JP6733386B2 - Coloring composition for color filter and color filter - Google Patents

Description

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

In recent years, from the viewpoint of power consumption, increasing the brightness of color filters has become a trend.
When a color filter having high brightness is used, light transmittance is high, so that the number of backlights which are light sources can be reduced and power consumption can be suppressed.

It is known that it is effective to use a dye as a colorant, as in Patent Document 1, in order to realize high brightness of a color filter. However, as described in, for example, Patent Document 2, the dye has a tendency to be inferior in fastness such as heat resistance and light resistance as compared with a pigment, and therefore, at 230° C. or higher in the manufacturing process of the color filter. There is a problem that the heat resistance is inferior during the firing of. Therefore, a solution has been studied as in Patent Document 3, but the current situation is that the color filter does not have sufficient resistance.

JP-A-6-75375 JP-A-8-327811 JP, 2012-098522, A

An object of the present invention is to provide a highly bright color filter coloring composition excellent in heat resistance and solvent resistance capable of withstanding a heat treatment at 230° C., and a high lightness formed by using the color filter coloring composition. To provide a simple color filter.

The present inventors, as a result of extensive studies in order to achieve the above objects, salt formation of an organic resin having a strong acidity and an acrylic resin having a cation site, by a specific ionic acrylic resin, acidic It has been found that even when a dye is used, a color filter having high brightness and excellent solvent resistance and heat resistance can be obtained.

That is, the present invention includes an acid dye, a binder resin, an organic solvent, and a structural unit represented by the following general formula (1), and has a maximum molar absorption coefficient ε in the visible light region (wavelength 400 nm to 700 nm). And an ionic acrylic resin [C] having a value of 0 or more and 3000 or less, and a coloring composition for a color filter.

[In the general formula (1), R ₁₀₁ represents a hydrogen atom or an alkyl group which may have a substituent. R _{102 to} R ₁₀₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent or an aryl group which may have a substituent, and R ₁₀₂ Two or more of _{102 to} R ₁₀₄ may combine with each other to form a ring. Q is an optionally substituted alkylene group, an optionally substituted arylene group, _{-CONH-R 105} - or _{-COO-R 105} - _{represents, R 105} is a substituent Represents an alkylene group which may be present. Z ⁻ represents an anion having a group selected from the group consisting of a cyano group, a nitro group and a halogenated hydrocarbon group, PF ₆ ⁻ or BF ₄ ⁻ . ]

The present invention also relates to the above-mentioned colored composition for a color filter, wherein the acidic dye is at least one selected from the group consisting of anthraquinone-based acidic dyes and xanthene-based acidic dyes.

In the present invention, Z ⁻ is an anion represented by the following general formula (1a), an anion represented by the following general formula (1b), an anion represented by the following general formula (1c) or a general formula (1d). The present invention relates to the above coloring composition for a color filter, which is an anion represented.

[In the general formula (1a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halogen atom, and when R ¹ and Hal are present in plural, they may be the same. May be different. c represents an integer of 1 to 6. ]

[In General Formula (1b), R ² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a cyano group, B represents a boron atom, and Hal represents a halogen atom. , R ² and Hal each may be the same or different. d represents an integer of 1 to 4. ]

[In the general formula (1c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group or an FSO ₂ group, and R ³¹ and R ³² are both In the case of a halogenated hydrocarbon group which may have a sulfonyl group, they may combine with each other to form a ring. However, at least one of R ³¹ and R ³² is a halogenated hydrocarbon group or a cyano group. ]

[In the general formula (1d), R ⁴ represents a halogenated hydrocarbon group which may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

The present invention also relates to the above coloring composition for a color filter, wherein R ¹ in the general formula (1a) is a fluorinated alkyl group or a fluorinated aryl group, and Hal is a fluoro group.

The present invention also relates to the above coloring composition for a color filter, wherein R ² in the general formula (1b) is a fluorinated alkyl group or a fluorinated aryl group, and Hal is a fluoro group.

Further, the present invention is characterized in that R ³¹ or R ³² in the general formula (1c) is a group represented by the general formula (1c-1) or a group represented by the general formula (1c-2). The present invention relates to a coloring composition for a color filter.

General formula (1c-1)

[In General Formula (1c-1), R ⁵ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ — or R 5 ¹⁷ COOR ¹⁸ CFH— (R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or an aryl group which may have a substituent, and R ¹⁸ represents an alkylene group), n represents an integer of 1 or more, and “*” represents a bond. When both R ⁵ are fluorinated alkyl groups, they may be bonded to each other to form a ring. ]

General formula (1c-2)

[In the general formula (1c-2), R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, an alkoxy group or an alkylsulfonyl group, and “*” is Represents a bond. However, at least one of R ^{6 to} R ¹⁰ is a fluorine atom or a fluorinated alkyl group. ]

In the present invention, R ⁴ in the general formula (1d) is a group represented by the following general formula (1d-1) or a group represented by the following formula (1d-2). A coloring composition for use.

General formula (1d-1)

[In General Formula (1d-1), R ¹¹ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ -or R. ¹⁷ COOR ¹⁸ CFH— (R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or an aryl group which may have a substituent, and R ¹⁸ represents an alkylene group), n represents an integer of 1 or more, and “*” represents a bond. When both R ¹¹ are fluorinated alkyl groups, they may be bonded to each other to form a ring. ]

General formula (1d-2)

[In the general formula (1d-2), R ^{12 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, an alkoxy group or an alkylsulfonyl group, and “*” is , Represents a bond. However, at least one of R ^{12 to} R ¹⁶ is a fluorine atom or a fluorinated alkyl group. ]

The present invention also relates to the above coloring composition for a color filter, wherein the acidic dye is a salt-forming compound and/or a sulfonic acid amide compound.

The present invention also relates to the above coloring composition for a color filter, wherein the acidic dye is a xanthene-based acidic dye.

The present invention also relates to the above-mentioned color filter coloring composition, which further contains an organic pigment.

The present invention also relates to the above coloring composition for a color filter, which further comprises a polyfunctional monomer and/or a photopolymerization initiator.

The present invention also relates to a color filter characterized by comprising a filter segment formed from the above coloring composition for a color filter on a base material.

The coloring composition for a color filter of the present invention can achieve heat resistance and solvent resistance to a high temperature of 230° C. in the manufacturing process of a color filter by combining an acid dye and a specific ionic acrylic resin. Further, by using the composition, a high brightness filter segment can be formed. A low power consumption color liquid crystal display device can be manufactured using the color filter of the present invention.

First, various components of the color filter coloring composition of the present invention will be described.
In addition, in this application, when it describes with "(meth)acrylate", "(meth)acrylic acid", or "(meth)acrylamide", unless otherwise specified, "acrylate and/or methacrylate", respectively. It shall mean “acrylic acid and/or methacrylic acid” or “acrylamide and/or methacrylamide”.
Further, “C.I.” mentioned below means a color index (C.I.).

The coloring composition for a color filter of the present invention has an acid dye, a binder resin, a maximum molar extinction coefficient ε in the visible light region of 0 or more and 3000 or less, and a structure represented by the following general formula (1). It contains an ionic acrylic resin (C) containing a unit and an organic solvent.

[In the general formula (1), R ₁₀₁ represents a hydrogen atom or an alkyl group which may have a substituent. R _{102 to} R ₁₀₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent or an aryl group which may have a substituent, and R ₁₀₂ Two or more of _{102 to} R ₁₀₄ may combine with each other to form a ring. Q is an optionally substituted alkylene group, an optionally substituted arylene group, _{-CONH-R 105} - or _{-COO-R 105} - _{represents, R 105} is a substituent Represents an alkylene group which may be present. Z ⁻ represents an anion having a group selected from the group consisting of a cyano group, a nitro group and a halogenated hydrocarbon group, PF ₆ ⁻ or BF ₄ ⁻ . ]

《Colorant》
The coloring composition for a color filter of the present invention contains an acid dye as a coloring agent. By using an acid dye, even if an ionic acrylic resin (C) is added, it does not form a salt and does not affect the solvent solubility of the coloring material itself. Therefore, it is brighter than a conventional color filter using only a pigment. And a color filter having a higher solvent resistance than that of using a basic dye can be obtained.

<Acid dye>
Acid dyes are water-soluble dyes that have acid groups such as sulfonic acid groups and carboxyl groups in the dye molecule, or the structure of their salts.Protein-based fibers such as wool, silk and nylon, leather and paper. -It is widely used as ink and food coloring.

Some of the acid dyes are classified as direct dyes, and the direct dyes are a generic name for those excellent in dyeability of cellulosic fibers. Further, the acid dye in the present invention, in addition to those generally classified as the above-mentioned acid dye, a lake pigment obtained by laking an acid dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid. It also includes forms such as inorganic salts, salt-forming compounds of acidic dyes and nitrogen-containing compounds, and sulfonic acid amide compounds of acidic dyes. Among these, in particular, a salt-forming compound with a nitrogen-containing compound, or a sulfonic acid amide compound of an acidic dye, since it will be excellent in the resistance of the dye, it can be a coloring composition excellent in fastness, preferable. Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness, and more preferably, a compound having an onium base is a resin having a cationic group in its side chain.

As the direct dye, an azo dye, a thiazole dye, an anthraquinone dye, an oxazine dye, a phthalocyanine dye, or the like can be used. The dyes that can be used are illustrated below by color index (CI) numbers.

Examples of azo dyes include CI Direct Yellow 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95, 98, 102, 109, 129, 136. 141;
CI Direct Orange 41,46,56,61,64,70,96,97,106,107;
CI Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221, 222, 232, 233, 243, 246, 250;
CI Direct Violet 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
CI Direct Blue 51,57,71,81,84,85,90,93,94,95,98,100,101,113,149,150,153,160,162,163,164,166 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245. 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275;
CI direct green 27,34,37,65,67,68,69,72,77,79,82 etc. are mentioned. Examples of thiazole dyes include CI Direct Yellow 54.

Examples of dioxazine dyes include CI Direct Blue 97, 99, 106, 107, 108, 109, 190, 293. Examples of the anthraquinone type dye include CI Direct Blue 77. Examples of phthalocyanine dyes include CI Direct Blue 86, 87, 189, 199.

Other direct dyes include CI Direct Yellow 38, 43, 47, 58, 68, 108, 138; CI Direct Orange 34, 39, 50, 52, 57, 65, 68; CI Direct Red 91, 92, 96, 105, 184, 220, 234, 241; CI Direct Violet 59; CI Direct Blue 80, 114, 115, 117, 119, 137, 155, 156, 158. , 159, 161, 171, 173; CI Direct Green 25, 31, 32, 63, 66 and the like.

As an acid dye other than the direct dye, an azo dye, a xanthene dye, a phthalocyanine dye, an anthraquinone dye, a quinoline dye, an azine dye, an indigoid dye, or the like can be used.

Examples of azo 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.

CI acid blue 249 is mentioned as a phthalocyanine type dye. Examples of quinoline dyes include CI Acid Yellow 3. Examples of azine dyes include CI Acid Blue 59 and 102. Examples of the indigoid dye include CI Acid Blue 74. Other dyes include CI Acid Violet 49; CI Acid Brown 19; CI Acid Blue 7, 9, 74, 112, 126, 167; CI Acid Green 9; C.I. I. Food green 3 etc. are mentioned.

Examples of xanthene 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 Phloxine PB (Edible Red No. 104)), C.I. I. Acid Red 94, 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. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30 and the like can be mentioned.

Examples of the anthraquinone dyes include CI acid red 82, 92; CI acid violet 41, 42, 43; CI acid blue 14, 22, 25, 40, 45, 78, 80, 127: 1, 129, 145, 167, 230; CI acid green 25, 27 and the like.

Of these, preferable examples include xanthene-based acid dyes and anthraquinone-based acid dyes from the viewpoint of color developability. The xanthene-based acidic dye exhibits a red color and a purple color, and has a dye form. The xanthene-based acid dye used in the present invention has a transmittance of 90% or more in a 650 nm region in a transmission spectrum, a transmittance of 75% or more in a region of 600 nm and a transmittance of 5% or less in 550 nm, and a region of 400 nm. It is preferable that the transmittance is 70% or more. More preferably, the transmittance is 95% or more in the 650 nm region, the transmittance is 80% or more in the 600 nm region, the transmittance at 550 nm is 10% or less, and the transmittance is at least 75% in the 400 nm region. Among the above, C.I. I. Acid Red 52, 87, 92, 94, 289, 388 is preferably used. Further, as the xanthene-based acid dye, it is preferable to use a rhodamine-based acid dye from the viewpoint of excellent color development.

As the anthraquinone-based acid dye, anthraquinone-based acid dye, which is diaminoanthraquinonesulfonic acid, is preferable in that it exhibits heat resistance and light resistance while exhibiting color developability, color reproducibility, and high brightness. The reason why these are excellent in heat resistance and light resistance is presumed to be that the structure is stabilized by the hydrogen bond between the carbonyl group portion of the anthraquinone skeleton and the amino group portion.

Among them, the anthraquinone-based acid dye represented by the following general formula (2) is preferable because the coloring composition for a color filter is excellent in heat resistance and light resistance.

General formula (2)

[In the general formula (2), R ₁₇ and R ₁₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Is an alicyclic group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an alkoxyl group which may have a substituent. R _{19 to} R ₂₄ each independently represent a hydrogen atom or a SO ₃ M group, and at least one of R _{19 to} R ₂₄ is a SO ₃ M group or an alkyl group substituted with a SO ₃ M group. , An aryl group, an alicyclic group, an alkenyl group, an alkynyl group or an alkoxyl group. M represents a hydrogen ion or a sodium ion. ]

In the general formula (2),
As the alkyl group which may have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, Decyl group, dodecyl group, octadecyl group, chloromethyl group, bromomethyl group, hydroxymethyl group, cyanomethyl group, nitromethyl group, methoxymethyl group, aminomethyl group, dimethylaminomethyl group, acetonyl group, ethoxycarbonylmethyl group, diethylaminocarboxymethyl group Group, p-hydroxyphenylmethyl group, methylthiomethyl group, ethylthiomethyl group, butylthiomethyl group, phenylthiomethyl group, methylsulfinylmethyl group, methylsulfonylmethyl group, ethylsulfonylmethyl group, benzenesulfonylmethyl group, p- Toluenesulfonylmethyl group, salicyl group, anisyl group, etc.;
Examples of the aryl group which may have a substituent include a phenyl group, p-tolyl group, xylyl group, mesityl group, cumenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, chlorophenyl group, bromophenyl group, fluoro group. Phenyl group etc.;,
Examples of the alicyclic group which may have a substituent include a cyclohexyl group, a cyclopentyl group, a cyclohexenyl group, a norbornyl group, a bornyl group, a menthyl group, a pinanyl group and an adamantyl group;
Examples of the alkenyl group which may have a substituent include a vinyl group, a 2-propenyl group, an isopropenyl group, a butenyl, a styryl group, a cinnamyl group and the like;
Examples of the alkynyl group which may have a substituent include an ethynyl group and a propynyl group,
The alkoxyl group which may have a substituent includes a methoxy group, a tert-butoxy group, a benzyloxy group and the like;
Examples of the aryloxy group which may have a substituent include a phenoxy group, a p-tolyloxy group, a p-fluorophenoxy group, a p-nitrophenoxy group and the like.

As the substituent which may have, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonic acid group, a carboxyl group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group. , A cyano group, an amino group and the like. Further, in the present invention, a sulfonate group is also synonymous with a sulfonate group.

_Also, if at least one of R 19 _{to R 24} is SO ₃ M group, a substituted alkyl group substituted with SO ₃ M group, SO ₃ M aryl group substituted with a group, with SO ₃ M group has been being alicyclic group, SO ₃ M alkenyl group substituted with a group, an alkynyl group substituted with SO ₃ M group, or any of alkoxyl group substituted with SO ₃ M group.

Specific structural formulas of preferable anthraquinone-based acid dyes are shown below, but the invention is not limited thereto.

The anthraquinone-based acid dye used in the present invention has a transmission spectrum of more than 80% in the 440 nm region, a transmittance of 75% or more in the 450 nm region, and a transmittance of 10% or less in the 550 nm region. Is preferred.

(Salt forming compound)
The acidic dye used in the present invention is preferably a salt-forming compound of an acidic dye and a nitrogen-containing compound, such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound and the like, and functional groups thereof. It is preferable to perform salinization using a resin component having a group to obtain a salt forming compound of a xanthene-based acid dye, since high heat resistance, light resistance, and solvent resistance can be imparted. Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in its side chain, so that lightness and resistance are improved. It can be an excellent coloring composition.

[Resin with a cationic group in the side chain]
The resin having a cationic group in the side chain for obtaining a salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure is available. From the viewpoint of the like, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and considering storage stability (heat stability), ammonium salts, iodonium salts, and sulfonium salts are used. Is more preferable. More preferably, it is an ammonium salt.

The resin having a cationic group in its side chain is an alkali resin containing a structural unit represented by the following general formula (3), wherein the cationic group in the general formula (3) is an anionic group of a xanthene-based acid dye. A salt-forming compound can be obtained by forming a salt.

General formula (3)

[In the general formula (3), R ⁵¹ represents a hydrogen atom or an alkyl group which may have a substituent. R ^{52 to} R ⁵⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁵² Two or more of ^{52 to} R ⁵⁴ may combine with each other to form a ring. Q is an optionally substituted alkylene group, an arylene group which may have a substituent group, ^{-CONH-R 55} - or ^{-COO-R 55} - ^{represents, R 55} has a substituent Represents an alkylene group which may be present. Y ⁻ represents an inorganic or organic anion. ]

The alkyl group which may have a substituent, the alkenyl group which may have a substituent and the aryl group which may have a substituent in the general formula (3) have the same meanings as those in the general formula (2). Is. Moreover, the alkylene group which may have a substituent and the arylene group which may have a substituent in Q of the general formula (3) have an alkyl group which may have a substituent and a substituent. It is a group obtained by removing one hydrogen atom from an optionally substituted aryl group.

(Salt formation)
The salt-forming compound of the acid dye and the resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969. As an example using the xanthene-based acid dye, after dissolving the xanthene-based acid dye in water, a quaternary ammonium salt compound may be added and a chlorination treatment may be performed with stirring. Here xanthene acid sulphonic groups in the dye _(-SO 3 H), forming a portion of the sodium sulfonate groups ammonium group _(-SO 3 Na) moiety and quaternary ammonium salt compound _(NH ^{4 +)} is bonded A salt compound is obtained. Further, instead of water, methanol and ethanol are also solvents that can be used during salinization.

The salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (3) and an acid dye are stirred or shaken. It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain represented by) with an aqueous solution of an acid dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized, and these are ion-bonded, and the ion-bonded portion becomes water-insoluble and is deposited. On the contrary, since the salt consisting of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water. The resin having a cationic group in the side chain and the acidic dye to be used may each be a single type or a plurality of types having different structures.

(Sulfonamide compound)
The acidic dye used in the present invention may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an acidic dye. The sulfonic acid amide compound of an acidic dye which can be preferably used in the acidic dye of the present invention is obtained by chlorinating an acidic dye having —SO ₃ H or —SO ₃ Na by a conventional method to convert —SO ₃ H into —SO ₂ Cl. Can be prepared by reacting this compound with an amine having a —NH ₂ group. Further, as the amine compound which can be preferably used in sulfonamidation, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3-(2-ethylhexyloxy)propylamine, 3-ethoxypropyl It is preferable to use amine, cyclohexylamine and the like.

An example of using a xanthene-based acid dye is C.I. I. To obtain a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3-(2-ethylhexyloxy)propylamine, C.I. I. Acid Red 289 was sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. It is sufficient to obtain a sulfonic acid amide compound of Acid Red 289. Also, C.I. I. When a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3-(2-ethylhexyloxy)propylamine is used, C.I. I. Acid Red 52 was sulfonyl chlorided and then reacted with theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. It suffices to obtain a sulfonic acid amide compound of Acid Red 52.

With other acid dyes such as anthraquinone acid dyes, the sulfonic acid amide compound can be obtained by the same method.

<Other colorants>
The coloring composition of the present invention may further contain another dye, an organic pigment or the like as a coloring agent in addition to the acid dye. In particular, organic pigments are preferable because they can broaden the chromaticity range and have excellent durability. These pigments can be used singly or in a mixture of two or more kinds at an arbitrary ratio as needed.

As the organic pigment, diketopyrrolopyrrole pigment, azo pigment such as azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, or anthraquinone such as violanthrone Examples thereof include pigments, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, slene pigments and metal complex pigments.

Specifically as these organic pigments,
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151. , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208. , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254. 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. it can.

Examples of orange pigments that work similarly to red pigments include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61 and the like can be used. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 254, C.I. I. It is particularly preferable to use Pigment Red 177.

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

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, or 180.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

<Refinement of pigment>
The pigment used in the present invention can be micronized by performing a salt milling treatment or the like. The primary particle diameter of the pigment is preferably 20 nm or more because the dispersion in the pigment carrier is good. Further, it is preferably 100 nm or less because a filter segment having a high contrast ratio can be formed. A particularly preferable range is 25 to 85 nm. The primary particle size of the pigment may be measured, for example, by directly measuring the size of the primary particle from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, for example, the minor axis diameter and the major axis diameter of each primary particle of each pigment are measured in nm unit, and the average is taken as the primary particle diameter of the pigment particle, and then the sphere having the obtained particle diameter is measured. Assuming that, the volume of the particles is calculated, this operation is performed for 100 pigment particles, and the number average particle diameter is calculated by calculating based on the particle diameter and the volume of each pigment particle.

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

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used, but it is preferable to use sodium chloride (salt) from the viewpoint of cost. From the viewpoint of both treatment efficiency and production efficiency, 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.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, 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 subjected to the salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin, and the like can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the above 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.

(Dispersion aid)
When preparing a pigment dispersion, to prevent aggregation of the pigment, to maintain the finely dispersed state of the pigment, to produce a color filter with high brightness and high contrast ratio and high color purity, pigment derivative, resin type dispersion It is preferable to add a dispersion aid such as an agent.

The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more based on 100 parts by weight of the pigment. From the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less, based on 100 parts by weight of the pigment.

The pigment derivative is a compound in which a basic or acidic substituent is introduced into an organic dye. The organic dye also includes a pale yellow aromatic polycyclic compound that is not generally called a dye, such as naphthalene, anthraquinone, and acridone. Examples of the pigment derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and JP-A-9-. Those described in Japanese Patent No. 176511 can be used, and these can be used alone or in combination of two or more kinds.

A resin-type dispersant having excellent pigment dispersibility and having a large effect of preventing reaggregation of the pigment after dispersion can be added to the coloring composition for a color filter of the present invention. The resin-type dispersant can be used in an amount of preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment.

The resin-type dispersant has an acidic group or a basic group because it is adsorbed on the surface of the pigment by using an acidic group or a basic group as an anchor, and the repulsion effect of the polymer effectively acts to maintain dispersion stability. It is preferably a polymer. The acidic group is preferably a sulfone group because of its excellent adsorption properties, and the basic group is preferably an amino group because of its excellent adsorption properties. Further, the combined use of the pigment derivative having an acidic group and the resin type dispersant having a basic group, or the combined use of the pigment derivative having a basic group and the resin type dispersant having an acidic group has good compatibility with the resin. Therefore, it is preferable.

As the resin-type dispersant having an acidic group or a basic group, a comb polymer having a structure in which a branch polymer part is graft-bonded to a trunk polymer part having an acidic group or a basic group has an excellent steric repulsion effect of the branch polymer part. Therefore, it is preferable because it is more soluble in an organic solvent. Further, a comb polymer having a molecular structure in which two or more branch polymers are graft-bonded to one molecule of the trunk polymer is more preferable for the above reason.

Examples of commercially available resin type dispersants include DisPerByk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 manufactured by Big Chemie. 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-TerrA-U, 203, 204, or BYK-P104, P104S, 220S, or LACtimon, LACtimon-WS, or Bykumen. , SOLUPERSE-3000, 9000, 13240, 13650, 13940, 17,000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000 manufactured by Lubrizol Japan. , 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, manufactured by Fuka Chemicals. LP4560,120,150,1501,1502,1503 etc. are mentioned.

《Binder resin》
The coloring composition for a color filter of the present invention further contains a binder resin. By containing a binder resin, the dispersion stability of the coloring composition of the present invention becomes better, and when a colored pixel layer of a color filter is formed using the coloring composition for a color filter, there is little pigment aggregation, and development It is possible to obtain a colored pixel layer having excellent properties and pattern shape.

The binder resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Further, a thermoplastic resin is preferable, and when it is used in the form of an alkali-developing colored resist material, it is preferable to use an alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used to further improve the photosensitivity. In particular, when an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used for an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the photocuring density is increased, and as a result, the resistance is improved, which is more preferable.

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, polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin. Above all, it is preferable to use an acrylic resin.

Examples of the alkali-soluble resin copolymerized with the acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and 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 thereof include isobutylene/(anhydrous) maleic acid copolymer. Above all, 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 it has high heat resistance and transparency.

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

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

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

Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted compounds. Examples thereof include monocarboxylic acid, and these may be used alone or in combination of two or more kinds.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These may be used alone or in combination of two or more kinds. I don't care. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride, or use a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to leave the remaining anhydride. It is also possible to hydrolyze the group. In addition, when etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

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

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

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

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but they are not limited thereto. Alternatively, two or more types can be used together.

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

When the binder resin is used as a photosensitive coloring composition for a color filter, it is preferable to use a resin having an acid value of 20 to 300 mgKOH/g from the viewpoint of dispersibility, penetrability, developability and resistance of the pigment. When the acid value is less than 20 mgKOH/g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, no fine pattern will remain.

The binder resin is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the colorant since it has good film-forming properties and various resistances. Since the colorant concentration is high and good color characteristics can be exhibited. It is preferably used in an amount of 1000 parts by weight or less.

<<Ionic acrylic resin [C]>>
The colored composition of the present invention contains an ionic acrylic resin [C] represented by the following general formula (1) and having a maximum molar absorption coefficient ε in the visible light region of 0 or more and 3000 or less, As a result, even when an acid dye is used, the color filter has excellent heat resistance and high brightness.

[In the general formula (1), R ₁₀₁ represents a hydrogen atom or an alkyl group which may have a substituent. R _{102 to} R ₁₀₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent or an aryl group which may have a substituent, and R ₁₀₂ Two or more of _{102 to} R ₁₀₄ may combine with each other to form a ring. Q is an optionally substituted alkylene group, an optionally substituted arylene group, _{-CONH-R 105} - or _{-COO-R 105} - _{represents, R 105} is a substituent Represents an alkylene group which may be present. Z ⁻ represents an anion having a group selected from the group consisting of a cyano group, a nitro group and a halogenated hydrocarbon group, PF ₆ ⁻ or BF ₄ ⁻ . ]

The alkyl group which may have a substituent, the alkenyl group which may have a substituent and the aryl group which may have a substituent in the general formula (1) have the same meanings as those in the general formula (2). Is. Further, the alkylene group which may have a substituent and the arylene group which may have a substituent in Q of the general formula (1) have an alkyl group which may have a substituent and a substituent. It is a group obtained by removing one hydrogen atom from an optionally substituted aryl group.

Here, the maximum value of the molar extinction coefficient ε in the visible light region (wavelength 400 nm to 700 nm) is adjusted by diluting 0.1 g of the ionic acrylic resin [C] with ethyl lactate to 0.250 L to prepare a solution. It is determined by measuring the absorption spectrum in the visible light region with an ultraviolet-visible spectrophotometer and calculating it using the Lambert-Beer's law. It is preferable that the maximum molar extinction coefficient ε in the visible light region (400 to 700 nm) is 0 or more and 3000 or less from the viewpoint of color clarity. Further, the ionic acrylic resin [C] is more preferably a case where the maximum value of the molar extinction coefficient ε in the wavelength range is 0 or more and 2000 or less, and still more preferably 0 or more and 1000 or less.

<Z ⁻ in the general formula (1)>
Z ⁻ represents a cyano group, a nitro group, an anion having a halogenated hydrocarbon group, PF ₆ ⁻ , or BF ₄ ⁻ , but Z ^{− additionally} contains a phosphorus atom, a boron atom, a nitrogen atom or a sulfur atom. It may be. Among these, an anion having a halogenated hydrocarbon group is preferable because it can have particularly excellent heat resistance, and in particular, an anion represented by the general formula (1a) and a general formula (1b) are preferable. ), an anion represented by the general formula (1c), or an anion represented by the general formula (1d), a color filter having a high brightness can be obtained even after heating and baking at 230° C. or higher, It is preferable. Further, a sulfonic acid having a halogenated hydrocarbon group (-SO ₃ H), sulfonimide acid (-SO ₂ NHSO ₂ -), if having a conjugate base of sulfonmethide acid (-SO ₂ NH-), the more acidity It is preferable to introduce a conjugated base of a strong organic acid as an anion part.

<Anion having a cyano group>
The anion having a cyano group is not particularly limited, and examples thereof include anions having a monovalent hydrocarbon group substituted with a cyano group, and the monovalent hydrocarbon group is a substituent other than the cyano group. May have. As the monovalent hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group and an alkylaryl group are preferable, an aryl group is more preferable, and a phenyl group is particularly preferable.

<Anion having a nitro group>
The anion having a nitro group is not particularly limited, and examples thereof include anions having a monovalent hydrocarbon group substituted with a nitro group, and the monovalent hydrocarbon group is a substituent other than the nitro group. May have. As the monovalent hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group and an alkylaryl group are preferable, an aryl group is more preferable, and a phenyl group is particularly preferable.

<Anion having halogenated hydrocarbon group>
The halogenated hydrocarbon group refers to a monovalent hydrocarbon group substituted with a halogen atom, and examples of the halogen atom include a fluoro group, a chloro group, a bromo group, and an iodo group. Therefore, it is preferable to have a fluoro group. Further, it may have a substituent other than a halogen atom.
As the hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group and an alkylaryl group are preferable, and an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, An alkylaryl group having 7 to 20 carbon atoms is more preferable. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, an amyl group and a tertiary group. Examples thereof include amyl group, hexyl group, heptyl group, octyl group, isooctyl group, tertiary octyl group and 2-ethylhexyl group. Further, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. Examples of the alkylaryl group include groups in which an aryl group having 6 to 14 carbon atoms is substituted with the above alkyl group having 1 to 8 carbon atoms.

That is, a perfluoroalkyl group having 1 to 6 carbon atoms (more preferably 1 to 4) in the fluorinated alkyl group and a perfluoroalkyl group having 6 to 14 carbon atoms (more preferably 6 to 10) in the fluorinated aryl group. The aryl group is preferably a perfluoroalkylaryl group having 7 to 20 carbon atoms (more preferably 7 to 16 carbon atoms) in the fluorinated alkylaryl group.
Specifically, for example, CF ₃ group, CF ₃ CF ₂ group, (CF ₃ ) ₂ CF group, CF ₃ CF ₂ CF ₂ group, CF ₃ CF ₂ CF ₂ CF ₂ group, (CF ₃ ) ₂ CFCF ₂ Group, CF ₃ CF ₂ (CF ₃ )CF group, (CF ₃ ) ₃ C group, pentafluorophenyl group, phenyl group substituted with CF ₃ group, and the like.

The halogen atom can replace a part or all of the hydrogen atoms of the hydrocarbon group, but especially the hydrogen atom of the hydrocarbon group is a halogen atom, preferably 80 mol% or more, more preferably 90% mol or more, It is particularly preferred that the substitution is 100 mol %. Thereby, heat resistance can be further improved.

(Anion represented by general formula (1a))
The anion represented by the general formula (1a) is an anion having a phosphorus atom and a halogenated hydrocarbon group.

[In the general formula (1a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halogen atom, and when R ¹ and Hal are present in plural, they may be the same. May be different. c represents an integer of 1 to 6. ]

Examples of Hal include a fluoro group, a chloro group, a bromo group, and an iodo group, and a fluoro group is preferable.

R ¹ represents a halogenated hydrocarbon group, and as the halogenated hydrocarbon group, the halogenated hydrocarbon group described in the description of the anion having a halogenated hydrocarbon group as Z ⁻ in the general formula (1) is used. A group can be mentioned. In the present invention, R ¹ is preferably a fluorinated alkyl group or a fluorinated aryl group. Of these, a fluorinated aryl group is preferable, and a pentafluorophenyl group is particularly preferable.

Representative examples of the anion represented by the general formula (1a), for ^{_{example, (CF 3) 3 PF 3}} -, (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 ^{− and the} like. Among them, PF ₆ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , (n-CF ₇ ) ₃ PF ₃ ⁻ , (n−C ₄ F ₉ ) ₃ PF _{3 ^{-, [(CF 3) 2}} CF] 3 PF 3 -, [(CF 3) 2 CF] 2 PF 4 -, [(CF 3) 2 CFCF 2] 3 PF 3 -, [(CF 3) 2 CFCF 2 ] ₂ PF ₄ ⁻ is preferable.

(Anion represented by general formula (1b))
The anion represented by the general formula (1b) is an anion having a boron atom and a halogenated hydrocarbon group.

[In General Formula (1b), R ² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a cyano group, B represents a boron atom, and Hal represents a halogen atom. , R ² and Hal each may be the same or different. d represents an integer of 1 to 4. ]

Examples of Hal include a fluoro group, a chloro group, a bromo group, and an iodo group, and a fluoro group is preferable.

R ² is a halogenated hydrocarbon group, a cyano group or a nitro group or a phenyl group substituted with a cyano group, the halogenated hydrocarbon group, in Formula (1) described above, Z ^- halogenated hydrocarbons as The halogenated hydrocarbon group mentioned in the description of the anion having a hydrogen group can be mentioned. In the present invention, R ² is preferably a halogenated hydrocarbon group, more preferably a fluorinated alkyl group or a fluorinated aryl group.

Representative examples of the anion represented by the general formula (1b), for ^{_{example, (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 -, (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 -, (n}} -C 3 F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 ^{_{-, (n-C 6 F}} 13) 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) -, tetrakis (penta Examples thereof include fluorophenyl)borate anion. Among them, BF ₄ ⁻ , B(CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , tetrakis (penta). The fluorophenyl)borate anion is preferred.

(Anion represented by general formula (1c))
The anion represented by the general formula (1c) is an anion having a nitrogen atom and a halogenated hydrocarbon group.

[In the general formula (1c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group or an FSO ₂ group, and R ³¹ and R ³² are both In the case of a halogenated hydrocarbon group which may have a sulfonyl group, they may combine with each other to form a ring. However, at least one of R ³¹ and R ³² is a halogenated hydrocarbon group or a cyano group. ]

R ³¹ and R ³² each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group, or an FSO ₂ group, and the halogenated hydrocarbon group is represented by the above general formula ( In 1), the halogenated hydrocarbon group mentioned in the description of the anion having a halogenated hydrocarbon group can be mentioned as Z ⁻ . Further, R ³¹ and R ³² may form an aliphatic saturated hydrocarbon ring structure.

In the present invention, R ³¹ and R ³² are each independently preferably a halogenated hydrocarbon group linked by a sulfonyl group, and among them, a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group is preferable, and particularly, Preferably, the group represented by the general formula (1c-1) or the group represented by the general formula (1c-2) is particularly excellent in heat resistance.

The halogenated hydrocarbon group which may be linked by a sulfonyl group is not particularly limited, and a halogenated alkylsulfonyl group can be appropriately selected and used. The alkyl group forming the skeleton of the halogenated alkylsulfonyl group may be linear or branched, and preferably has 1 to 8 carbon atoms. Specific examples of the alkyl group include those similar to the alkyl group in the halogenated hydrocarbon group. Alternatively, a fluoro group is preferable as the halogen atom in the alkylensulfonyl group. The halogen atom can replace a part or all of the hydrogen atoms of the hydrocarbon group, but from the viewpoint of heat resistance, the hydrogen atom of the hydrocarbon group is preferably a halogen atom, preferably 80 mol% or more, and more preferably Those substituted by 90% mol or more, particularly preferably 100 mol% are preferable.

General formula (1c-1)

[In General Formula (1c-1), R ⁵ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ — or R 5 ¹⁷ COOR ¹⁸ CFH— (R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or an aryl group which may have a substituent, and R ¹⁸ represents an alkylene group), n represents an integer of 1 or more, and “*” represents a bond. When both R ⁵ are fluorinated alkyl groups, they may be bonded to each other to form a ring. ]

General formula (1c-2)

[In the general formula (1c-2), R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, an alkoxy group or an alkylsulfonyl group, and “*” is Represents a bond. However, at least one of R ^{6 to} R ¹⁰ is a fluorine atom or a fluorinated alkyl group. ]

In the general formula (1c-1) and the general formula (1c-2), the alkyl group may be linear or branched, and the carbon number of the alkyl group is 1 to 12 (more preferably 1 to 8). Is preferred. The alicyclic hydrocarbon group may be a bridged alicyclic hydrocarbon group having 2 to 4 rings, and the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms (more preferably 3 to 12 carbon atoms). The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from nitrogen atom, oxygen atom and sulfur atom. The aryl group is preferably an aryl group having 6 to 14 carbon atoms (more preferably 6 to 10 carbon atoms), and particularly preferably a phenyl group. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a trifluoromethyl group, and the position and number of the substituent are arbitrary. When it has two or more groups, the substituents may be the same or different. R ²¹ represents a methylene group or an alkylene group, but a methylene group or an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable from the viewpoint of easy production. The upper limit of n is preferably 10, and more preferably 8.

Suitable anions among the anions represented by the general formula (1c) include, for example, [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ )N(CF ₃ SO ₂ )] ⁻ , and [(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}] -, [(FSO 2) N {CF 3 CF ^{_{2 (CF 3) CFSO 2}}} ] -, [(FSO 2) N {(CF 3) 3 CSO 2}] -, [(CF 3 SO 2) 2 N] -, [(CF 3 CF 2 SO 2) ^{_{2 N] -, [(CF}} 3 CF 2 CF 2 SO 2) 2 N] -, (CF 3 CF 2 CF 2 CF 2 SO 2) 2 N] -, [{(CF 3) 2 CFCF 2 SO 2} ^{_{2 N] -, [{CF}} 3 CF 2 (CF 3) CFSO 2} 2 N] -, [{(CF 3) 3 CSO 2} 2 N] -, or the following compounds and the like.

(Anion represented by general formula (1d))
The anion represented by the general formula (1d) is an anion having a sulfur atom and a halogenated hydrocarbon group.

[In the general formula (1d), R ⁴ represents a halogenated hydrocarbon group which may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

R ⁴ represents a halogenated hydrocarbon group which may have a nitrogen atom or an oxygen atom, and the halogenated hydrocarbon group is a halogenated hydrocarbon group represented by Z ⁻ in the above-mentioned general formula (1). The halogenated hydrocarbon group mentioned in the description of the anion having a group can be mentioned. R ⁴ may be linked by —O—, —CO—, —COO—, —CO—NH— or the like.

In the present invention, R ⁴ is preferably a group represented by the general formula (1d-1) or a group represented by the following formula (1d-2) because it is particularly excellent in heat resistance.

General formula (1d-1)

[In General Formula (1d-1), R ¹¹ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ -or R. ¹⁷ COOR ¹⁸ CFH— (R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or an aryl group which may have a substituent, and R ¹⁸ represents an alkylene group), n represents an integer of 1 or more, and “*” represents a bond. When both R ¹¹ are fluorinated alkyl groups, they may be bonded to each other to form a ring. ]

General formula (1d-2)

[In the general formula (1d-2), R ^{12 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, an alkoxy group or an alkylsulfonyl group, and “*” is , Represents a bond. However, at least one of R ^{12 to} R ¹⁶ is a fluorine atom or a fluorinated alkyl group. ]

In formulas (1d-1) and (1d-2), R ¹¹ represents a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ — or R 11. ¹⁷ COOR ¹⁸ CFH- is preferable, and a fluorine atom, an alicyclic hydrocarbon group, a perfluoroalkoxy group, R ¹⁷ COOCH ₂ CH ₂ -or R ¹⁷ COOCH ₂ CH ₂ CFH- is particularly preferable. R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group. The alkyl group may be linear or branched, and the alkyl group has 1 to 12 carbon atoms. (More preferably 1 to 8). The alicyclic hydrocarbon group may be a bridged alicyclic hydrocarbon group having 2 to 4 rings, and the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms (more preferably 3 to 12 carbon atoms). The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from nitrogen atom, oxygen atom and sulfur atom. The aryl group is preferably an aryl group having 6 to 14 carbon atoms (more preferably 6 to 10 carbon atoms), and particularly preferably a phenyl group. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a trifluoromethyl group, and the position and number of the substituent are arbitrary. When it has two or more groups, the substituents may be the same or different. R ²¹ represents a methylene group or an alkylene group, but a methylene group or an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable from the viewpoint of easy production. The upper limit of n is preferably 10, and more preferably 8.
Further, in the formula (1d-2), at least three of R ^{12 to} R ¹⁶ are preferably a fluorine atom or a fluorinated alkyl group.

Typical examples of the anion represented by the general formula (1d) include the anions shown below.

<<Method for producing ionic acrylic resin [C]>>
The ionic acrylic resin of the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in its side chain and an ionic compound containing Z ⁻ of the general formula (1) are stirred or vibrated. It can be easily obtained by mixing an aqueous solution of a resin having a cationic group with an aqueous solution of an ionic compound containing Z ⁻ of the general formula (1) under stirring or vibration. In the aqueous solution, the cationic group of the resin and the Z ⁻ site of the ionic compound containing Z ⁻ of the general formula (1) are ionized, and these are ionically bonded, and the ionically bonded portion becomes insoluble in water and precipitates. On the contrary, since the salt consisting of the counter anion of the resin and the counter cation of the ionic compound containing Z ⁻ of the general formula (1) is water-soluble, it can be removed by washing with water or the like. The resin having a cationic group in the side chain and the ionic compound containing Z ⁻ of the general formula (1) to be used may each be only a single type or may be a plurality of types having different structures. ..

As the aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent is used to dissolve the resin having a cationic group in the side chain and the ionic compound containing Z- of the general formula (1). May be. As the water-soluble organic solvent, methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2-(methoxymethoxy)ethanol, 2- Butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone , Diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone 1,2-hexanediol, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

《Polyfunctional monomer》
As the polyfunctional monomer, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane It is possible to increase polyfunctional monomers having an acidic group such as various acrylic acid esters and methacrylic acid esters such as tri(meth)acrylate, or photopolymerizable monomers in which polymerization is partially induced by radicals.

(Polyfunctional monomer having an acidic group)
Examples of the polyfunctional monomer having an acidic group include, for example, esterification products of poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohol and (meth)acrylic acid, and dicarboxylic acids; polyvalent carboxylic acids, and monohydroxyalkyl. Examples thereof include esterified products with (meth)acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and other monohydroxyoligoacrylates or monohydroxyoligomethacrylates. And a free carboxyl group-containing monoester of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, or oligoesterification products containing a free carboxyl group with monohydroxy monomethacrylates.

Further, a compound represented by the following general formula (5) can also be preferably used.
General formula (5)
_{(H 2 C = C (R} c) COO) m'-X- (OCOCH (R d) CH 2 S (R d) COOH) n '
[In general formula (5), R _c is a hydrogen atom or a methyl group, R _d is a hydrocarbon group having 1 to 12 carbon atoms, X is an (m+n)-valent organic group having 3 to 60 carbon atoms, and m′ is 2 The integer of -18, n'represents the integer of 1-3. ]

Here, the compound represented by the following general formula (5) can be easily obtained, for example, by the following method.
(1) A method of esterifying a compound giving an organic group represented by X with acrylic acid to acrylate, and then adding a mercapto compound to the obtained compound. (2) Adding a compound giving an organic group represented by X After modification with an isocyanate compound, the obtained compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound (3) A compound giving an organic group represented by X is acryl A method of esterifying with an acid to acrylate, followed by modification with a polyisocyanate compound and adding a mercapto compound to the obtained compound.

Examples of the compound giving the organic group represented by X include pentaerythritol, pentaerythritol-modified caprolactone, pentaerythritol-polyisocyanate modified product, dipentaerythritol, dipentaerythritol-caprolactone modified product, dipentaerythritol-polyisocyanate modified product I can list things.

Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

The content of the polyfunctional 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>
As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenone system such as morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Compounds, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, and other benzoin compounds, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4- Benzoyl-4'-methyldiphenyl sulfide, benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2 -(P-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4, 6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)- s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4 -Trichloromethyl(4'-methoxystyryl)-6-triazine and other triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O- Benzoyl oxime)], O-(acetyl)-N-(1-phenyl-2-oxo-2-(4′-methoxy-naphthyl)ethylidene)hydroxylamine, and other oxime ester compounds, bis(2,4,6) -Trimethylbenzoyl)phenylphosphine oxide, phosphine compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)- Imidazole compounds such as 4,4′,5,5′-tetra(p-methylphenyl)biimidazole, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone, borate compounds, A carbazole-based compound, a titanocene-based compound or the like is used. These photopolymerization initiators can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

Among these, it is more preferable to include an acetophenone compound or an oxime ester compound as the photopolymerization initiator. Since the acetophenone compound and the oxime ester compound have extremely high sensitivity, the content of the photopolymerization initiator can be reduced. As a result, the brightness as a color filter can be improved, which is preferable.

These photopolymerization initiators are preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant in the color filter coloring composition, and are 10 to 150 parts by weight from the viewpoint of photocurability and developability. More preferably.

<<sensitizer>>
The coloring composition for color filters of the present invention may contain a sensitizer. As the sensitizer, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, Polymethine dyes such as anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, merocyanine derivative, oxonole derivative, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline Derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphy Examples thereof include a azine derivative, a naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyrylium derivative, a tetraphyllin derivative, an anulene derivative, a spiropyran derivative, a spirooxazine derivative, a thiospiropyran derivative, a metal arene complex, an organic ruthenium complex, and a Michler's ketone derivative. These sensitizers may be used alone or in a mixture of two or more at an arbitrary ratio, if necessary.

More specific examples include Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadasaburo Ikemori et al., Special Examples of the sensitizer include those described in "Functional Material" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near infrared region may be contained. Among the above-mentioned sensitizers, particularly preferable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

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 coloring composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

"Organic solvent"
The coloring composition for a color filter of the present invention sufficiently disperses a colorant in a dye carrier such as a binder resin or a polyfunctional monomer, and has a dry film thickness of 0.2 to 10 μm on a transparent substrate such as a glass substrate. It is used to facilitate the application as described above to form a filter segment or a black matrix.

Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene. , N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, 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 mono. Ethyl 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, di Propylene 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 monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, acetic acid Examples thereof include n-amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester. These solvents may be used alone or in admixture of two or more kinds at an arbitrary ratio if necessary.

The solvent can be used in an amount of 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

《Multifunctional thiol》
The coloring composition for a color filter of the present invention may contain a polyfunctional thiol. The polyfunctional thiol is a compound having two or more thiol (SH) groups. By using the polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, since it functions as a chain transfer agent, a thiyl radical that is less susceptible to polymerization inhibition by oxygen is generated. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol having an SH group bonded to an aliphatic group such as methylene or ethylene is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. Nate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionate 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 as a mixture of two or more kinds at an arbitrary ratio according to need.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, and more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant. Better development resistance can be obtained by using 0.05 parts by weight or more of the polyfunctional thiol. When a monofunctional thiol having one thiol (SH) group is used, such improvement in development resistance cannot be obtained.

《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 its 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 BYK 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 together. The content of the leveling agent is usually preferably 0.003 to 1.0 part by weight based on 100 parts by weight of the total weight of the coloring composition.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a small hydrophilicity even though having a hydrophilic group, when added to the coloring composition, It has the characteristic of low surface tension lowering ability, and it is useful that it has good wettability to the glass plate in spite of the low surface tension lowering ability. Those that can sufficiently suppress the charging property can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

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. It may be of a linear block copolymer type in which alternately and repeatedly bonded. 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. -207, but not limited thereto.

Anionic, cationic, nonionic or amphoteric surfactants can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Examples of anionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyldiphenyletherdisulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples thereof include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate. Examples thereof include polyethylene glycol monolaurate and the like; alkylbetaine such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based or silicone-based surfactants.

<<UV absorber, polymerization inhibitor>>
The coloring composition for color filters of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By including an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl). -1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, etc. Hydroxyphenyltriazine type, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, Benzotriazoles such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'. , 4,4'-Tetrahydroxybenzophenone and other benzophenones, phenyl salicylates, p-tert-butylphenyl salicylates and other salicylates, ethyl-2-cyano-3,3'-diphenyl acrylates and other cyanoacrylates System, 2,2,6,6,-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, poly [[6-[(1,1,3,3-Tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl) Imino] and the like. These ultraviolet absorbers may be used alone or in combination of two or more at an arbitrary ratio as needed.

Examples of the polymerization inhibitor include hydroquinone such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, and the like And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine and other nitroso compounds, and ammonium salts or aluminum salts thereof. These polymerization inhibitors can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant in the coloring composition. Better resolution can be obtained by using 0.01 parts by weight or more of the ultraviolet absorber or the polymerization inhibitor.

"Antioxidant"
The coloring composition for color filters of the present invention may contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant enhances the transmittance of the coating film in order to prevent the resin and the photopolymerization initiator contained in the color filter coloring composition from being oxidized and yellowing due to a thermal process during thermosetting or ITO annealing. be able to. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented and a high transmittance of the coating film can be obtained.

Preferable antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants and sulfide-based antioxidants. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant. These antioxidants can be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

As the hindered phenolic antioxidant, 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5- Di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and the like can be mentioned.

Among hindered amine antioxidants, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4- Piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4) -Butane tetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6- Tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4- Diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and 1-( Polycondensate with 2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like.

As the phosphorus-based antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine- 6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2- Illy)oxy]ethyl]amine, and ethylbisphosphite bis(2,4-ditert-butyl-6-methylphenyl).

Examples of the sulfide-based antioxidant include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and 2,4-bis[(octylthio)methyl]- Examples thereof include o-cresol and 2,4-bis[(laurylthio)methyl]-o-cresol.

The content of the antioxidant is preferably 0.1 to 5% by weight based on 100% by weight of the total solid content of the color filter coloring composition. When the amount of the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small, and when the amount is more than 5% by weight, the hardness is significantly reduced and the sensitivity of the color filter coloring composition is greatly reduced.

《Other ingredients》
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent in order to improve the adhesion to a transparent substrate, or an amine compound having a function of reducing dissolved oxygen. Can be made.

Examples of the silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, vinyltrimethoxysilane and other vinylsilanes, γ-methacryloxypropyltrimethoxysilane and other (meth)acrylsilanes, β-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy) Epoxysilanes such as cyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β (Aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ Examples thereof include aminosilanes such as -aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the coloring agent in the coloring composition.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4 Examples include 2-ethylhexyl dimethylaminobenzoate and N,N-dimethylparatoluidine.

<<Method for producing colored composition for color filter>>
The coloring composition for a color filter of the present invention comprises a colorant containing an acid dye in a colorant carrier such as a binder resin and/or a solvent, and various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader and an attritor. To produce a colorant dispersion, and a photopolymerization initiator, a binder resin, a polyfunctional monomer, an ionic acrylic resin [C], a sensitizer, and a sensitizer may be added to the colorant dispersion. A functional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, a solvent, and other components can be mixed and stirred for production. The ionic acrylic resin [C] can obtain the same effect when it is used in the production of the colorant dispersion or is added later to the colorant dispersion.

When the colorant, especially the pigment, is dispersed in the binder resin and/or the solvent, a dispersion aid such as a resin type pigment dispersant, a surfactant or a pigment derivative may be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a large effect of preventing reaggregation of the pigment after dispersion, a coloring composition for a color filter obtained by dispersing the pigment in a resin and/or a solvent using the dispersion aid. When a material is used, a color filter having excellent transparency can be obtained. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment.

Further, the coloring composition for a color filter of the present invention can also be produced by mixing an acidic dye, another coloring agent and the like separately dispersed in a coloring agent carrier. Furthermore, when the solubility of the acid dye or other coloring agent is high, specifically, the solubility in the solvent to be used is high, and it is dissolved by stirring, and if foreign matter is not confirmed, the fineness as described above is obtained. It is not necessary to manufacture it in a dispersed manner.

The coloring composition for a color filter is mixed with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, a sintering filter, a membrane filter or the like. It is preferable to remove dust.

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

As the transparent substrate, a glass plate of soda lime glass, low-alkali borosilicate glass, non-alkali aluminoborosilicate glass, or the like, or a resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is 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 for driving the liquid crystal after paneling.

The contrast of the liquid crystal display panel can be further enhanced by forming the black matrix in advance before forming the filter segment on the transparent substrate. As the black matrix, chromium, a 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 the black matrix is not limited thereto, and the coloring composition for a color filter of the present invention is used. A black matrix formed from is preferred. It is also possible to previously form a thin film transistor (TFT) on the transparent substrate or the reflective substrate and then form the filter segment. By forming the filter segment and/or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the brightness can be improved.

The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

The formation of each color filter segment and the black matrix by the photolithography method is performed by the following method. That is, the coloring composition for a color filter prepared as a coloring composition for a solvent developing type or an alkali developing type coloring color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern, which is provided in contact or non-contact with the film.

Then, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developing solution, or spraying the developing solution with a spray or the like to remove the uncured portion and form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by the development, heating can be applied if necessary. The photolithography method can form the filter segment and the black matrix with higher accuracy than the printing method.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid pour) developing method, or the like can be applied. In order to increase the ultraviolet exposure sensitivity, after coating and drying the color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is coated and dried to prevent polymerization inhibition by oxygen. After forming the film, ultraviolet exposure can be performed.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film and the like are formed on the color filter as needed.

The color filter is attached to the counter substrate using a sealant, liquid crystal is injected from the injection port provided in the sealing section, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is placed on the outside of the substrate. A liquid crystal display panel is manufactured by pasting.

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, in an Example, "part" and "%" represent a "mass part" and "mass %", respectively. PGMEA and PGMAc both represent propylene glycol monomethyl ether acetate. Further, the average primary particle diameter of the pigment, the weight average molecular weight (Mw) of the resin, the ammonium salt value of the resin having a cationic group in the side chain, and the method of calculating the molar extinction coefficient are as follows.

(Average primary particle diameter of pigment)
A solvent (for example, propylene glycol monomethyl ether acetate) is added to the powder of the pigment, a small amount of a dispersant (for example, DISperbyk-161: a dispersant by Big Chemie) is added, and the mixture is treated with ultrasonic waves for 1 minute to prepare a measurement sample. Then, using a transmission (TEM) electron microscope, three photographs (for three fields of view) in which 100 or more primary particles of the pigment can be confirmed are prepared, and the sizes of 100 primary particles are measured in order from the upper left. .. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured in nm units, and the average is taken as the primary particle diameter of the pigment particles, and a total of 300 distributions are created in 5 nm increments. The number average particle diameter is calculated by approximating the median value in 5 nm increments (for example, 8 nm in the case of 6 nm or more and 10 nm or less) as the particle diameter of these particles, and calculating based on each particle diameter and the number thereof.

(Polymerization average molecular weight (Mw))
The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Ammonium salt value of resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the chain is a value obtained by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent amount of potassium hydroxide, It represents the ammonium salt value of the solid content.

(Calculation method of molar extinction coefficient)
0.1 g of each sample was placed in a volumetric flask, and then diluted with ethyl lactate to 0.250 L. The absorption spectrum of this solution was measured with an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), and the visible light range (using Lambert-Beer's law). The maximum value [ε M] of the molar extinction coefficient ε at 400 nm to 700 nm) was calculated.

<Method for producing acrylic resin solution>
(Acrylic resin solution (B-1))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer was charged with 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80° C., and the inside of the reaction vessel was filled with nitrogen. After substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd., were added through a dropping pipe. )) 7.4 parts and a mixture of 0.4 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a solid content of 30% by weight and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was adjusted to 20% by weight in the resin solution synthesized above. Ether acetate was added to obtain an acrylic resin solution (B-1) which was an alkali-soluble resin.

<Method for producing resin having cationic group in side chain>
(Resin 1 having a cationic group in the side chain)
75.1 parts of isopropyl alcohol was charged into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride methacrylate salt, and 15.6 parts of methyl ethyl ketone were homogenized. Then, the mixture was placed in a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield from the solid content was 98% or more and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50°C. Then, 72 parts of isopropyl alcohol was added to obtain Resin 1 having 40% by weight of the resin component and having a cationic group in the side chain. The ammonium salt value of the obtained resin was 33 mgKOH/g.
Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Further, the ammonium salt value of the resin having a cationic group in the side chain was determined by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent amount of potassium hydroxide. The value represents the ammonium salt value of the solid content.

(Resin 2 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile). (6) and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield from the solid content was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. Methyl chloride (3.2 parts) and ethanol (22.0 parts) were added thereto, reacted at 50°C for 2 hours, heated to 80°C over 1 hour, and further reacted for 2 hours. Thus, a resin 2 having a resin component of 47% by weight and having a cationic group in the side chain was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Resin 3 having a cationic group in the side chain)
75.1 parts of isopropyl alcohol was charged into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 18.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 24.8 parts of 2-ethylhexyl methacrylate, 2.5 parts of methacrylic acid, 15.0 parts of hydroxyethyl methacrylate, dimethylaminoethylmethyl chloride methacrylate salt. After homogenizing 12.2 parts and 15.6 parts of methyl ethyl ketone, the mixture was placed in a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7280, and the mixture was cooled to 50°C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 3 having 40% by weight of the resin component and having a cationic group in the side chain. The ammonium salt value of the obtained resin was 33 mgKOH/g.

(Resin 4 having a cationic group in the side chain)
75.1 parts of isopropyl alcohol was charged into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 27.5 parts of (3-ethyloxetan-3-yl)methyl methacrylate, 2.5 parts of methacrylic acid, 57.8 parts of t-butyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride methacrylate, and methyl ethyl ketone. After homogenizing 15.6 parts, the mixture was placed in a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield from the solid content was 98% or more and the weight average molecular weight (Mw) was 7510, and the mixture was cooled to 50°C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 4 having 40% by weight of the resin component and having a cationic group in the side chain. The ammonium salt value of the obtained resin was 33 mgKOH/g.

(Resin 5 having a cationic group in the side chain)
75.1 parts of isopropyl alcohol was charged into a 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 21.5 parts of (3-ethyloxetan-3-yl)methyl methacrylate, 2.5 parts of methacrylic acid, 51.6 parts of t-butyl methacrylate, 24.4 parts of dimethylaminoethyl methyl chloride methacrylate, and methyl ethyl ketone. After homogenizing 15.6 parts, the mixture was placed in a dropping funnel, attached to a 4-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield from the solid content was 98% or more and the weight average molecular weight (Mw) was 7030, and the mixture was cooled to 50°C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 5 having 40% by weight of the resin component and having a cationic group in the side chain. The ammonium salt value of the obtained resin was 65 mgKOH/g.

<Method for producing salt forming compound of acid dye>
(Salt-forming compound (A-1))
C. I. A salt-forming compound (A-1) comprising Acid Red 52 and Resin 1 having a cationic group in its side chain was produced.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise to the resin solution. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and 32 parts of C.I. I. A salt-forming compound (A-1) of Acid Red 52 and Resin 1 having a cationic group in its side chain was obtained. At this time, C.I. in the salt-forming compound (A-1) was used. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Salt-forming compound (A-2))
C. I. A salt-forming compound (A-2) composed of Acid Red 289 and Resin 2 having a cationic group in its side chain was produced.
To 2000 parts of water, 51 parts of the resin 2 having a cationic group in the side chain is added, and after sufficiently stirring and mixing, the mixture is heated to 60°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Red 289 is dissolved is prepared, and the resin solution is dropped little by little. After the dropping, the mixture is stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and 32 parts of C.I. I. A salt-forming compound (A-2) of Acid Red 289 and Resin 2 having a cationic group in its side chain was obtained.

(Salt-forming compound (A-3))
C. I. A salt-forming compound (A-3) consisting of Acid Blue 112 and Resin 1 having a cationic group in its side chain was produced.
To 2000 parts of a 10% aqueous methanol solution, 51 parts of resin 1 having a cationic group in the side chain is added, and the mixture is sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Blue 112 is dissolved is prepared, and the resin solution is dropped little by little. After the dropping, the mixture is stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and 31 parts of C.I. I. A salt-forming compound (A-3) of Acid Blue 112 and Resin 1 having a cationic group in its side chain was obtained.

(Salt-forming compound (A-4))
C. I. A salt-forming compound (A-4) consisting of Acid Blue 93 and Resin 1 having a cationic group in its side chain was produced.
To 2000 parts of a 10% aqueous solution of N,N-dimethylformamide, 51 parts of Resin 1 having a cationic group in the side chain is added, and after sufficiently stirring and mixing, the mixture is heated to 70°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Blue 93 is dissolved is prepared, and the resin solution is dropped little by little. After the dropping, the mixture is stirred at 70° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 29 parts of C.I. I. A salt-forming compound (A-4) of Acid Red 93 and Resin 1 having a cationic group in its side chain was obtained.

(Salt-forming compound (A-5))
C. I. A salt-forming compound (A-5) consisting of Acid Red 249 and Resin 1 having a cationic group in its side chain was produced.
To 2000 parts of 20% acetic acid, 51 parts of the resin 1 having a cationic group on the side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 60° C. to ammonium chloride the tertiary amino group of the side chain. .. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Red 249 is dissolved is prepared, and the solution is gradually added dropwise to the ammonium chloride resin solution. After the dropping, the mixture is stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and 33 parts of C.I. I. A salt-forming compound (A-5) of Acid Red 249 and Resin 1 having a cationic group in its side chain was obtained.

(Salt-forming compound (A-6))
C. I. A salt-forming compound (A-6) consisting of Acid Red 52 and distearyldimethylammonium chloride (coatamine D86P) was produced.
To 2000 parts of a 10% aqueous sodium hydroxide solution, 11.5 parts of Kotamine D86P is added, and after sufficiently stirring and mixing, the mixture is heated to 60°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise to the above solution little by little. After the dropping, the mixture is stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a drier, and 17 parts of C.I. I. A salt-forming compound (A-6) of Acid Red 289 and coatamine D86P was obtained.

(Salt-forming compound (A-7))
C. I. A salt-forming compound (A-7) consisting of Acid Blue 112 and monolauryltrimethylammonium chloride (coatamine 24P) was produced.
To 2000 parts of a 7% aqueous sodium hydroxide solution, 8.1 parts of ketamine 24P is added, sufficiently stirred and mixed, and then heated to 50°C. On the other hand, 90 parts of water to 10 parts of C.I. I. An aqueous solution in which Acid Blue 112 is dissolved is prepared and added dropwise to the above solution little by little. After the dropping, the mixture is stirred at 50° C. for 120 minutes to sufficiently carry out the reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried to remove water with a drier, and then 16 parts of C.I. I. A salt-forming compound (A-7) of Acid Blue 112 and coatamine 24P was obtained.

(Sulfonamide compound (A-8))
C. I. Acid Red 52 was converted to a sulfonyl chloride by a conventional method and then reacted with theoretical equivalent of 2-ethylhexylamine in dioxane to give C.I. I. A sulfonic acid amide compound (A-8) of Acid Red 52 was obtained. (Based on the description in JP-A-6-194828.) At this time, C.I. in the sulfonic acid amide compound (A-8) was used. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

<Method for producing dye-containing resin solution>
(Dye-containing resin solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a dye-containing resin solution (DA-1).
Salt-forming compound (A-1): 20.0 parts PGMAc: 80.0 parts

(Dye-containing resin solution (DA-2 to 8))
Hereinafter, except that the salt-forming compound (A-1) was changed to the salt-forming compounds (A-2 to 8) shown in Table 1, the dye-containing resin solution (DA-1) was prepared in the same manner as the dye-containing resin solution (DA-1). DA-2 to 8) were produced.

The prepared dye-based pigment-containing solutions are summarized in Table 1.

<Method for producing finely treated pigment>
(Red miniaturized pigment (PR-1))
Red pigment C.I. I. Pigment Red 254 (PR254) (BASF's "Irgafore Red B-CF") 152 parts, chemical formula (6) dye derivative 8 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts stainless steel 1 gallon kneader (Inoue Seisakusho) (Made by the company) and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and the solvent, and then 80 It was dried at ℃ for one day and night to obtain a red finely treated pigment (PR-1). The average primary particle diameter of the obtained pigment was 35 nm.

Chemical formula (6)

(Red micronized pigment (PR-2))
Red pigment C.I. I. Pigment Red 177 (PR177) (BASF's "Chlomophthal Red A2B") 500 parts, sodium chloride 3500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120°C for 8 hours. .. Next, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating at 70°C to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. Then, a red micronized pigment (PR-2) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Blue miniaturized pigment (PB-1))
Blue pigment C.I. I. Pigment Blue 15:6 (PB15:6) (“Ryonor Blue ES” manufactured by Toyo Color Co., Ltd.) 500 parts, sodium chloride 2500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and 120 The mixture was kneaded at 12°C for 12 hours. Next, this kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating at 70°C to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. Then, a blue miniaturized pigment (PB-1) was obtained. The average primary particle diameter of the obtained pigment was 25 nm.

(Purple miniaturized pigment (PV-1))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (PV23) ("Fast Violet RL" manufactured by Clariant) 500 parts, sodium chloride 2500 parts, and polyethylene glycol (manufactured by Tokyo Kasei Co., Ltd.) 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 120° C. for 12 hours. Next, this mixture was poured into about 5 liters of warm water, stirred with a high speed mixer for about 1 hour while heating to about 70° C. to form a slurry, which was then filtered and washed with water to remove sodium chloride and diethylene glycol, It was dried at 80°C for a whole day and night to obtain a purple finely treated pigment (PV-1). The average primary particle diameter of the obtained pigment was 30 nm.

<Method of preparing pigment dispersant solution>
A pigment dispersant (“Ajsper PB821” manufactured by Ajinomoto Fine-Techno Co., Inc.) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution having a nonvolatile content of 30% by weight.

<Method for producing pigment dispersion>
(Pigment dispersion (P-R1))
After uniformly mixing 12 parts of the red micronized pigment (PR-1), 33 parts of an acrylic resin solution (B-1), 5 parts of a pigment dispersant solution, and 50 parts of ethylene glycol monomethyl ether acetate with stirring, the diameter was adjusted to 0. Using 5 mm zirconia beads, the pigment was dispersed in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 3 hours and then filtered through a 5 µm filter to obtain a pigment dispersion (P-R1) of PR254. ..

(Pigment dispersion (P-R2) to (P-V1))
Pigment dispersion (P-R2)-in the same production method as the pigment dispersion (P-R1), except that the red miniaturization-treated pigment (PR-1) was changed to the miniaturization-treated pigment shown in Table 2. (P-V1) was produced.

<Method for producing ionic acrylic resin [C]>
(Ionic acrylic resin (C-1))
A salt-forming compound (C-1) comprising 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium and Resin 1 having a cationic group in its side chain was prepared by the following procedure. Manufactured.
To 2000 parts of water, 51 parts of the resin 1 having a cationic group on the side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 4.4 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium in 90 parts of water was prepared, and a little was added to the resin solution. Drop by drop. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a dryer, and 20 parts of 1, 1, 2, 2, A salt-forming compound (C-1) of 3,3-hexafluoropropane-1,3-disulfonimide potassium and Resin 1 having a cationic group in the side chain was obtained. At this time, the content of the active ingredient derived from potassium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide in the salt-forming compound (C-1) was 16% by weight. ..

(Ionic acrylic resin (C-2))
A salt-forming compound (C-2) comprising 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium and a resin 3 having a cationic group in its side chain was prepared by the following procedure. Manufactured.
51 parts of the resin 3 having a cationic group was added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 4.4 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium in 90 parts of water was prepared, and a little was added to the resin solution described above. Drop by drop. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a dryer, and 20 parts of 1, 1, 2, 2, A salt-forming compound (C-2) of 3,3-hexafluoropropane-1,3-disulfonimide potassium and Resin 3 having a cationic group in its side chain was obtained. At this time, the content of the active ingredient derived from potassium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide in the salt-forming compound (C-2) was 16% by weight. ..

(Ionic acrylic resin (C-3))
A salt-forming compound (C-3) comprising 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium and a resin 4 having a cationic group in its side chain was prepared by the following procedure. Manufactured.
To 2000 parts of water, 51 parts of Resin 4 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 4.4 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium in 90 parts of water was prepared, and a little was added to the resin solution. Drop by drop. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a dryer, and 20 parts of 1, 1, 2, 2, A salt forming compound (C-3) of potassium 3,3-hexafluoropropane-1,3-disulfonimide and the resin 4 having a cationic group in the side chain was obtained. At this time, the content of the active ingredient derived from potassium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide in the salt-forming compound (C-3) was 16% by weight. ..

(Ionic acrylic resin (C-4))
A salt-forming compound (C-4) comprising 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium and a resin 5 having a cationic group in its side chain was prepared by the following procedure. Manufactured.
51 parts of the resin 5 having a cationic group was added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 8.8 parts of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium in 90 parts of water was prepared, and a little was added to the resin solution described above. Drop by drop. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a dryer, and 23 parts of 1, 1, 2, 2, A salt-forming compound (C-4) of 3,3-hexafluoropropane-1,3-disulfonimide potassium and Resin 5 having a cationic group in the side chain was obtained. At this time, the content of the active ingredient derived from potassium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide in the salt-forming compound (C-3) was 28% by weight. ..

(Ionic acrylic resin (C-5))
A salt-forming compound (C-5) composed of lithium tetrakis(pentafluorophenyl)borate and Resin 1 having a cationic group in its side chain was produced by the following procedure.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 10.1 parts of lithium tetrakis(pentafluorophenyl)borate in 90 parts of water was prepared and added dropwise to the above resin solution little by little. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried with a drier to remove water, and 24 parts of tetrakis(pentafluorophenyl)boric acid is added. A salt-forming compound (C-5) of lithium and Resin 1 having a cationic group in its side chain was obtained. At this time, the content of the active ingredient derived from lithium tetrakis(pentafluorophenyl)borate in the salt-forming compound (C-5) was 31% by weight.

(Ionic acrylic resin (C-6))
A salt-forming compound (C-6) consisting of lithium trifluoromethanesulfonate and Resin 1 having a cationic group in its side chain was produced by the following procedure.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 2.1 parts of lithium trifluoromethanesulfonate in 90 parts of water was prepared and added dropwise to the resin solution. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a drier, and 18 parts of lithium trifluoromethanesulfonate and side chains are attached. A salt-forming compound (C-6) with resin 1 having a cationic group was obtained. At this time, the content of the active ingredient derived from lithium trifluoromethanesulfonate in the salt-forming compound (C-6) was 8% by weight.

(Ionic acrylic resin (C-7))
A salt-forming compound (C-7) consisting of 1-ethyl-3-methylimidazolium hexafluorophosphate and Resin 1 having a cationic group in its side chain was produced by the following procedure.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution in which 3.8 parts of 1-ethyl-3-methylimidazolium hexafluorophosphate was dissolved in 90 parts of water was prepared and added dropwise to the resin solution. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 16 parts of 1-ethyl-3-methylimidazo was used. A salt-forming compound (C-7) of lithium hexafluorophosphate and Resin 1 having a cationic group in the side chain was obtained. At this time, the content of the active ingredient derived from 1-ethyl-3-methylimidazolium hexafluorophosphate in the salt-forming compound (C-7) was 8% by weight.

(Ionic acrylic resin (C-8))
A salt-forming compound (C-8) consisting of 1-hexyl-3-methylimidazolium tetrafluoroborate and Resin 1 having a cationic group in its side chain was produced by the following procedure.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 2.6 parts of 1-hexyl-3-methylimidazolium tetrafluoroborate in 90 parts of water was prepared and added dropwise to the resin solution. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a drier, and 15 parts of 1-hexyl 3-methylimidazolium. A salt-forming compound (C-8) of tetrafluoroborate and Resin 1 having a cationic group in its side chain was obtained. At this time, the content of the active ingredient derived from 1-hexyl-3-methylimidazolium tetrafluoroborate in the salt-forming compound (C-8)) was 5% by weight.

(Ionic acrylic resin (C-9))
A salt-forming compound (C-9) composed of sodium hexakis(trifluoromethane)phosphate and Resin 1 having a cationic group in its side chain was produced by the following procedure.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution prepared by dissolving 6.1 parts of sodium hexakis(trifluoromethane)phosphate in 90 parts of water was prepared and added dropwise to the resin solution. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried with a drier to remove water, and 21 parts of sodium hexakis(trifluoromethane)phosphate is dried. To obtain a salt-forming compound (C-9) with Resin 1 having a cationic group in its side chain. At this time, the content of the active ingredient derived from sodium hexakis(trifluoromethane)phosphate in the salt-forming compound (C-9)) was 22% by weight.

(Ionic acrylic resin (C-10))
A salt-forming compound (C-10) consisting of lithium tetrakis(pentachlorophenyl)borate and Resin 1 having a cationic group in its side chain was produced by the following procedure.
To 2000 parts of water, 51 parts of Resin 1 having a cationic group was added, and after sufficiently stirring and mixing, the mixture was heated to 60°C. On the other hand, an aqueous solution in which 14.0 parts of lithium tetrakis(pentachlorophenyl)borate was dissolved in 90 parts of water was prepared and added dropwise to the above resin solution little by little. After the dropping, the mixture was stirred at 60° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dripping the reaction solution on a filter paper and observing the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried to remove water, and 27 parts of lithium tetrakis(pentachlorophenyl)borate is dried. To obtain a salt-forming compound (C-10) with resin 1 having a cationic group in its side chain. At this time, the content of the active ingredient derived from lithium tetrakis(pentachlorophenyl)borate in the salt-forming compound (C-10)) was 38% by weight.

In addition, other compounds (I-1 to 5) are shown in Table 3. The ionic acrylic resins (C-1 to 10) were all almost colorless compounds, and the maximum molar extinction coefficient was 1000 [L/(mol·cm)] or less. On the other hand, the maximum value of the molar extinction coefficient of the other compound (I-1 to 3) is 1000 [L/(mol·cm)] or less, and that of the other compound (I-5) is 25000 [L/ (mol·cm)] and the other compound (I-5) was 43000 [L/(mol·cm)].

<Preparation of colored composition for color filter>
[Example 1]
(Coloring composition (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a colored composition (R-1).
Pigment dispersion (P-R1): 35.0 parts Dye-containing resin solution (DA-1): 10.0 parts Acrylic resin solution (B-1): 9.0 parts Ionic acrylic resin (C-1): 1.0 part Polyfunctional monomer (D-1): 3.0 parts Photopolymerization initiator (E-1): 1.0 part Solvent (PGMAc): 40.0 parts

[Examples 2 to 41, Comparative Examples 1 to 20]
(Coloring composition (R-2 to 61)
Pigment dispersion, dye-containing resin solution or dye, acrylic resin solution, ionic acrylic resin (C), other compound (I), polyfunctional monomer, photopolymerization initiator, and type and amount of solvent (parts by weight) Coloring compositions (R-2 to 61) were obtained in the same manner as the coloring composition (R-1) except that was changed to the composition shown in Tables 4 to 5.

The abbreviations in Tables 4 to 5 are shown below.
Polyfunctional monomer (D-1): dipentaerythritol hexaacrylate photopolymerization initiator (E-1): 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4 -Morpholinyl)phenyl]-1-butanone

<Evaluation of coloring composition>
The coating film of the obtained coloring composition (R-1 to 61) was tested by the following method. The test results are shown in Tables 6-7.

(Evaluation of brightness (Y) of red coloring composition)
For Examples 1 to 15 (coloring compositions (R-1 to 15)) and Comparative Examples 1 to 7 (coloring compositions (R-41 to 48), x=0.657, y=0. It was applied on a glass substrate to a film thickness of 320 and exposed to ultraviolet light through a mask having a predetermined pattern.After that, an alkali developing solution was sprayed to remove the uncured portion to form a desired pattern. About the obtained coating film, the brightness before and after the heat treatment at 230° C. for 20 minutes was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co.) in an oven. The change in brightness (Y) is preferably 0 or more and 0.4 or less, and more preferably 0 or more and 0.2 or less.

(Evaluation of lightness (Y) of blue coloring composition)
For Examples 16 to 41 (coloring compositions (R-16 to 41)) and Comparative Examples 8 to 20 (coloring compositions (R-49 to 61), x=0.141, y=0. A glass substrate having a thickness of 084 was applied, and UV exposure was performed through a mask having a predetermined pattern.After that, an alkali developing solution was sprayed to remove the uncured portion to form a desired pattern. With respect to the obtained coating film, the brightness before and after the heat treatment at 230° C. for 20 minutes was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co.) in an oven. The change in brightness (Y) is preferably 0 or more and 0.3 or less, and more preferably 0 or more and 0.1 or less.

When the chromaticity is shifted, a pigment dispersion and a coloring composition in which the ratio of the dye or the dye-containing solution is changed are prepared appropriately, and the chromaticity is measured and a calibration curve is drawn to obtain the brightness at the desired chromaticity. Was calculated.

(Solvent resistance)
The coloring composition for a color filter was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after prebaking at 70° C. for 20 minutes, ultraviolet exposure was performed using a super high pressure mercury lamp at a saturated exposure amount of +100 mJ/cm ² through a mask for exposing the stripe pattern. After the exposure, the film was developed with an alkaline developer for 90 seconds to form stripe-shaped filter segments of each color on the substrate. The developed substrate was heat-treated at 230° C. for 60 minutes. After immersing a part of the substrate in N-methylpyrrolidone (NMP) for 30 minutes, the chromaticity before and after the immersion was measured with a C light source using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, the chromaticity change rate ΔE*ab was calculated by the following calculation formula using the measured chromaticity.

ΔE*ab=√((L*(2)- L*(1)) ² + (a*(2)- a*(1)) ² +( b*(2)- b*(1)) ² )

The chromaticity change ΔE*ab before and after immersion in NMP is preferably 0 or more and less than 3, and more preferably 0 or more and less than 2.

From Tables 6 to 7, the coloring composition for a color filter containing the acidic dye of the present invention and the ionic acrylic resin (C) showed excellent lightness. Among them, Z ⁻ of the ionic compound represented by the general formula (1) is an anion represented by the general formula (1a), an anion represented by the general formula (1b), an anion represented by the general formula (1c), or In the case of the anion represented by the general formula (1d), the heat resistance and the lightness were particularly excellent, and the solvent resistance was also particularly good.

It was also confirmed that the color composition for a color filter of the present invention can provide an excellent color filter having excellent heat resistance and solvent resistance and high brightness.

Claims (12)

An acid dye, a binder resin, an organic solvent, and a structural unit represented by the following general formula (1), and a maximum molar absorption coefficient ε in the visible light region (wavelength 400 nm to 700 nm) is 0 or more and 3000 or less. A coloring composition for a color filter, which comprises a certain ionic acrylic resin [C].

[In the general formula (1), R ₁₀₁ represents a hydrogen atom or an alkyl group which may have a substituent. R _{102 to} R ₁₀₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent or an aryl group which may have a substituent, and R ₁₀₂ Two or more of _{102 to} R ₁₀₄ may combine with each other to form a ring. Q is an optionally substituted alkylene group, an optionally substituted arylene group, _{-CONH-R 105} - or _{-COO-R 105} - _{represents, R 105} is a substituent Represents an alkylene group which may be present. Z ⁻ represents an anion having a group selected from the group consisting of a cyano group, a nitro group and a halogenated hydrocarbon group, PF ₆ ⁻ or BF ₄ ⁻ . ] The coloring composition for a color filter according to claim 1, wherein the acidic dye is at least one selected from the group consisting of anthraquinone-based acidic dyes and xanthene-based acidic dyes. Z ⁻ is an anion represented by the following general formula (1a), an anion represented by the following general formula (1b), an anion represented by the following general formula (1c) or an anion represented by the following general formula (1d). The coloring composition for a color filter according to claim 1 or 2.
[In the general formula (1a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halogen atom, and when R ¹ and Hal are present in plural, they may be the same. May be different. c represents an integer of 1 to 6. ]
[In General Formula (1b), R ² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a cyano group, B represents a boron atom, and Hal represents a halogen atom. , R ² and Hal each may be the same or different. d represents an integer of 1 to 4. ]
[In the general formula (1c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group or an FSO ₂ group, and R ³¹ and R ³² are both In the case of a halogenated hydrocarbon group which may have a sulfonyl group, they may combine with each other to form a ring. However, at least one of R ³¹ and R ³² is a halogenated hydrocarbon group or a cyano group. ]
[In the general formula (1d), R ⁴ represents a halogenated hydrocarbon group which may be linked by a linking group having a nitrogen atom or an oxygen atom. ] The coloring composition for a color filter according to claim 3, wherein R ¹ in the general formula (1a) is a fluorinated alkyl group or a fluorinated aryl group, and Hal is a fluoro group. The coloring composition for a color filter according to claim 3, wherein R ² in the general formula (1b) is a fluorinated alkyl group or a fluorinated aryl group, and Hal is a fluoro group. The color according to claim 3, wherein R ³¹ or R ³² in the general formula (1c) is a group represented by the general formula (1c-1) or a group represented by the general formula (1c-2). Coloring composition for filters.
General formula (1c-1)

[In General Formula (1c-1), R ⁵ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ — or R 5 ¹⁷ COOR ¹⁸ CFH— (R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or an aryl group which may have a substituent, and R ¹⁸ represents an alkylene group), n represents an integer of 1 or more, and “*” represents a bond. When both R ⁵ are fluorinated alkyl groups, they may be bonded to each other to form a ring. ]

General formula (1c-2)

[In the general formula (1c-2), R ^{6 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, an alkoxy group or an alkylsulfonyl group, and “*” is Represents a bond. However, at least one of R ^{6 to} R ¹⁰ is a fluorine atom or a fluorinated alkyl group. ] The color filter according to claim 3, wherein R ⁴ in the general formula (1d) is a group represented by the following general formula (1d-1) or a group represented by the following formula (1d-2). Coloring composition.
General formula (1d-1)

[In General Formula (1d-1), R ¹¹ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ¹⁷ COOR ¹⁸ -or R. ¹⁷ COOR ¹⁸ CFH— (R ¹⁷ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or an aryl group which may have a substituent, and R ¹⁸ represents an alkylene group), n represents an integer of 1 or more, and “*” represents a bond. When both R ¹¹ are fluorinated alkyl groups, they may be bonded to each other to form a ring. ]
General formula (1d-2)

[In the general formula (1d-2), R ^{12 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, an alkoxy group or an alkylsulfonyl group, and “*” is , Represents a bond. However, at least one of R ^{12 to} R ¹⁶ is a fluorine atom or a fluorinated alkyl group. ] The acid dye is a salt-forming compound and/or a sulfonic acid amide compound, The coloring composition for a color filter according to claim 1. The coloring composition for a color filter according to claim 1, wherein the acidic dye is a xanthene-based acidic dye. Furthermore, the coloring composition for color filters of any one of Claims 1-9 containing an organic pigment. The coloring composition for a color filter according to any one of claims 1 to 10, further comprising a polyfunctional monomer and/or a photopolymerization initiator. A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 1 on a substrate.