye that is not a specific structure of the present application as a colorant was observed to have very large fluorescence, so the contrast ratio and light resistance were greatly inferior to those of the examples. The voltage holding ratio and heat resistance were inferior to those of the examples.
In addition, the resist material (R-19 to 36) containing a specific cationic dye containing fluorine-containing boron anion in the counter is a resist material (R-1) containing a cationic dye not containing fluorine-containing boron anion in the counter. ~ 18, 37 ~ 44), heat resistance and contrast ratio were good.

<Manufacture of color filters>
First, the blue photosensitive coloring composition and the green photosensitive coloring composition used for preparation of a color filter were produced. In addition, the photosensitive coloring composition (R-19) was used about red.

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Pigment paste (PP-1) 24.0 parts Pigment paste (PP-2) 10.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Preparation of green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).
Pigment paste (PP-4) 17.0 parts Pigment paste (PP-5) 17.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (R-19) was applied on the substrate with a spin coater so as to have a thickness of 2.0 μm to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. Formed. By the same method, the green photosensitive coloring composition (RG-1) of the present invention has a thickness of 2 μm, and the blue photosensitive coloring composition (RB-1) has a thickness of 2 μm. Each was coated to form a green filter segment and a blue filter segment to obtain a color filter.

  By using the red photosensitive coloring composition (R-19) of the present invention, it was possible to produce a color filter having a high contrast ratio and high brightness.

Claims (6)

A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant contains a xanthene dye represented by the following general formula (1): object.

General formula (1)
[R ¹ and R ^{2 in} General Formula (1) each independently represent a hydrogen atom, an aryl group which may have a substituent, or an alkyl group which may have a substituent. R ¹ and R ² may be linked to form a cyclic structure. A represents a divalent linking group, and B represents an oxygen atom, or a hydrogen atom or a nitrogen atom having a substituent. R ^{3 to} R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted cycloalkyl group having 3 to 8 carbon atoms. Or a phenyl group which may have a substituent. R ^{7 to} R ⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a chlorine atom.
p and q each independently represent an integer of 1 to 3, and r represents an integer of 1 to 4.
Anion ⁻ represents an organic or inorganic anion. ]   The coloring composition for a color filter according to claim 1, wherein A in the general formula (1) is an alkylene group which may have a substituent, and B is an oxygen atom. In the general formula (1), Anion ^- are, according to claim 1 or 2, wherein a color filter for coloring composition, characterized in that a fluorine-containing boron anion. Xanthene dyes
In the acryloyl group of the acryloyl group-containing compound obtained by esterification reaction between the carboxyl group of the compound represented by the general formula (2) and the hydroxyl group of the compound having a hydroxyl group and an acryloyl group,
The coloring composition for a color filter according to any one of claims 1 to 3, which is a xanthene dye obtained by Michael addition reaction of an amino group of a primary amine compound or a secondary amine compound.

General formula (2)
  Furthermore, the coloring composition for color filters in any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator. A color filter comprising a filter segment formed from the colored composition for color filter according to claim 1 on a substrate.