JP2020181038A - Coloring composition, photosensitive coloring composition, color filter, and liquid crystal display device - Google Patents

Abstract

To provide a coloring composition, a photosensitive coloring composition, a color filter and a liquid crystal display device, which have low viscosity and good stability of viscosity over time and can suppress foreign matter in a film after development.SOLUTION: A coloring composition contains a red pigment (A), a resin type dispersant (B) and a binder resin (C), and the resin type dispersant contains a dispersant of (B1) type which contains a basic resin type dispersant (b1), a phosphoric acid resin type dispersant (b2), and a carboxylic acid resin type dispersant (b4) or (B2) type which contains salt (b3) of a compound represented by the general formula (1) or a compound represented by the general formula (2) and the basic resin type dispersant (b1), and the carboxylic acid resin type dispersant (b4).SELECTED DRAWING: Figure 1

Description

The present invention relates to a coloring composition used for producing a color filter used for a liquid crystal display device, a solid-state image sensor, an organic EL display device, a quantum dot display device, electronic paper, and the like.

Color filters used in liquid crystal display devices, solid-state image sensors, etc. are high in liquid crystal display devices and solid-state image sensors manufactured by forming fine patterns by photolithography using a photosensitive coloring composition. Further improvement is required for image quality and high definition, and further refinement of color filters is also required.

Patent Document 1 discloses a coloring composition using a block polymer having a quaternary ammonium base as a dispersant.

JP-A-2002-31713

However, the conventional coloring composition has a problem that the viscosity with time is low and foreign matter is generated in the film after development.

An object of the present invention is to provide a coloring composition, a photosensitive coloring composition, a color filter, and a liquid crystal display device, which have a low viscosity, good viscosity stability over time, and can suppress foreign substances in a film after development. To do.

The coloring composition of the present invention contains a red pigment (A), a resin-type dispersant (B), and a binder resin (C).
The resin type dispersant contains the following dispersant (B1) or (B2).
(B1) A resin-type dispersant containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4).
(B2) A salt (b3) of the compound represented by the following general formula (1) or the compound represented by the general formula (2) and the basic resin type dispersant (b1), and the carboxylic acid type resin type dispersant (b4). Resin type dispersant containing.

However, in the general formula (1) and the general formula (2), R ¹ and R ² are independently hydrogen atom, hydroxyl group, linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and vinyl. Represents a phenyl or benzyl group, which may have a group, a substituent, or —OR ⁴ , where R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. It represents a phenyl group or a benzyl group which may have a group, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or —OR ⁴ .

According to the above invention, it is possible to provide a coloring composition having a low viscosity, good viscosity stability over time, and capable of suppressing foreign substances in the film after development.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

The terminology of the present specification is defined. Unless otherwise specified, the terms "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are used, respectively. , "Acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid". "CI" as used herein means a color index (CI). Colorants include pigments and dyes.

The coloring composition of the present invention contains a red pigment (A), a resin-type dispersant (B), and a binder resin (C).
The resin type dispersant contains the following dispersant (B1) or (B2).
(B1) A resin-type dispersant containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4).
(B2) A salt (b3) of the compound represented by the following general formula (1) or the compound represented by the general formula (2) and the basic resin type dispersant (b1), and the carboxylic acid type resin type dispersant (b4). Resin type dispersant containing.

However, in the general formula (1) and the general formula (2), R ¹ and R ² are independently hydrogen atom, hydroxyl group, linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and vinyl. Represents a phenyl or benzyl group, which may have a group, a substituent, or —OR ⁴ , where R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. It represents a phenyl group or a benzyl group which may have a group, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or —OR ⁴ .

When the coloring composition of the present invention contains the dispersant of (B1) or (B2), the dispersion stability of the red pigment (A) is greatly improved. Therefore, the viscosity with time is good, and the dispersed state of the red pigment (A) can be maintained in the film after development by the photolithography method, and the generation of foreign substances due to the aggregation of the red pigments can be suppressed.

<Red pigment (A)>
As the red pigment (A), a known pigment can be used. It is preferable to use a yellow pigment in combination with the coloring composition in order to adjust the color tone of the film. In addition, other organic pigments, inorganic pigments, dyes and the like can be used in combination with the coloring composition in order to obtain desired optical properties.
Red pigment (A), eg, 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, 277, 278, 279, 280, 281 and 282, 283, 284, 285, 286, 287, 291295, 296 and the like can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291, 295, 296, more preferably C.I. I. Pigment Red 177, 254, 291, 295, 296.

(Yellow pigment)
The yellow pigment is, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231 and 233 and the like. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231,233 are preferred.

Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, etc. Synthetic iron black and the like can be mentioned.

<Dye>
Examples of the dye include acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, construction dyes, sulfide dyes and the like. In addition, a derivative of a dye and a rake pigment obtained by raked a dye can also be mentioned.

The dye is an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of the acidic dye; an acidic dye, a quaternary ammonium salt compound, a tertiary amine compound, or a secondary amine compound. Alternatively, a salt-forming compound with a primary amine compound; a resin component having these amino groups and a salt-forming compound such as an acidic dye can be mentioned.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness. The compound having an onium base is preferably a resin having a cationic group in the side chain.

Examples of the basic dye include organic acids, perchloric acids, and salt-forming compounds with these metal salts. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments.

The chemical structure of the dyes is, for example, azo dyes, disazo dyes, azomethine dyes (Indoaniline dyes, Indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , Polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples thereof include dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Kinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. The specific structure of dyes is "New Edition Dye Handbook" (edited by Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colorists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986). It is described in.

<Pigment miniaturization>
The red pigment (A) is preferably mixed with other raw materials after undergoing a miniaturization treatment. Examples of the miniaturization treatment method include wet grinding, dry grinding, dissolution and precipitation, and the like. Among these, salt milling treatment by the kneader method, which is a kind of wet grinding, is preferable. The average primary particle size of the red pigment (A) after the miniaturization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. With an appropriate particle size, the dispersibility is further improved and the contrast ratio of the coating film is further improved. The average primary particle diameter is an average value of about 20 particles arbitrarily selected from a magnified image of a TEM (transmission electron microscope). If there is a vertical axis length and a horizontal axis length of the particles, the vertical axis length is used.

The salt milling treatment is a batch type of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, for example, a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like. This is a process in which a water-soluble inorganic salt and a water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a continuous kneader. 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 width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve a water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120 ° C. or higher because it is difficult to volatilize due to a temperature rise during salt milling. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, and the like. 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, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

Resin can be used during the salt milling process. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

In the present specification, the red pigment (A) is essential, and other pigments and dyes can be used in appropriate combinations.

<Resin type dispersant (B)>
The resin type dispersant (B) includes the following dispersants (B1) or (B2).
(B1) A resin-type dispersant containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4).
(B2) A salt (b3) of the compound represented by the following general formula (1) or the compound represented by the general formula (2) and the basic resin type dispersant (b1), and the carboxylic acid type resin type dispersant (b4). Resin type dispersant containing.

General formula (1) General formula (2)

However, in the general formula (1) and the general formula (2), R ¹ and R ² are independently hydrogen atom, hydroxyl group, linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and vinyl. Represents a phenyl or benzyl group, which may have a group, a substituent, or —OR ⁴ , where R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. It represents a phenyl group or a benzyl group which may have a group, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or —OR ⁴ .

The amount of the resin-type dispersant (B) used is preferably about 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the red pigment (A). Dispersion stability is further improved when an appropriate amount is used.

<Basic resin type dispersant (b1)>
The basic resin type dispersant (b1) is, for example, a copolymer obtained by radical polymerization of a monomer mixture containing an ethylenically unsaturated monomer having a basic group. The basic resin type dispersant (b1) is a dispersant having a pigment-affinitive moiety containing a basic group adsorbed on the pigment and a moiety compatible with the binder resin.

Here, the basic group is a functional group having a nitrogen atom. Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocycle. The basic resin-type dispersant (b1) contains a nitrogen atom having a functional group containing a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, and the like in the side chain. Examples thereof include acrylic block copolymers, random copolymers, and urethane resin type dispersants.

The basic resin type dispersant (b1) preferably has an amide bond. The basic resin type dispersant (b1) is composed of a group consisting of a unit represented by the following general formula (b1-1), a unit represented by the following general formula (b1-2), and a unit represented by the following general formula (b1-3). It is preferable to have one or more selected.

In the general formula (b1-1), R ^{9 to} R ¹¹ each independently represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent, and R ^{9 to} R ¹¹ Two or more of them may be bonded to each other to form a cyclic structure. R ¹² represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.

In the general formula (b1-2), R ¹³ and R ¹⁴ each independently represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent, and R ¹³ and R ¹⁴ are They may be combined with each other to form a cyclic structure. R ¹² represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

In formula ^{(b1-3), R 15} is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group or, It represents OR ²⁰ , and R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ¹⁶ and R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a methyl group, an ethyl group, or a phenyl group. R ¹² represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

As R ^{9 to} R ¹¹ in the general formula (b1-1), an alkyl group having 1 to 4 carbon atoms which may have a substituent and an aralkyl group having 7 to 16 carbon atoms which may have a substituent may be used. A group is more preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group are more preferable.

As R ¹³ and R ¹⁴ in the general formula (b1-2), an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are more preferable. preferable.

In ^{R 15} in the general formula (b1-3), the alkyl group having 1 to 18 carbon atoms, linear, branched, and cyclic alkyl group. For example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group and the like can be mentioned.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 8 carbon atoms. For example, a benzyl group, a phenethyl group, an α-methylbenzyl group, a 2-phenylpropan-2-yl group and the like can be mentioned.
Examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group. Examples thereof include an acetyl group and a benzoyl group.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferable, a hydrogen atom and a methyl group are more preferable, and a methyl group is most preferable.

In the general formula (b1-1), the general formula (b1-2) and the general formula (b1-3), the divalent linking group × is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, and the like. ^{-CONH-R 21 -, - COO} -R 22 - are preferred. However, examples of R ²¹ and R ²² include a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, and an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms. ^-CONH-R 21 Among them -, - ^{COO-R 22} - are preferred. Further, as the Y ⁻ of the counter anion of the above general formula (b1-1), Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like can be mentioned.

The ethylenically unsaturated monomer forming the unit represented by the general formula (b1-1) is, for example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethyl. Benzylammonium chloride, alkyl (meth) acrylate-based quaternary ammonium salts such as (meth) acryloyloxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) ) Alkyl (meth) acryloylamide-based quaternary ammonium salts such as acryloylaminoethyldimethylbenzylammonium chloride, dimethyldialylammonium methylsulfate, trimethylvinylphenylammonium chloride and the like can be mentioned.

The ethylenically unsaturated monomer forming the unit represented by the general formula (b1-2) is, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N. (Meta) acrylates having a tertiary amino group such as −dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylamino Examples thereof include (meth) acrylamides having a tertiary amino group such as ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide.

Examples of the ethylenically unsaturated monomer forming the unit represented by the general formula (b1-3) include compounds represented by the following general formulas (b1-3-1) to (b1-3-11).

In the general formulas (b1-3-1) to (b1-3-11), R ¹² represents a hydrogen or methyl group.

(In the general formula ^(B1-3-1), compound ^{R 12} is a methyl group) Of these 2,2,6,6-tetramethyl-piperidyl methacrylate, 1,2,2,6,6-pentamethyl preferably (compound ^{R 12} is a methyl group in the general formula (b1-3-2)) piperidyl methacrylate, especially 1,2,2,6,6 pentamethylpiperidyl methacrylate are preferred.

The unit represented by the general formula (b1-1), the unit represented by (b1-2), and the unit represented by (b1-3) can be contained alone or in combination of two or more.

Units other than the unit represented by the general formula (b1-1), the unit represented by (b1-2), and the unit represented by (b1-3) can be formed by using the following other monomers.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), and tertiary butyl (meth) acrylate. , Isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate , Tridecyl (meth) acrylates, isomyristyl (meth) acrylates, stearyl (meth) acrylates, and linear or branched alkyl (meth) acrylates such as isostearyl (meth) acrylates;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meta) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meta) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate , Diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, Triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth) ) (Poly) alkylene glycol (meth) acrylates having an aromatic ring such as acrylate;
Alkyloxys such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meta) acrylates having a silyl group;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethyl Siloxane (silicone macromer);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin; In addition, nitriles such as (meth) acrylonitrile can be mentioned.
In addition, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; vinyl acetate; fatty acid vinyls such as vinyl propionate, etc. Can be mentioned.

Further, a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. Carboxyl group-containing ethylenically unsaturated monomers include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2-. (Meta) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone ( Meta) acrylate and the like can be mentioned.

Further, even if an ethylenically unsaturated monomer containing an amino group other than the structural units represented by the general formula (b1-1), the general formula (b1-2) and the general formula (b1-3) is used in combination. Good.

The weight average molecular weight of the basic resin type dispersant (b1) is usually preferably 1,000 to 100,000. Dispersion stability and developability are further improved by an appropriate molecular weight.

<Phosphoric acid resin type dispersant (b2)>
The phosphoric acid-based resin type dispersant (b2) is a resin having a phosphoric acid bond [(−O) ₃ P = O] in the molecule. The phosphoric acid-based resin-type dispersant (b2) is preferably a resin-type dispersant containing the following (b2-1) or (b2-2).

<Phosphoric acid resin type dispersant (b2-1)>
General formula (3) (HO−) _3-n −PO− (OR ⁵ ) _n
(In the general formula (3), R ⁵ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)

The dispersant represented by the general formula (3) can suppress the reaggregation of the red pigment (A) after dispersion. Therefore, a color filter having excellent transparency can be formed. Further, since the dispersant represented by the general formula (3) has high autolysis, for example, when the die coat type coating device is temporarily stopped, if the colored composition solidifies at the tip of the discharge port, coating is started again. Then, the solidified product can be dissolved.

The dispersant represented by the general formula (3) is, for example, using monoalcohol as an initiator, ring-opening addition of a cyclic ester (first step) to produce a polyester having a hydroxyl group at one end, and then phosphate esterification (). It can be manufactured by performing the second step).

As the monoalcohol, any of primary, secondary and tertiary alcohols can be used. For example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, Examples thereof include stearyl alcohol, oleyl alcohol and hexadecyl alcohol. Of these, lauryl alcohol, N-hexanol, and hexadecyl alcohol are preferable.

The first step is to carry out ring-opening addition polymerization of ε-caprolactone or the like using monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out by a known method, for example, by charging a reactor connected to a dehydration tube and a condenser with monoalcohol, ε-caprolactone and a polymerization catalyst, and carrying out the addition reaction under a nitrogen stream. When a low boiling point monoalcohol is used, it can be reacted under pressure using an autoclave. No solvent or a suitable dehydrating solvent such as toluene or xylene can be used for the reaction. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product.

The reaction temperature in the first step is 120 ° C. to 220 ° C., preferably 160 ° C. to 210 ° C. If the reaction temperature is less than 120 ° C, the reaction rate is extremely slow, and if it exceeds 220 ° C, side reactions other than the addition reaction of ε-caprolactone, for example, decomposition of the ε-caprolactone adduct into ε-caprolactone monomer, cyclic ε-caprolactone dimer Is likely to occur.
The number of moles of ε-caprolactone added per mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles. If the number of added moles is less than 1 mol, it becomes difficult to obtain the effect as a dispersant, and if it is larger than 50 mol, the molecular weight of the reaction product becomes too large, which tends to cause deterioration of dispersibility and fluidity.

The polymerization catalyst is, for example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodo, tetrabutylammonium iodo, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium bromide. Tertiary ammonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium In addition to quaternary phosphonium salts such as iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, and organic carboxylics such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate. Examples thereof include alkali metal ammonium such as acid acid, sodium ammonium and potassium ammonium, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride. The amount of the catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When an appropriate amount is used, a sufficient polymerization rate can be obtained.

Phosphoric acid esterification (second step) is carried out by reacting one or a combination of two or more phosphoric acid esterifying agents such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, and phosphorus oxychloride. It can be performed. Of these, one or more phosphoric acid esterifying agents selected from the group consisting of orthophosphoric acid, polyphosphoric acid and phosphorus pentoxide are preferable because they do not have by-products such as hydrochloric acid gas and do not require special equipment.

As for the charging ratio of the phosphoric acid esterifying agent, the molar ratio of the phosphorus atom in the phosphoric acid esterifying agent to the hydroxyl group of the polyester residue having a hydroxyl group at one end is preferably 0.5 to 1.5. It is more preferably 0 to 1.3, and most preferably 1.05 to 1.2. If the molar ratio of phosphorus atom to hydroxyl group is less than 0.5, phosphoric acid esterification to hydroxyl group tends to be insufficient or the amount of by-product of phosphoric acid diester tends to increase. There is a tendency that an increase effect commensurate with the amount added cannot be obtained.

The reaction temperature in the second step is not particularly limited, but is preferably 40 ° C. to 130 ° C., more preferably 50 ° C. to 110 ° C., and most preferably 60 ° C. to 100 ° C. If the reaction temperature is lower than these ranges, the esterification reaction may be insufficient and the phosphate esterifying agent may remain. If the reaction temperature is higher than these ranges, by-products are likely to be formed and the ester is formed. Decomposition of the chemical reaction product tends to occur easily.

As the dispersant represented by the general formula (3) in the present specification, it is preferable to use a phosphoric acid ester of n = 1 and a phosphoric acid ester of n = 2 in combination. The molar ratio of n = 1 and n = 2 is preferably 100: 1 to 100:30. This further improves the pigment dispersibility.

Further, the dispersant represented by the general formula (3) preferably R ⁵ is a structure represented by the following general formula (3-1).
General formula (3-1)-(R ⁵¹ -COO-) _m -R ⁵²
(In the general formula (3-1), R ⁵¹ represents a lactone residue, R ⁵² represents a monoalcohol residue, and m represents an integer of 1 to 50.
When m in the structure represented by the general formula (3-1) is 2 or more, R ⁵ in the dispersant represented by the general formula (3) becomes a polycaprolactone residue. As a result, the dispersibility of the pigment is improved, and the solubility of the solidified product is further improved.

<Phosphoric acid resin type dispersant (b2-2)>
The phosphoric acid-based resin-type dispersant (b2-2) is a resin-type dispersant that is a copolymer of an ethylenically unsaturated monomer having a phosphoric acid group and another ethylenically unsaturated monomer. .. The dispersant is described in JP-A-2003-253878 and JP-A-2008-161737.

<Salt (b3) of the compound represented by the general formula (1) or the compound represented by the general formula (2) and the basic resin type dispersant (b1)>
The resin-type dispersant (B2) is a salt (b3) of a compound represented by the following general formula (1) or a compound represented by the general formula (2) and a basic resin-type dispersant (b1), and a carboxylic acid type. Contains a resin-type dispersant (b4).

General formula (1) General formula (2)

However, in the general formula (1) and the general formula (2), R ¹ and R ² are independently hydrogen atom, hydroxyl group, linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and vinyl. Represents a group, a phenyl or benzyl group which may have a substituent, or —OR ³ , where R ³ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. It represents a phenyl or benzyl group which may have a group, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of R ¹ and R ² contains a carbon atom.

Examples of the compound represented by the general formula (1) include monobutyl phosphate, dibutyl phosphate, methyl phosphate, dibenzyl phosphate, diphenyl phosphate, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate and the like.

Examples of the compound represented by the general formula (2) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfate, monoethylsulfate, monon-propylsulfuric acid and the like. A hydrate such as p-toluenesulfonic acid monohydrate may be used.

As described above, the salt (b3) of the basic resin type dispersant (b1) is exemplified by the basic resin type dispersant (b1) and the compound represented by the general formula (1), or the general formula (2). ) Represents a salt with the one exemplified by the compound.

<Carboxylic acid resin type dispersant (b4)>
The carboxylic acid resin type dispersant (b4) preferably contains the following (b4-1) or (b4-2). In the present specification, the carboxylic acid-based resin is a resin having a carboxyl group.

<Carboxylic acid resin type dispersant (b4-1)>
The carboxylic acid-based resin-type dispersant (b4-1) is a resin-type dispersant containing a polyester moiety having a carboxyl group and a vinyl polymer moiety.
The polyester moiety having a carboxyl group is a reaction product of a hydroxyl group-containing compound and a kind of acid anhydride compound selected from the group consisting of tetracarboxylic acid anhydride and tricarboxylic acid anhydride. The acid anhydride group of the acid anhydride compound reacts with the hydroxyl group in the hydroxyl group-containing vinyl polymer.

First, the polyester part will be described. The polyester portion has a plurality of ester groups derived from the reaction between the acid anhydride group and the hydroxyl group.

[Tetracarboxylic dianhydride]
Tetracarboxylic dianhydride is a compound having two acid anhydride groups. The tetracarboxylic acid dianhydride is, for example, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1, 2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic hydride, 2,3,5-tricarboxycyclopentylacetic hydride, 3,5,6 − Tricarboxynorbornan-2-acetate dianhydride, 2,3,4,5-tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride such as bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, pyro Merit acid dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride , 3,3', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride , 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4' -Tetraphenylsilane Tetracarboxylic acid dianhydride, 1,2,3,4-furtetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'- Perfluoroisopropyridendiphthalic hydride, 3,3', 4,4'-biphenyltetracarboxylic hydride, bis (phthalic acid) phenylphosphine oxide hydride, p-phenylene-bis (triphenylphthalate) Acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4 '-Diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) ) Fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] Fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples thereof include succinic acid dianhydride or aromatic tetracarboxylic dianhydride such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride. Among these, aromatic tetracarboxylic dianhydride is preferable in terms of excellent adsorptivity to the red pigment (A).

The tetracarboxylic dianhydride can be used alone or in combination of two or more.

[Tricarboxylic acid anhydride]
A tricarboxylic acid anhydride is a compound having one acid anhydride group and one carboxyl group. Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride and an aromatic tricarboxylic acid anhydride.

Aliphatic tricarboxylic acid anhydrides include, for example, 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propen-1,2,3-tricarboxylic acid-1. , 2-Anhydride, 1,3,4-Cyclopentanetricarboxylic acid anhydride and the like.

The aromatic tricarboxylic acid is, for example, benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalene tricarboxylic acid. Anhydrous (1,2,4-naphthalentricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalentricarboxylic acid anhydride, 1,2,8-naphthalentricarboxylic acid anhydride Etc.), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2,3,2'- Examples thereof include biphenyltricarboxylic acid anhydride, 3,4,4′-biphenylmethanetricarboxylic acid anhydride, 3,4,4′-biphenylsulfonetricarboxylic acid anhydride and the like. Among these, aromatic tricarboxylic acid anhydrides are preferable in terms of excellent adsorptivity to the red pigment (A).

In the synthesis of the carboxylic acid resin type dispersant (b4-1), the molar ratio of the acid anhydride group to the hydroxyl group in the hydroxyl group in the acid anhydride group of the acid anhydride compound and the hydroxyl group-containing vinyl polymer is acid anhydride. Group / hydroxyl = 0.5 to 1.5 is preferable. When used in the above molar ratio, if it is smaller than 0.5 or larger than 1.5, there are many parts that do not react, and the desired dispersant is often not obtained.

[Hydroxy group-containing compound]
Examples of the hydroxyl group-containing compound include monoalcohols having one hydroxyl group and polyols having two or more hydroxyl groups, and polyols are preferable. The hydroxyl group-containing compound serves as a starting point for bonding with the vinyl polymer moiety.
Examples of the hydroxyl group-containing compound include a compound having two hydroxyl groups and one thiol group, and a one-terminal hydroxyl group-containing vinyl polymer. The hydroxyl group-containing compounds include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2 -Mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol , 2-Mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like.

The carboxylic acid resin type dispersant (b4-1) is preferably (b4-1-1) or (b4-1-2).

<Carboxylic acid resin type dispersant (b4-1-1)>
The vinyl polymer moiety of the carboxylic acid resin type dispersant (b4-1-1) is one or more thermocrosslinkable functional groups selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, and a blocked isocyanate group. It preferably contains a group as well as a carboxyl group. The vinyl polymer moiety is obtained by polymerizing a thermally crosslinkable functional group-containing ethylenically unsaturated monomer and a carboxyl group ethylenically unsaturated monomer.

(Ethylene unsaturated monomer having a hydroxyl group)
The ethylenically unsaturated monomer having a hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate. And (meth) acrylates having hydroxyl groups such as hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate; N- (2- (2- It has hydroxyl groups such as N- (hydroxyalkyl) (meth) acrylamide such as hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (2-hydroxybutyl) (meth) acrylamide. (Meta) acrylamide; vinyl ethers having hydroxyl groups such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether; 2-hydroxy Examples thereof include allyl ethers having a hydroxyl group such as ethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, 2- (or 3- or 4-) hydroxybutyl allyl ether and the like.

Further, ethylene obtained by adding an alkylene oxide and / or a lactone to a hydroxyalkyl (meth) acrylate, an alkyl-α-hydroxyalkyl acrylate, an N- (hydroxyalkyl) (meth) acrylamide, a hydroxyalkyl vinyl ether or a hydroxyalkyl allyl ether. The sex-unsaturated monomer is also an ethylenically unsaturated monomer having a hydroxyl group. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide. When two or more kinds of alkylene oxides are used in combination, the binding form may be either random or / or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, and ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms. Both alkylene oxide and lactone can be added.

(Ethylene unsaturated monomer having an oxetane group)
Examples of the ethylenically unsaturated monomer having an oxetane group include (vinyloxyalkyl) alkyloxetane, (meth) acryloyloxyalkyl oxetane, and [(meth) acryloyloxyalkyl] alkyl oxetane. Of these, methyl methacrylate (3-ethyloxetane-3-yl) methyl is preferable. Examples of commercially available products include ETERNALCOLL OXMA (methacrylic acid (3-ethyloxetane-3-yl) methyl) (manufactured by Ube Industries, Ltd.).

(Ethylene unsaturated monomer having a tert-butyl group)
Examples of the ethylenically unsaturated monomer having a tert-butyl group include tert-butyl methacrylate and tert-butyl acrylate.

(Ethylene unsaturated monomer having a blocked isocyanate group)
Ethyl unsaturated monomers having a blocked isocyanate group are 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl. Examples thereof include methacrylate.
Commercially available products include, for example, Karenz MOI-BM (2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate) (manufactured by Showa Denko Co., Ltd.) and Karenz MOI-BP (2-[(3,3). 5-Dimethylpyrazolyl) carbonylamino] ethylmethacrylate) (manufactured by Showa Denko Co., Ltd.) and the like.

The content of the thermally crosslinkable functional group-containing ethylenically unsaturated monomer is preferably 5 to 90% by mass, more preferably 20 to 60% by mass in the entire ethylenically unsaturated monomer. When an appropriate amount is contained, durability and dispersion stability are further improved.

Ethylene unsaturated monomer having a carboxyl group)
Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Among these, (meth) acrylic acid is preferable in terms of copolymerizability.

[Other ethylenically unsaturated monomers]
Other ethylenically unsaturated monomers can be used for the synthesis of the vinyl polymer moiety.
Other ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Alkyl (meth) acrylates such as acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate; phenyl Aromatic (meth) acrylates such as (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate; heterocyclic (meth) acrylate such as tetrahydrofurfuryl (meth) acrylate. Classes; alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylates and ethoxypolyethylene glycol (meth) acrylates; N-substituted (meth) acrylamides such as meta) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholin; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl Amino group-containing (meth) acrylates such as (meth) acrylate; nitriles such as (meth) acrylonitrile; styrenes such as styrene and α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether , Vinyl ethers such as isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

<Carboxylic acid resin type dispersant (b4-1-2)>
The vinyl polymer portion of the carboxylic acid resin type dispersant (b4-1-2) preferably contains an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable in terms of reactivity.
The method for producing the carboxylic acid-based resin-type dispersant (b4-1-2) is, for example, to synthesize a reactive functional group-containing vinyl polymer and then have a functional group capable of reacting with the reactive functional group (meth). ) A method of reacting the acrylate can be mentioned. Examples of the combination of functional groups include (1) a combination of glycidyl methacrylate and a polymer having a hydroxyl group or a carboxyl group, and (2) a combination of methacryloyloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxyl group. ..
A polymer having a hydroxyl group or a carboxyl group can be synthesized by subjecting a polymer having a glycidyl group or an acid anhydride group to a ring-opening reaction. Such a dispersant is described in, for example, Japanese Patent Application Laid-Open No. 2011-157416.

<Carboxylic acid resin type dispersant (b4-2)>
The carboxylic acid resin type dispersant (b4-2) is a dispersant represented by the following general formula (4). The dispersant is described, for example, in JP-A-2007-140487.
Formula _{(4) (HOOC-) m -R} 6 - (- COO - [- R 8 -COO-] n -R 7) t
(In the formula, R ⁶ is a tetravalent aromatic tetracarboxylic acid residue, R ⁷ is a monoalcohol residue, R ⁸ is a lactone residue, m is 2 or 3, and n is an integer of 1 to 50. , T represents (4-m).)

<Commercially available resin type dispersant>
Other resin-type dispersants can be used in combination with the coloring composition of the present specification. Other commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by Big Chemie Japan. 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykumen, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, manufactured by Japan Lubrizol , 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500. Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by BASF, etc. 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine Techno Examples thereof include azisper PA111, PB711, PB821, PB822, PB824 manufactured by the same company.

<Dye derivative>
A dye derivative can be used for the coloring composition, if necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and a basic substituent such as an amine salt, a sulfonamide group, or a tertiary amino group at the terminal thereof. Examples thereof include compounds and compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indol, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, the diketopyrrolopyrrole dye derivatives are JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine-based. The dye derivatives are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, Patent No. 5735266, and the anthraquinone-based dye derivatives are JP-A-63-246674, JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet, quinacridone-based dye derivatives are JP-A-48-54128, JP-A-03-9961 and JP-A-2000-273383, Dioxazine-based dye derivatives are JP-A-2011-162662, and thiazineindigo-based dye derivatives are JP-A-2007-314785, Triazine-based dye derivatives. Is JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681. , Benzoisoindole-based dye derivatives are JP-A-2009-57478, and quinophthalone-based dye derivatives are JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012. -226110, naphthol dye derivatives are JP2012-208329, JP2014-5439, and azo dye derivatives are JP2001-172520, JP2012-1722092, acidic. Substituents are referred to in JP-A-2004-307854, and basic substituents are referred to in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. Examples include the described dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group or a basic group. , A compound having a substituent such as a neutral group is synonymous with a dye derivative.

<Binder resin (C)>
The coloring composition of the present specification contains a binder resin (C). The binder resin (C) is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin (C) includes, for example, a thermoplastic resin, a thermosetting resin, an active energy ray-curable resin, and the like. The active energy ray-curable resin may have an active energy ray-reactive functional group in the thermoplastic resin or the thermosetting resin. Further, the binder resin (C) is preferably an alkali-soluble resin from the viewpoint of developability in terms of physical properties. Alkali solubility is for imparting development solubility in the alkali development step at the time of producing a color filter, and an acidic group is required.

The binder resin (C) can be used alone or in combination of two or more.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant containing the red pigment. When an appropriate amount is contained, a film can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
The thermoplastic resin is, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, etc. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble thermoplastic resin is, for example, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, or an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (maleic anhydride) copolymer and the like. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of improving developability, heat resistance, and transparency. The alkali-soluble thermoplastic resin preferably has an ethylenically unsaturated double bond for photocuring.

<Active energy ray-curable alkali-soluble resin>
It is preferable to have an active energy ray-curable alkali-soluble resin and an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the methods (i) and (ii) shown below. Due to the effect of the active energy rays, the resin is three-dimensionally crosslinked to increase the crosslink density and improve the chemical resistance.

[Method (i)]
In method (i), for example, an ethylenically unsaturated monomer having an ethylenically unsaturated monomer is copolymerized with another monomer to form a side chain epoxy group of the copolymer. The carboxyl group of an unsaturated monobasic acid having a double bond is subjected to an addition reaction. Next, it is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by reacting the generated hydroxyl group with a polybasic acid anhydride.

Ethylene unsaturated monomers having an epoxy group include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and the like. And 3,4-epoxycyclohexyl (meth) acrylates. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, cyano-substituted products and the like. Examples include carboxylic acid.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride was used to remain. It is also possible to hydrolyze the anhydride group.

As a method similar to the method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and another monomer are copolymerized with a part of the side chain carboxyl group of the copolymer obtained. This is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction.

[Method (ii)]
In the method (ii), the ethylenically unsaturated monomer having an isocyanate group is added to the side chain hydroxyl group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method of reacting a monomeric isocyanate group.

The ethylenically unsaturated monomer having a hydroxyl group includes, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and the like. Examples thereof include hydroxyalkyl methacrylates such as glycerol mono (meth) acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide with hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. 2-Hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. Therefore, glycerol mono (meth) acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. Be done.

Other monomers that can constitute the alkali-soluble resin include N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphoric acid ester group-containing ethylenically unsaturated monomers, in addition to the other ethylenically unsaturated monomers described above. Examples thereof include monomers and carboxyl group-containing ethylenically unsaturated monomers.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-. 4-Methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimoleimide, N, N'-1,4-phenylenedi maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitro) Phenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, Examples thereof include N-succinimidyl-6-maleimidehexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin. The alkyleneoxy group-containing monomer includes, for example, EO-modified cresol acrylate, n-nonylphenoloxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenylacrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, and paracumylphenol. Examples thereof include EO or propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomer already described can be used.

The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. is there.

<Alkali-soluble resin without ethylenically unsaturated double bond>
The coloring composition of the present specification may contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 3,000 or less, preferably 4,000, in order to impart alkali development solubility. More preferably 20,000 or less. Further, the value of Mw / Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably in the range of 70 or more and 180 or less, and more preferably 90 or more and 170 or less. The range. If the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

Each raw material used for synthesizing the binder resin (C) can be used alone or in combination of two or more.

<Thermosetting compound (CE)>
The coloring composition can contain a thermosetting compound (CE) together with the binder resin (C). For example, when a color filter is produced using a coloring composition for a color filter, the thermosetting compound (CE) reacts at the time of firing the filter segment to increase the crosslink density of the coating film by containing the thermosetting compound. As a result, the heat resistance of the filter segment is improved, pigment aggregation during firing of the filter segment is suppressed, and the contrast ratio is improved.

Examples of the thermosetting compound include low molecular weight compounds and high molecular weight compounds such as resins.
Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. In the coloring composition for a color filter, an epoxy compound and an oxetane compound are preferable.

(Epoxy compound (CE-1))
Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted Polycondensate of dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol Polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. Polycondensate with (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyldimethanol , Α, α, α', α'-biphenyldimethanol, etc.), and phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) , Polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based Examples include epoxy resin.

Commercially available products of epoxy compounds include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more). Is a product name: Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (Product Name: Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (Product Name: Nippon Kayaku Co., Ltd.), JER 1032H60 (Product Name: Japan Epoxy Resin Co., Ltd.) ), JER 157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin), EPPN-201 (trade name; manufactured by Nippon Kayakusha), JER152, JER154 (trade name; manufactured by Japan Epoxy Resin), EOCN-102S , EOCN-103S, EOCN-104S, EOCN-1020 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (trade name; manufactured by Daicel Chemical Industry Co., Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (the above are trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H , TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.) and the like.

The blending amount of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the colorant. Heat resistance is further improved when an appropriate amount is blended.

(Oxetane compound (CE-2))
An oxetane compound is a compound having one or more oxetane groups.

Compounds having one oxetane group include, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-. 3- (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3-( Triethoxysilyl) propoxy] methyl} oxetane and the like. Examples of commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

Compounds having two oxetane groups include, for example, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-bis) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycosbis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycolbis (3-Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis ( 3-Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) -modified bisphenol A-bis (3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -Oxetanylmethyl) ether and the like. Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Compounds having three or more oxetane groups include, for example, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl-). 3-Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl) -3-Oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (3-ethyl-3-oxetanylmethyl) ether For example, a polymer obtained by radically polymerizing a (meth) acrylic monomer such as the oxetane-modified phenol novolac resin described in Patent No. 3783462 and the above-mentioned OXE-30 can be mentioned.

The content of the oxetane compound is usually preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is contained, water stains on the coating film are improved and chemical resistance is further improved.

The thermosetting compound can be used alone or in combination of two or more.

(Melamine compound)
The melamine compound is a compound having a melamine ring structure. Examples thereof include low molecular weight compounds and high molecular weight compounds such as resins. In the present specification, a methylol type or an ether type is preferable, and a melamine compound having an average number of methylol groups and / or ether groups of 5.0 or more per melamine ring is more preferable. When the number of methylol groups and / or ether groups is appropriate, a good crosslinked structure can be easily obtained, and the contrast ratio and solvent resistance are further improved.

Commercially available products include, for example, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS- 001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 ( Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries Co., Ltd.) and the like. Among these, the number of methylol groups and / or ether groups per melamine ring is 5.0 or more on average, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30. , MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries) Is preferable.

(Hardener)
The coloring composition may contain a curing agent (curing accelerator) in order to assist the curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but the curing agent is not particularly limited to these, and can react with thermosetting compounds. If so, any curing agent may be used. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-Dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2 -Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. it can. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

<Polymerizable compound (D)>
The photosensitive coloring composition of the present invention contains a coloring composition, a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) contains a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.

The polymerizable compound (D) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl. (Meta) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate , Phenoxytetraethylene glycol (meth) acrylate, Phenoxyhexaethylene glycol (meth) acrylate, Trimethylolpropane PO-modified tri (meth) acrylate, Trimethylolpropane EO-modified tri (meth) acrylate, Isocyanuric acid EO-modified di (meth) acrylate , Isocyanuric acid EO modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate , Bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate , (Meta) acrylic acid ester of methylolated melamine, various acrylic acid esters and methacrylate esters such as epoxy (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether. , Pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

These commercially available products are KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303 manufactured by Nippon Kayaku Co., Ltd. , TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M-, manufactured by Toagosei Co., Ltd. 305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-221B, M-101A, Viscoat # 310HP, # 335HP, # 700, # 295, manufactured by Osaka Organic Co., Ltd. Examples thereof include # 330, # 360, #GPT, # 400, # 405, and NK ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

(Polymerizable compound having an acid group)
The polymerizable compound (D) can contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The photopolymerizable monomer having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a mono. Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

Commercially available products of photopolymerizable monomers having an acid group include Viscoat # 2500P manufactured by Osaka Organic Co., Ltd. and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. Can be mentioned.

(Polymeric compound having urethane bond)
The polymerizable compound (D) can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a (meth) acrylate having a hydroxyl group by reacting an alcohol with a polyfunctional isocyanate. Examples thereof include polyfunctional urethane acrylate obtained by the above-mentioned.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate , Glyoxide dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Commercially available products of polymerizable compounds having a urethane bond are AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd. Examples thereof include UA-160TM manufactured by Nakamura Chemical Industry Co., Ltd., UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd.

The polymerizable compound (D) can be used alone or in combination of two or more.

The blending amount of the polymerizable compound (D) is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is blended, curability and developability are further improved.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On, 1-Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) ) Phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetphenone compounds such as butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2 Thioxanthone compounds such as −methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloro). Methyl) -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- (naphtho-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) Triazine compounds such as -6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl- , 2- (O-benzoyl oxime)], or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Oxym ester compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrene quinone, camphorquinone , Ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferable.

As for the commercially available photopolymerization initiator (E), all acetphenone compounds are manufactured by IGM Resins and are "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1. -On), "Omnirad 369E" (2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone), "Omnirad 379EG" (2- (dimethyl) Amino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) and phosphine compounds are all manufactured by IGM Resins and are "Omnirad 819" (bis). (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide) and the like.

The photopolymerization initiator (E) can be used alone or in combination of two or more.

(Oxime ester compound)
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency. To.

Commercially available oxime ester compounds are available from BASF, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), etanone, 1. -[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA), TRONLY TR -PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Joshu Strong New Materials Co., Ltd.) and the like can be mentioned. Further, the oxime ester-based photopolymerization described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, etc. Initiators can also be mentioned.

The content of the photopolymerization initiator (E) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is blended, photocurability and developability are further improved.

<Sensitizer (H)>
The photosensitive coloring composition can contain a sensitizer (H).
The sensitizer (H) includes, for example, chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone. Polymethine dyes such as derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonor derivatives, aclysine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin Derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphy Razine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyllin derivative, anurene derivative, spiropyrane derivative, spiroxazine derivative, thiospiropyrane derivative, metal arene complex, organic ruthenium complex, or Michler ketone derivative, α-a Syroxyester, acyloxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone. Among these, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives can be mentioned. 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 and the like can be mentioned. In addition, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And "Special Functional Materials" (1986, CMC), the sensitizer described in

Commercially available products of the sensitizer (H) are "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis (diethylamino) benzophenone manufactured by Chemark Chemical Co., Ltd.). ) Etc. can be mentioned.

The sensitizer (E) can be used alone or in combination of two or more.

The content of the sensitizer (E) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (E). When an appropriate amount is contained, curability and developability are further improved.

<Thiol chain transfer agent (I)>
The photosensitive coloring composition may contain a thiol-based chain transfer agent as the chain transfer agent. By using thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, a chile radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated, so that the obtained coloring composition becomes highly sensitive. ..

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more thiol groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propantristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakisthioglycolate, Pentaerythritol Tetrakisthiopropionate, Tristrimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine And so on. , Preferred include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent (I) can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the film surface.

<Polymerization inhibitor (J)>
The photosensitive coloring composition may contain a polymerization inhibitor. As a result, exposure to the mask due to diffracted light can be suppressed during exposure by the photolithography method, so that a pattern having a desired shape can be easily obtained.

The polymerization inhibitor (J) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, Alkylcatechol compounds such as 4-t-butylcatechol and 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4 Alkyl resorcinol compounds such as −propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butyl Hydroquinone, alkylhydroquinone compounds such as 2,5-di-t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine Examples thereof include phosphine oxide compounds such as oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles of the coating film, pattern resolution and the like are improved.

<UV absorber (K)>
The photosensitive coloring composition can contain an ultraviolet absorber (K). The ultraviolet absorber is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based compounds, triazine-based organic compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating film is further improved, and good resolution can be obtained.

Benzotriazole compounds include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3. , 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2' -Hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1, Mix of 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) ) Phenzotriazole, 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- ( Reaction product of 3- (2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol ], 2- (2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-2-yl) -6-t-butyl-4-methylphenol, 2-( 3,5-Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3 -T-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5- (5) -Chloro-2H-benzotriazole-2-yl) phenyl] propionate can be mentioned.

Triazine-based compounds include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4,6-]. Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) Reaction product of -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester, 2,4-bis "2-hydroxy-4-butoxy" Phenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyloxy) ) Phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris ( 2-Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like can be mentioned.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-. Octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone , 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of the salicylic acid ester compound include phenyl salicylate, -p-octylphenyl salicylate, and -t-butylphenyl salicylate.

<Antioxidant (L)>
The photosensitive coloring composition may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and the thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process at the time of heat curing or ITO annealing, and allows the coating film to permeate. The rate can be improved.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound containing no halogen atom.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferable from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

Hindered phenolic antioxidants include, for example, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H). , 3H, 5H) -trione, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2- t-Butyl-5-methylphenol), 3- (3,5-di-t-butyl-4-hydroxyphenyl) stearyl propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8 , 10-Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3 , 5-Tris (3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2' -Methylenebis (6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (Dodecylthiomethyl) -o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [ 3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis [3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2'-thio- Bis- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis- (4, 6-Dimethyl-phenol), 2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, etc. Can be mentioned.

Hindered amine antioxidants include, for example, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6). −Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine , Poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) ) Imino] -Hexamethylene- [(2,2,6,6-tetramethyl-4-piperidyl) Imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol and 3, Ester of 5,5-trimethylhexanoic acid, 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-diazadecan-1,10-diamine, bisdecanediate (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,5) 1 dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, poly [[6-morpholino-s-triazine-2,4 -Diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, 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 And so on.

Phosphorus antioxidants include, for example, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis (4,6). -Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4' -Isopropyridene diphenyldiphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecylphosphite, tris (isodecyl) phosphite, triphenylphosphite, tetrakis (2,4-di-t-butylphenyl)- 4,4-biphenyldiphoshonito, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropyridene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (Nonylphenyl) Pentaerythritol diphosphite, Phenylbisphenol A Pentaerythritol diphosphite, Tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, Hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodiumbis (4-t-butylphenyl) phos Fight, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2,4) -Dit-butyl-6-methylphenyl) and the like.

Sulfur-based antioxidants include, for example, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], 3,3'-. Ditridecyl thiobispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o- Examples thereof include cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.

The antioxidant can be used alone or in combination of two or more.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the coloring composition because the transmittance, spectral characteristics, and sensitivity are good.

<Leveling agent (M)>
The photosensitive coloring composition may contain a leveling agent. As a result, the coatability of the composition on the transparent substrate and the drying property of the coating film are further improved. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.

Examples of the fluorine-based surfactant include compounds having a fluorocarbon chain.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, and polyoxyethylene octyl. Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedi sylated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene tetraoleate Solbit, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples thereof include alkanolamide and alkylimidazoline.

Examples of the cationic surfactant include alkylquaternary ammonium salts such as alkylamine salts, lauryltrimethylammonium chlorides, stearyltrimethylammonium chlorides, and cetyltrimethylammonium chlorides, and ethylene oxide adducts thereof.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanol lauryl sulfate. Examples thereof include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like.

Examples of the amphoteric surfactant include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

The surfactant can be used alone or in combination of two or more.

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the non-volatile content of the photosensitive coloring composition. Within this range, the balance between the coatability of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

<Storage stabilizer>
The photosensitive coloring composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include phosphine and phosphine.

The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the colorant (A).

<Adhesion improver>
The photosensitive coloring composition may contain an adhesion improver. As a result, the adhesion between the coating film and the base material is further improved. In addition, the photolithography method facilitates the formation of narrow patterns. Examples of the adhesion improver include a silane coupling agent and the like.

Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. (Meta) acrylic silanes such as 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-) Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Melcaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. Examples thereof include sulfides and isocyanates such as 3-isocyanatepropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is contained, the light sensitivity of the photosensitive coloring composition is improved, the adhesion of the coating film is further improved, and the resolution of the pattern is further improved.
<Solvent>
The photosensitive coloring composition may contain a solvent. As a result, the viscosity of the photosensitive coloring composition can be easily adjusted, so that a film having a smooth surface can be easily formed. The solvent may be appropriately selected according to the purpose of use and may be contained in an appropriate amount.

Examples of the solvent include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), and an ether ester solvent. (Solvent containing -COO- and -O- in the molecule), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O -, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid. Examples thereof include butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl. Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Examples thereof include ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenyletol, methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-. Ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate , 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol Examples thereof include monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate and the like.

Ketone solvents include, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, Examples include isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Among these, a solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable in terms of coatability and dryness. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are further preferable.

The solvent can be used alone or in combination of two or more.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition is subjected to a dispersion treatment using, for example, a red pigment (A) and a resin-type dispersant (B) to prepare a pigment dispersion. Then, the pigment dispersion, the binder resin (C), the photopolymerizable compound (D), and the photopolymerizable initiator (E) can be mixed and produced. It is preferable to use a dispersion aid (dye derivative or surfactant) when producing the pigment dispersion.
The photosensitive coloring composition is preferably prepared as a solvent-developing coloring composition or an alkali-developing coloring composition.

For the dispersion treatment, for example, a disperser such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used.

<Dispersed particle size of pigment>
The average dispersed particle size of the red pigment (A) is preferably 30 to 200 nm, more preferably 40 to 120 nm. Within this range, the viscosity can be suppressed and the dispersion stability is further improved.

As a method for measuring the dispersed particle size of the pigment, it is preferable to use Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method). The device settings include an absorption mode for particle permeability, a non-spherical particle shape, and an average diameter of D50. When the solvent used for the dispersion is used as the diluting solvent for the measurement and the sample treated with ultrasonic waves is measured immediately after the sample preparation, the result with little variation can be obtained.

<Removal of coarse particles>
In the present specification, it is preferable to remove the coarse particles contained therein after the stage of the pigment dispersion or the preparation of the photosensitive coloring composition. As a result, foreign matter can be removed from the coating film, so that a fine pattern can be easily formed.
The removal is preferably performed by, for example, a method such as centrifugation, a sintering filter, or a membrane filter. As a result, foreign matter such as coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles can be removed. As described above, the photosensitive coloring composition preferably contains substantially no particles of 0.5 μm or more, and preferably does not contain 0.3 μm or less.

<Color filter>
As used herein, a color filter comprises a substrate (also referred to as a transparent substrate) and a filter segment formed from a photosensitive coloring composition. The color filter segment (hereinafter, also referred to as a filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant to be used. Further, the color filter may separately have a magenta color filter segment, a cyan color filter segment, and a yellow filter segment as the color filter segment. A reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate that uses an aluminum electrode or a metal thin film as a reflective surface. As used herein, one of the filter segments is formed from a photosensitive coloring composition containing the red pigment (A).

<Manufacturing method of color filter>
It is preferable that the color filter first forms a black matrix on the substrate and then forms a filter segment. A thin film transistor (TFT) can be formed on the base material in advance, and then a black matrix can be formed.
Examples of the black matrix include a multilayer film of chromium and chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed.

The filter segment can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
Since the printing method can form a pattern only by repeating printing and drying of the photosensitive coloring composition prepared as a printing ink, it is low cost and excellent in mass productivity as a manufacturing method of a color filter. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

In the electrodeposition method, a color filter is produced by electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the transparent substrate. Further, in the transfer method, a filter segment is formed on the peeled surface of the peelable sheet. Next, this filter segment is transferred to a transparent substrate to prepare it.

In the photolithography method, for example, a photosensitive coloring composition containing a colorant having a certain color tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (light irradiation) through a mask having a predetermined pattern. Then, the developer is immersed in a solvent or an alkaline developer, or the developer is sprayed with a spray or the like for development, and the uncured portion is removed to obtain a desired pattern. By performing this step in the same manner using a photosensitive coloring composition having a colorant having another color tone, a color filter having filter segments of each color can be produced. Further, a second film (oxygen blocking film) can be further formed on the first film before exposure by using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film is not in contact with oxygen, so that the exposure sensitivity is further improved. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment. The photolithography method is preferable because it can produce a color filter with higher accuracy than the printing method.

Examples of the coating apparatus include spray coating, spin coating, slit coating, roll coating and the like. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. In addition, a defoaming agent or a surfactant can be added to the developing solution.

The color filter of the present invention is bonded to a facing substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by laminating the outside of the surface. This color liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convencend bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as).

In the present specification, the color filter can be used for applications such as a solid-state image sensor, an organic EL display device, a quantum dot display device, electronic paper, and a head-mounted display, in addition to the liquid crystal display device.

<Liquid crystal display device>
The liquid crystal display device of the present specification includes a color filter.
The liquid crystal display device includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED in that the red reproduction region is widened. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 provided with the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to be separated from each other, and a liquid crystal LC is enclosed between them.

The liquid crystal LC is oriented according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence). A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on the TFT (thin film transistor) array 12. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on the transparent protective film (not shown), and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

Further, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED, and have a wavelength (λ3) at which the emission intensity is maximized in the range of 430 nm to 485 nm. ), The wavelength (λ4) at which the light emission intensity is maximized in the range of 530 nm to 580 nm, the wavelength (λ5) at which the light emission intensity is maximum in the range of 600 nm to 650 nm, and the wavelength λ3. The ratio of the light emission intensity I3 to the light emission intensity I4 at the wavelength λ4 (I4 / I3) is 0.2 or more and 0.4 or less, and the ratio of the light emission intensity I3 at the wavelength λ3 to the light emission intensity I5 at the wavelength λ5 (I5 / I3). Has a white LED light source (LED1) having a spectral characteristic of 0.1 or more and 1.3 or less, and a wavelength (λ1) having a maximum emission intensity in the range of 430 nm to 485 nm, and is in the range of 530 nm to 580 nm. Has a second emission intensity peak wavelength (λ2), and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less. A white LED light source (LED2) having a wavelength is preferable.

Specific examples of the LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of the LED2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. In the production examples and the examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

Prior to the embodiment, each measurement method will be described.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows.

(Average molecular weight of resin)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , THF solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min.
The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 20 microliters. All molecular weights are polystyrene-equivalent values.

(Acid value of resin (mgKOH / g))
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to uniformly dissolve the solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo) ) Was titrated, and the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile component concentration of the resin solution.

(Amine value of basic resin type dispersant)
The amine value of the basic resin type dispersant is a value obtained by converting the measured total amine value (mgKOH / g) into a non-volatile component according to the method of ASTM D 2074.

<Manufacturing method of finely divided pigments>
<Manufacturing method of diketopyrrolopyrrole pigment>
(Diketopyrrolopyrrole pigment 1)
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecular sieve-dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere and heated to 100 ° C. with stirring to prepare an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. The cooled mixture was cooled to 75 ° C. using a high-speed stirring disperser while rotating a share disk having a diameter of 8 cm at 4000 rpm, and the alkali metal salt of the previously obtained diketopyrrolopyrrole compound was obtained. The solution was added in small portions. At this time, the rate at which the alkali metal salt of the diketopyrrolopyrrole compound is added at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at −5 ° C. or lower. Was added in small portions over approximately 120 minutes while adjusting. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, and the paste was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration through an ultrafilter was dried at 80 ° C. for 24 hours and pulverized to add 150.8 parts of diketopyrrolopyrrole pigment 1. Obtained.

(Diketopyrrolopyrrole pigment 2)
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following chemical formula (20) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in the reaction vessel 2. It was dissolved and this was added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were carried out to obtain 88.1 parts of diketopyrrolopyrrole pigment 2. ..

Chemical formula (20)

(Diketopyrrolopyrrole pigment 3)
The same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out except that 60.9 parts of 4-cyanobiphenyl was changed to 54.1 parts of 4-tert-butylbenzonitrile, and 83.9 parts of diketopyrrolopyrrole pigment 3 was added. Obtained.

(Diketopyrrolopyrrole pigment 4)
The same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide, and the diketopyrrolopyrrole pigment 4 was 87.0. I got a part.

(Diketopyrrolopyrrole pigment 5)
The same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide, and the diketopyrrolopyrrole pigment 5 was added to 86.9. I got a part.

(Diketopyrrolopyrrole pigment 6)
Diketopyrrolopyrrole pigment 6 was prepared in the same manner as in the production of diketopyrrolopyrrole pigment 2, except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide. I got one copy.

(Diketopyrrolopyrrole pigment 7)
While 220 parts of tert-amyl alcohol was placed in the reaction vessel 1 and cooled in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following chemical formula (21) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in the reaction vessel 2. It was dissolved and this was added dropwise to reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., 400 parts of methanol and 50 parts of acetic acid were added, and then filtration and washing with methanol were carried out to obtain 87.8 parts of diketopyrrolopyrrole pigment 7. ..

Chemical formula (21)

<Manufacturing of finely divided pigments>
(Manufacturing of refined pigment (A-1))
100 parts of diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water and stirred for 1 hour while heating at about 80 ° C. to form a slurry, which was filtered and washed with water to remove salt and diethylene glycol, then dried at 80 ° C. for 24 hours and pulverized. By doing so, 96.9 parts of a finely divided pigment (A-1) having a diketopyrrolopyrrole pigment was obtained.

(Manufacturing of refined pigment (A-2))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 2, the same procedure as in the production of the diketopyrrolopyrrole pigment (A-1) was carried out. A-2) 96.5 parts were obtained.

(Manufacturing of refined pigment (A-3))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 3, the same procedure as in the production of the diketopyrrolopyrrole pigment (A-1) was carried out. A-3) 98.1 parts were obtained.

(Manufacturing of refined pigment (A-4))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 4, the same procedure as in the production of the diketopyrrolopyrrole pigment (A-1) was carried out, and the diketopyrrolopyrrole-based micronizing pigment ( A-4) 98.0 parts were obtained.

(Manufacturing of refined pigment (A-5))
Except that 100 parts of the diketopyrrolopyrrole pigment 5 was changed to 100 parts of the diketopyrrolopyrrole pigment 5, the same procedure as in the production of the diketopyrrolopyrrole pigment (A-1) was carried out. A-5) 98.4 parts were obtained.

(Manufacturing of refined pigment (A-6))
Except that 100 parts of the diketopyrrolopyrrole pigment 6 was changed to 100 parts of the diketopyrrolopyrrole pigment 6, the same procedure as in the production of the refined pigment (A-1) was carried out, and the diketopyrrolopyrrole-based refined pigment ( A-6) 97.5 parts were obtained.

(Manufacturing of refined pigment (A-7))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 7, the same procedure as in the production of the diketopyrrolopyrrole pigment (A-1) was carried out. A-7) 97.5 parts were obtained.

(Manufacturing of refined pigment (A-8))
Diketopyrrolopyrrole Pigment 1 was prepared from commercially available C.I. I. Pigment Red 254 (BASF's "Irgazine Red D3656 HD") was changed to the same procedure as for the production of the fine pigment (A-1), and the diketopyrrolopyrrole fine pigment (A-8) 97 was used. . 3 copies were obtained.

(Manufacturing of refined pigment (A-9))
Anthraquinone red pigment C.I. I. Pigment Red 177 (Cynic's "Cinilex Red SR3C"): 500 parts, sodium chloride: 500 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 put 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. for 24 hours. Then, a refined pigment (A-9) was obtained.

(Manufacturing of refined pigment (A-10))
C. I. Pigment Red 242 (Clariant's "Novopalm Scarlet 4RF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a fine pigment (A-10).

(Manufacturing of refined pigment (A-11))
Commercially available C.I. I. Pigment Red 269 (PR269) (“Toner Magenta F8B” manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. This mixture is put into 4000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain 100 parts of a finely divided pigment (A-11).

<Manufacturing of refined yellow pigment>
(Refined yellow pigment (a-1 to 3))
Miniaturized quinophthalone pigments (a-1 to 3) were prepared from the quinophthalone pigments represented by the following chemical formula (56) to the quinophthalone pigments represented by the chemical formula (58) according to the examples of JP2012-226110A.

(Miniaturized Yellow Pigment a-1) (Miniaturized Yellow Pigment a-2)
Equation (56) Equation (57)

(Miniaturized yellow pigment a-3)
Equation (58)

(Refined yellow pigment (a-4))
C. I. Pigment Yellow 138 (BASF Japan's "Pariotor Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. .. This mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to make 95 parts fine. A yellow pigment (a-4) was obtained.

(Miniaturized yellow pigment (a-5))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by BASF Japan Ltd.), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader and kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a finely divided yellow pigment (a-5).

(Miniaturized yellow pigment (a-6))
100 parts of metal complex yellow pigment (CI Pigment Yellow 150, "Yellow Pigment E4GN" manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a finely divided yellow pigment (a-6). The average primary particle size was 36.6 nm.

(Miniaturized yellow pigment (a-7))
Yellow pigment C.I. I. Pigment Yellow 185 (“Paliotoll Yellow D1155” manufactured by BASF Japan Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1-gallon kneader and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put 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. for 24 hours. , A finely divided yellow pigment (a-7) was obtained.

<Dye derivative (b0)>
The following pigment derivatives were used.
Dye derivative (b0-1)


Dye derivative (b0-2)

Dye derivative (b0-3)
A dye derivative (b0-3) was obtained by the same production method as the quinophthalone compound (QL-c-1) described in Examples of JP-A-2015-172732.

Dye derivative (b0-4)
A dye derivative (b0-4) was obtained by the same production method as that of the quinophthalone compound (QL-f-1) described in Examples of JP-A-2015-172732.

Dye derivative (b0-3) Dye derivative (b0-4)

Dye derivative (b0-5)
Dye derivative (b0-5) according to the synthesis method described in Japanese Patent No. 4585781.
Al salt was obtained.

Dye derivative (b0-5)

<Manufacturing of basic resin type dispersant (b1) solution>
(Basic resin type dispersant (b1-1) solution)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst, and at 50 ° C. while flowing nitrogen. The mixture was stirred for 1 hour and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate was charged as an initiator, 5.6 parts of cuprous chloride and 133 parts of PGMAc were charged as a catalyst, and the temperature was raised to 110 ° C. under a nitrogen stream in the first block (B block). Polymerization was started. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate and 10 parts of methacryloyloxyethyl benzyldimethylammonium chloride as the second block (A block) monomer were added to this reactor, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of the non-volatile content, and the reaction solution was brought to room temperature. It was cooled to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20000, the molecular weight distribution Mw / Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin-type dispersant (b1-1) having an amine value of 169.8 mgKOH / g per non-volatile component was obtained. After cooling to room temperature, about 2 g of the resin-type dispersant 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 added to the previously synthesized basic resin-type dispersant (b1-1). Propylene glycol monomethyl ether acetate (PGMAc) was added so that the content was 30% by mass to prepare a basic resin-type dispersant (b1-1) solution.

(Basic resin type dispersant (b1-2) solution)
133 parts of PGMAc was charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110 ° C. while substituting with nitrogen. Add 177 parts of diethylaminoethyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) to the dropping tank until it becomes uniform. After stirring, the mixture was added dropwise to the reaction vessel over 2 hours, and then the reaction was continued at the same temperature for 3 hours. In this way, a basic resin-type dispersant (b1-2) having an amine value of 345 mgKOH / g per non-volatile component and a number average molecular weight (Mn) of 3000 was obtained.
A basic resin-type dispersant (b1-2) solution was prepared by diluting in the same manner as the resin-type dispersant (b1-1) solution.

(Basic resin type dispersant (b1-3) solution)
133 parts of PGMAc was charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110 ° C. while substituting with nitrogen. 1,2,2,6,6-pentamethylpiperidyl methacrylate 177 parts, methyl acrylate 3 parts, 2-hydroxyethyl methacrylate 20 parts, PGMAc 61 parts, and 2,2'-azobis (2,4-dimethylvalero) in a dropping tank. 6 parts of nitrile) was charged, stirred until uniform, and then added dropwise to the reaction vessel over 2 hours, after which the reaction was continued for 3 hours at the same temperature. In this way, a basic resin-type dispersant (b1-3) having an amine value of 201 mgKOH / g per non-volatile component and a number average molecular weight of 3,800 (Mn) was obtained. A solution of the basic resin type dispersant (b1-3) was prepared by diluting in the same manner as the solution of the basic resin type dispersant (b1-1).

(Basic resin type dispersant (b1-4) solution)
A flask equipped with a cooling tube and a stirrer was charged with 1.0 part of AIBN and 186 parts of propylene glycol monomethyl ether acetate, followed by 27 parts of methyl methacrylate, 27 parts of butyl methacrylate, 19 parts of 2-ethylhexyl methacrylate, 16 parts of benzyl methacrylate, and triethylene. 16 parts of glycol ethyl ether methacrylate and 3.6 parts of cumyldithiobenzoate were charged and replaced with nitrogen for 30 minutes. Then, with gentle stirring, the temperature of the reaction solution was raised to 60 ° C., and this temperature was maintained for 24 hours for living radical polymerization.
Next, to this reaction solution, 1.0 part of AIBN and 54 parts of dimethylaminoethyl methacrylate were dissolved in 108 parts of propylene glycol monomethyl ether acetate, and a solution subjected to nitrogen substitution for 30 minutes was added, and living radical polymerization was carried out at 60 ° C. for 24 hours. After that, a solution of the basic resin type dispersant (b1-4) was prepared by diluting in the same manner as the solution of the basic resin type dispersant (b1-1).

(Basic resin type dispersant (b1-5) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 500 parts of methyl methacrylate, 22 parts of thioglycerol, and 511 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., 0.50 part of AIBN was added, and then the reaction was carried out for 7 hours. After confirming that 95% had reacted by measuring the non-volatile content, the mixture was cooled to room temperature to obtain a 50% non-volatile solution of a vinyl polymer having a weight average molecular weight of 5200 and having two free hydroxyl groups at one terminal region. Then, 90.4 parts of isophorone diisocyanate, 45.1 parts of propylene glycol monomethyl ether acetate, and 0.11 part of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C., reacted for 3 hours, and then cooled to 40 ° C. to obtain a prepolymer solution having an isocyanate group. 22.2 parts of methyliminobispropylamine, 13.2 parts of dibutylamine, and 304.6 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel 2 equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer and heated to 100 ° C. .. The prepolymer solution was added dropwise thereto over 30 minutes, and after reacting for another 1 hour, the mixture was cooled to room temperature to complete the reaction. If necessary, a part of the solvent is removed by vacuum distillation, and then diluted in the same manner as the basic resin type dispersant (b1-1) solution to obtain the basic resin type dispersant (b1-5) solution. Prepared.

(Basic resin type dispersant (b1-6) solution)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and nitrogen was poured. While stirring at 50 ° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Funkryl FA-711MM manufactured by Hitachi Chemical Co., Ltd.) as a second block (A block) monomer were added to this reactor. The mixture was charged and stirred while maintaining a nitrogen atmosphere at 110 ° C., and the reaction was continued. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidylmethacrylate, the polymerization solution was sampled and the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was 98 when converted from the non-volatile content. After confirming that the content was greater than or equal to%, the reaction solution was cooled to room temperature to terminate the polymerization.
In this way, a basic base resin type dispersant (b1-6) having a piperidine skeleton having an amine value of 57 mgKOH / g per non-volatile component and a number average molecular weight of 4,500 (Mn) was obtained.
A basic base resin type dispersant (b1-6) solution was prepared by diluting in the same manner as the resin type dispersant (b1-1) solution.

(Basic resin type dispersant (b1-7) solution)
In the method for producing the pigment dispersant (1) described in Production Example 1 of Japanese Patent No. 5513691, [(3- (N, N-dimethylamino) propylacrylamide / methoxypolyethylene glycol methacrylate copolymer (23/77 weight) %) Quadrified product; quaternization rate 27 mol%)] is synthesized and diluted in the same manner as the resin type dispersant (b1-1) solution to form a basic group resin type dispersant (b1) having an amide bond. -7) A solution was prepared.

(Production of Phosphoric Acid Resin Type Dispersant (b2) Solution)
(Production of Phosphoric Acid Resin Type Dispersant (b2-1) Solution)
A reaction vessel equipped with a nitrogen gas introduction tube, a condenser, and a stirrer was charged with 186 g of lauryl alcohol, 571 parts of ε-caprolactone monomer, and 0.6 part of tetrabutyl titanate, replaced with nitrogen gas, and then heated at 120 ° C. for 3 hours. Stirred. The disappearance of the caprolactone monomer was confirmed by a GPC (gel permeation chromatography) RI detector using tetrahydrofuran as an eluent. After cooling to 40 ° C. or lower, it is mixed with 84.5 parts of polyphosphoric acid having an orthophosphoric acid equivalent content of 116%, gradually heated, heated at 80 ° C. for 6 hours with stirring, and the number average molecular weight of R1 is 760. , A phosphoric acid-based resin-type dispersant (b2-1) having an abundance ratio of n = 1 and 2 of 100: 12 was obtained. By adjusting the non-volatile content with PGMAc, a phosphoric acid-based resin-type dispersant (b2-1) solution having an acid value of 166 mgKOH / g per non-volatile content of 30% was obtained.

(Production of Phosphoric Acid Resin Type Dispersant (b2-2) Solution)
A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer were attached to a separable 4-neck flask, and 1500 parts of cyclohexanone was charged. The temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then 120 parts of methyl methacrylate was added from the dropping tube. 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, 120 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M-110” manufactured by Toa Synthetic Co., Ltd.), 6 parts of acid phosphoxyethyl methacrylate, A mixed solution of 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a phosphoric acid-based resin-type dispersant (b2-2) solution having a non-volatile content of 30% and a weight average molecular weight of 24,000.

(Production of salt (b3) solution of basic resin type dispersant)
(Salt (b3-1) solution of phenylphosphonic acid and a basic resin-type dispersant having an amino group)
In a 100 mL round bottom flask, 12.6 parts of a basic resin-type dispersant (methyl methacrylate / dimethylaminoethyl methacrylate: composition ratio 5/3) is dissolved in 35 parts of PGMAc to dissolve phenylphosphonic acid, which is a salt-forming component. To a basic resin-type dispersant having an amino group and phenylphosphonic acid by adding 2.4 parts (0.5 molar equivalent to dimethylaminoethyl methacrylate) and stirring at a reaction temperature of 40 ° C. for 2 hours. A solution of 30% by mass of non-volatile content of salt (b3-1) was prepared.

(Salt (b3-2) solution of phenylphosphonic acid, a basic resin-type dispersant having an amino group and an ammonium salt)
In a 100 mL round bottom flask, 12.6 parts of a basic resin-type dispersant (methyl methacrylate / dimethylaminoethyl methacrylate / dimethylaminoethyl methyl chloride salt: constituent weight ratio 3/3/2) is added to 35 parts of PGMAc. Is dissolved, 2.4 parts of phenylphosphonic acid, which is a salt-forming component (0.5 molar equivalent to dimethylaminoethyl methacrylate), is added, and the mixture is stirred at a reaction temperature of 40 ° C. for 2 hours to obtain phenylphosphonic acid. A 30% by mass solution of a salt (b3-2) of a basic resin-type dispersant having an amino group and an ammonium salt was prepared.

(Production of Carboxylic Acid Resin Type Dispersant (b4) Solution)
(Production of Carboxylic Acid Resin Type Dispersant (b4-1) Solution)
A reaction vessel equipped with a gas introduction tube, a temperature, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene were added as a catalyst, and the mixture was reacted at 100 ° C. for 7 hours. .. It was confirmed by measuring the acid value that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and PGMAc was added and diluted so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH / g. , A resin-type dispersant (b4-1) solution having a weight average molecular weight of 8500 was obtained.

(Production of Carboxylic Acid Resin Type Dispersant (b4-1-1) Solution)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were added. I prepared it. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted for 4 hours, and then reacted at 80 ° C. for 2 hours. Further, 30 parts of tert-butyl acrylate, 20 parts of ETERNALCOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl), manufactured by Ube Kosan Co., Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc are charged, and a reaction vessel is charged. 0.2 parts of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes while keeping the inside at 80 ° C. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers had reacted. PGMAc is added and diluted so that the non-volatile content is 30% in the non-volatile content measurement, and a carboxylic acid resin type dispersant (b4-1-) having an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000. 1) A solution was obtained. The vinyl polymer portion of the carboxylic acid resin type dispersant (b4-1-1) has tert-butyl, an oxetane group, and a carboxyl group as thermally crosslinkable functional groups.

(Production of Carboxylic Acid Resin Type Dispersant (b4-1-2) Solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged and nitrogen gas was used. After the substitution, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, and 200 parts of methyl acrylate in terms of non-volatile content. 50 parts of methacrylic acid and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours. (Second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and 2270 cm based on the isocyanate group by IR. The reaction was carried out until the disappearance of the peak of -1 was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a carboxylic acid resin type dispersant (b4-1-2) solution having a non-volatile content of 30%. The acid value of the obtained dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13000.

(Production of Carboxylic Acid Resin Type Dispersant (b4-2) Solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst were charged, and nitrogen gas was charged. After replacement with, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by measuring the non-volatile content, 73.3 parts of pyromellitic anhydride was added, and the reaction was carried out at 120 ° C. for 2 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. By adjusting the non-volatile content with PGMAc, a carboxylic acid resin type dispersant (b4-2) solution having a non-volatile content of 30% was obtained. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mgKOH / g.

<Production example of binder resin (C)>
(Preparation of binder resin (C-1) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) , 2, 2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20%. A binder resin (C-1) solution was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of binder resin (C-2) solution)
207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karens manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20%. Binder resin (C-2) was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C-3) solution)
370 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C., the inside of the flask was replaced with nitrogen, and then the parac was used from the dropping tube. Milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the non-volatile acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
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 PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. A binder resin (C-3) solution was prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin (C-4) solution)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.), and 40 parts of PGMAc, and use an n-dodecane as a chain transfer agent dropping tank. A well-stirred mixture of 8 parts of thiol and 32 parts of PGMAc was prepared.
After charging 395 parts of PGMAc in the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel became stable at 90 ° C., the dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the completion of the dropping, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged in the reaction vessel, and the mixture was allowed to react at 110 ° C. for 12 hours. It was. Then, 150 parts of PGMAc is added and cooled to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized resin solution. As described above, PGMAc was added to obtain a binder resin (C-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile component was 2 mgKOH / g.

<Manufacturing method of coloring composition (single color)>
[Example 1]
(Preparation of coloring composition (R-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 3 hours, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a colored composition (R-1) having a non-volatile component of 24.3% by mass.
Pigment (A-1): 20.5 parts Basic resin type dispersant ((b1-1): Non-volatile content 30% liquid): 1.0 part Phosphoric acid-based resin type dispersant ((b2-1): Non-volatile Minute 30% liquid): 0.5 part Carboxylic acid resin type dispersant ((b4-1): Non-volatile content 30% liquid): 0.5 part Binder resin (C-1: Non-volatile content 20% liquid): 16 .0 parts Solvent (P): 61.5 parts

[Examples 2-39, Comparative Examples 1-4, Production Examples 1-9]
(Preparation of coloring composition (R-2 to 52))
Coloring compositions (R-2 to 52) were prepared in the same manner as in Example 1 except that the material types and masses were changed as shown in Table 1.

<Manufacturing method of coloring composition (mixing of coloring materials)>
[Example 101]
(Preparation of coloring composition (X-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition (R-1: 24.3% non-volatile liquid): 40 parts Coloring composition (R-44: 24.3% non-volatile liquid): 16 parts Binder resin (C-1: 20% non-volatile liquid) ): 32 parts Solvent (P): 12 parts

[Examples 102 to 149, Comparative Example 101]
(Preparation of coloring composition (X-2 to 50))
Coloring compositions (X-2 to 50) were prepared in the same manner as in Example 101, except that the material types and masses were changed as shown in Table 2.

<Evaluation of coloring composition>
The obtained coloring compositions (R-1 to 43, X-1 to 50) were tested for viscosity and storage stability by the following methods. The evaluation criteria are as follows.
◎: Extremely good 〇: Good △: Practical use ×: Not suitable for practical use

(Measurement of viscosity characteristics)
The viscosity at a rotation speed of 20 rpm was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). The evaluation criteria are as follows.
◯: Viscosity 4.0 mPa · s or more and less than 20.0 mPa · s
X: Viscosity 20 mPa · s or more
(Storage stability)
The initial viscosity of the day after the coloring composition was prepared and the viscosity after aging at 40 ° C for 1 week were measured at 25 ° C using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). It was measured under the condition of 50 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change in viscosity with time was calculated by the following formula, and the storage stability was evaluated in two stages.
[Ratio of change in viscosity over time] = | ([Initial viscosity]-[Viscosity over time]) / [Initial viscosity] | × 100
◯: Change rate less than 5% ×: Change rate 5% or more

(Foreign matter evaluation)
The number of foreign substances in the coating film of the coating film obtained by applying the coloring composition on a 10 cm square glass substrate so that the dry coating film is about 2.0 μm and heat-treating at 230 ° C. for 1 hour in an oven. Was measured. The evaluation was carried out by observing the surface using a metallurgical microscope "BX60" (manufactured by Olympus System Corporation). The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured by transmission. The evaluation criteria are as follows.
⊚: The number of foreign substances is less than 5
〇: The number of foreign substances is 5 or more and less than 20
Δ: The number of foreign substances is 21 or more and less than 100
X: The number of foreign substances is 100 or more

<Manufacturing method of photosensitive coloring composition>
[Example 201]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (R-1: 20% non-volatile content): 50.0 parts Binder resin (C-2: 20% non-volatile content): 15.0 parts Thermosetting compound (CE-1): 1.0 part Heat Curable compound (CE-2): 1.0 part Photopolymerizable monomer (D): 3.0 parts Photopolymerization initiator (E): 1.8 parts Sensitizer (H): 0.2 parts Thiol-based chain transfer agent (I): 0.4 part Polymerization inhibitor (J): 0.1 part Ultraviolet absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M) : Non-volatile content 3%): 1.0 part Storage stabilizer (N): 0.1 part Silane coupling agent (O): 0.2 part Solvent (P): 26.0 parts

[Examples 202 to 290, Comparative Examples 201 to 205]
(Preparation of Photosensitive Coloring Compositions (Y-2 to 95))
Photosensitivity coloring compositions (Y-2 to 95) were prepared in the same manner as in Example 201, except that the types of the coloring composition and the binder resin solution of Example 201 were changed as shown in Table 4. Further, in the table, in Example 289, the binder resin (C-2) of Example 240 was changed to (C-3). Further, in Example 290, the binder resin (C-2) of Example 240 is changed to (C-4). The raw materials are as follows.

<Thermosetting compound (CE)>
-Epoxy compound (CE-1)
(CE-1-1) 1,2'-bis (hydroxymethyl) -1-butanol 1,2-
Epoxy-4- (2-oxylanyl) cyclohexane adduct [EHPE-3150 (manufactured by Daicel)],
(CE-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(CE-1-3) Trichloroisocyanuric acid triglycidyl (CE-1-1) to (CE-1--3) were mixed in equal amounts to prepare an epoxy compound (CE-1).
-Oxetane compound (CE-2):
3-Ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Polymerizable compound (D)>
(D-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D-2) Dipentaerythritol penta and hexaacrylate (E-2) [Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D-3) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-4) Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(D-5) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a reaction vessel having a polyfunctional urethane acrylate content of 1 liter and 5 mouths according to the following, and reacted at 60 ° C. for 8 hours to obtain a (meth) acryloyl group. A product containing the polyfunctional urethane acrylate (D-5) having the above was obtained. The proportion of the polyfunctional urethane acrylate (D-5) in the product was 70% by mass, and the balance was other photopolymerizable. It is occupied by monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(D-6) Bifunctional bisphenol A type (meth) acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D-7) Triacrylate ethoxylated isocyanuric acid [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
As described above, (D-1) to (D-7) were mixed in the same amount to prepare a photopolymerizable monomer (D).

<Photopolymerization initiator (E)>
(E-1) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan Ltd.)]
(E-2) 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [Irgacure 379 (manufactured by BASF Japan Ltd.)]
(E-3) 2,4,6-trimethylbenzoyludiphenyl-phosphine oxide [Lucillin TPO (manufactured by BASF Japan Ltd.)]
(E-4) 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole [biimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(E-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daiki Fine)]
(E-6) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) [Irgacure OXE02 (BASF Japan) Made by the company)]
(E-7) 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one [Irgacure 2959 (manufactured by BASF Japan Ltd.)]
(E-8) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [Irgacure 819 (manufactured by BASF Japan Ltd.)]
As described above, (E-1) to (E-8) were mixed in equal amounts to prepare a photopolymerization initiator (E).

<Sensitizer (H)>
(H-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis (diethylamino) benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to prepare a sensitizer (H).

<Thiol chain transfer agent (I)>
(I-1) Trimethylolethane ethanetris (3-mercaptobutyrate) [TEMB (manufactured by Showa Denko KK)]
(I-2) Trimethylolpropanetris (3-mercaptobutyrate) [TPMB (manufactured by Showa Denko KK)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropanetris (3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (I-1) to (I-5) were mixed in the same amount to prepare a thiol-based chain transfer agent (I).

<Polymerization inhibitor (J)>
(J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) t-Butylhydroquinone or more, (J-1) to (J-3) are mixed in equal amounts, and a polymerization inhibitor is added. It was designated as (J).

<UV absorber (K)>
(K-1) 2- [4-[(2-Hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine [TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol [TINUVIN900 (manufactured by BASF Japan Ltd.)]
As described above, (K-1) to (K-2) were mixed in the same amount to prepare an ultraviolet absorber (K).

<Antioxidant (L)>
(L-1) Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (L-2) 3,3'-dioctadecylthiodipropanoate (L-3) tris [2] , 4-Di- (t) -butylphenyl] phosphine (L-4) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-octylphenyl salicylate or higher, (L) -1) to (L-5) were mixed in the same amount to prepare an antioxidant (L).

<Leveling agent (M)>
Big Chemie "BYK-330" 1 copy,
1 copy of "Mega Fvck F-551" manufactured by DIC Corporation,
A mixed solution in which 1 part of "Emargen 103" manufactured by Kao Corporation is dissolved in 97 parts of PGMAc.

<Storage stabilizer (N)>
(N-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine ("TPP" manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (N-1) to (N-2) were mixed in the same amount to prepare a storage stabilizer (N).

<Adhesion improver (O)>
(O-1) 3-glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (O-1) to (O-4) were mixed in the same amount to prepare a silane coupling agent (O).

<Solvent (P)>
(P-1) PGMAc 30 parts (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) 10 parts or more of diproprene glycol methyl ether acetate and (P-1) to (P-6) were mixed in the above parts by mass to prepare a solvent (P).

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. The test results are shown in Table 5.
The meaning of the evaluation rank is as follows.
◎: Extremely good 〇: Good △: Practical use ×: Not suitable for practical use

(Development speed evaluation)
The photosensitive coloring composition was rotationally coated on a glass substrate having a thickness of 0.7 mm and a thickness of 10 mm × 10 mm using a spin coater so as to have a dry film thickness of 1.0 μm, and dried at 70 ° C. for 20 minutes. 2 ml of a 2 mass% potassium hydroxide aqueous solution was added dropwise to the coating film, and the time until the coating thickness was dissolved and disappeared was measured. The evaluation criteria are as follows.
◯: Less than 10 seconds Δ: 10 seconds or more, less than 15 seconds ×: 15 seconds or more

(Measurement of viscosity characteristics)
The same procedure as above was performed.

(Storage stability)
The same procedure as above was performed.

(Foreign matter evaluation)
The same procedure as above was performed.

(Solvent resistance evaluation)
The coloring composition was rotationally coated on a glass substrate using a spin coater so that the dry film thickness was 2.0 μm, and prebaked at 120 ° C. for 120 seconds. Then, after cooling this substrate to room temperature, ultraviolet rays were exposed through a photomask at intervals of 100 μm using an ultrahigh pressure mercury lamp. Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and post-baked at 230 ° C. for 30 minutes in a clean oven to carry out the substrate. Striped colored pixels were formed on the top. Next, the coated substrate was immersed in the N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and observed with an optical microscope for evaluation. The evaluation ranks are as follows.
〇: Good appearance and color without change
Δ: Wrinkles occur in some parts, but the color does not change and is good.
×: peeling or discoloration occurs

10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Orientation layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (9)

Contains red pigment (A), resin type dispersant (B), and binder resin (C).
A coloring composition in which the resin-type dispersant contains the following dispersant (B1) or (B2).
(B1) A resin-type dispersant (B2) containing a basic resin-type dispersant (b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4). A resin-type dispersant containing a salt (b3) of the compound represented by the above or the compound represented by the general formula (2) and a basic resin-type dispersant (b1), and a carboxylic acid-based resin-type dispersant (b4).

(However, in the general formula (1) and the general formula (2), R ¹ and R ² are independently hydrogen atoms, hydroxyl groups, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, respectively. vinyl group, an optionally substituted phenyl group or a benzyl group represents or -O-R ^4,, R ⁴ is a straight chain of 1 to 20 carbon atoms, branched chain or cyclic alkyl group, a vinyl group, Represents a phenyl or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that at least one of R ¹ and R ² contains a carbon atom. R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or —OR ⁴ ). The coloring composition according to claim 1, wherein the basic resin type dispersant (b1) has an amide bond. The coloring composition according to claim 1 or 2, wherein the phosphoric acid-based resin type dispersant (b2) contains the following (b2-1) or (b2-2).
(B2-1): Resin-type dispersant represented by the following general formula (3) General formula (3) (HO-) _3-n- PO- (OR ⁵ ) _n
(In the formula, R ⁵ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)
(B2-2): Resin-type dispersant which is a copolymer of an ethylenically unsaturated monomer having a phosphoric acid group and another ethylenically unsaturated monomer. The coloring composition according to any one of claims 1 to 3, wherein the carboxylic acid-based resin type dispersant (b4) contains the following (b4-1) or (b4-2).
(B4-1): A resin-type dispersant containing a polyester moiety having a carboxyl group and a vinyl polymer moiety.
The polyester moiety having a carboxyl group is a reaction product of a hydroxyl group-containing compound and a kind of acid anhydride group selected from the group consisting of tetracarboxylic acid anhydride and tricarboxylic acid anhydride.
(B4-2): Dispersant represented by the following general formula (4) General formula (4) (HOOC-) _m- R ^6- (-COO- [-R ^8- COO-] _n- R ⁷ ) _t
(In the formula, R ⁶ is a tetravalent aromatic tetracarboxylic acid residue, R ⁷ is a monoalcohol residue, R ⁸ is a lactone residue, m is 2 or 3, and n is an integer of 1 to 50. , T represents (4-m).) The coloring composition according to claim 4, wherein the carboxylic acid-based resin type dispersant (b4-1) is the following (b4-1-1) or (b4-1-2).
(B4-1-1): The vinyl polymer moiety contains one or more thermally crosslinkable functional groups selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, and a blocked isocyanate group, and a carboxyl group. Resin type dispersant.
(B4-1-2): A resin-type dispersant in which the vinyl polymer portion contains an ethylenically unsaturated group. The coloring composition according to any one of claims 1 to 5, further comprising a yellow pigment (a). A photosensitive coloring composition containing the coloring composition according to any one of claims 1 to 6, the polymerizable compound (D), and the photopolymerization initiator (E). A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 7. A liquid crystal display device including the color filter according to claim 8.