Coloring composition for color filters, color filters and display devices

Abstract

To provide a coloring composition for a color filter which is excellent in dispersibility and storage stability, and is excellent in development property when a coloring pattern is formed by a photolithographic method.SOLUTION: A coloring composition for a color filter contains a coloring agent (A), a resin type dispersant (B), a binder resin (C), and a solvent (D), in which the resin type dispersant (B) contains an aromatic carboxylic acid polyester site and a vinyl polymer site, and the vinyl polymer site is a polymer having one or more thermally crosslinkable group-containing monomer units selected from a hydroxyl group, an oxetane group, a tert-butyl group, a block isocyanate group and a (meth)acryloyl group, and a monomer unit having an alicyclic hydrocarbon group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a coloring composition used in the manufacture of color filters and the like used in liquid crystal displays, solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and the like. [Background technology]

[0002] Color filters incorporated in liquid crystal displays and organic electroluminescence displays use filter segments in which a coating made from a coloring composition in which pigments are finely dispersed is patterned by photolithography. Refining the pigments can increase the brightness and contrast of color filters, but on the other hand, there are problems such as the viscosity of the coloring composition increasing over time and deteriorating heat resistance and solvent resistance. In recent years, dyes have also been attracting attention as coloring materials in order to achieve high contrast ratios and high brightness that cannot be achieved with pigments. Dyes are generally soluble in solvents and polymers, and are stable in color filter coloring compositions without causing aggregation. In addition, color filters obtained using coloring liquids in which the dyes are dispersed can achieve high contrast ratios and have excellent light transmittance because the dyes are dispersed at the molecular level. However, coloring compositions containing dyes have problems such as poorer heat resistance, light resistance, and chemical resistance than coloring compositions using pigments as colorants.

[0003] Therefore, Patent Document 1 discloses a coloring composition using a block-type resin-type dispersant. Patent Document 2 discloses a coloring composition containing a resin having a carboxyl group-containing monomer unit, a polycyclic alicyclic monomer unit, and an aromatic ring-containing monomer. Patent Document 3 discloses a coloring composition combining a dye multimer and a pigment dispersed with a resin-type dispersant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2002-31713 A [Patent Document 2] JP 2013-210444 A [Patent Document 3] JP 2013-195854 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the coloring composition of Patent Document 1 had a problem with developability when forming a pattern by photolithography (the peeled coating adheres to other parts of the substrate). The coloring composition of Patent Document 2 had good developability but had a problem with storage stability. Patent Document 3 had improved heat resistance, light resistance, and chemical resistance, but had a problem with poor developability.

[0006] An object of the present invention is to provide a coloring composition for color filters which is excellent in dispersibility and storage stability, and which has excellent developability when a colored pattern is formed by a photolithography method. [Means for solving the problem]

[0007] The coloring composition for color filters of the present invention comprises a colorant (A), a resin-type dispersant (B), a binder resin (C), and a solvent (D), The resin-type dispersant (B) contains an aromatic carboxylic acid polyester portion and a vinyl polymer portion, The vinyl polymer portion is a polymer having one or more thermally crosslinkable group-containing monomer units selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, a blocked isocyanate group, and a (meth)acryloyl group, and a monomer unit having an alicyclic hydrocarbon group. Effect of the Invention

[0008] According to the present invention described above, it is possible to provide a coloring composition for color filters, which has excellent dispersibility and storage stability, and has excellent developability when a colored pattern is formed by a photolithography method, a color filter, and a display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] First, the terms used in this specification are defined. When "(meth)acrylate", "(meth)acrylic acid", or "(meth)acrylamide" is written, it means "acrylate and / or methacrylate", "acrylic acid and / or methacrylic acid", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" means color index (CI). The polymerizable unsaturated group is a vinyl group, a (meth)acryloyl group, or the like. The monomer is a compound containing a polymerizable unsaturated group. The resin-type dispersant (B) may be simply called a "dispersant".

[0010] The coloring composition for color filters of the present invention (hereinafter also referred to as a coloring composition) contains a colorant (A), a resin-type dispersant (B), a binder resin (C), and a solvent (D), The resin-type dispersant (B) contains an aromatic carboxylic acid polyester portion and a vinyl polymer portion, The vinyl polymer portion is a polymer having one or more thermally crosslinkable group-containing monomer units selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, a blocked isocyanate group, and a (meth)acryloyl group, and a monomer unit having an alicyclic hydrocarbon group. The coloring composition of the present invention is preferably used by forming a coating by coating. In the coloring composition of the present invention, the aromatic carboxylic acid polyester moiety in the resin type dispersant (B) enhances dispersibility and contributes to developability. In addition, the alicyclic hydrocarbon group in the vinyl polymer moiety in the resin type dispersant (B) acts as a steric hindrance and suppresses the aggregation of colorant dispersion particles over time after dispersion, thereby improving the storage stability of the coloring composition for color filters. This improves the dispersibility, storage stability, and developability of the coloring composition.

[0011] <Coloring agent> The colorant (A) can be any colorant (pigment, dye) that can be used in color filters. Pigments include organic pigments and inorganic pigments, with organic pigments being preferred. In addition, dyes are preferably used in combination with pigments from the viewpoint of coloring power.

[0012] The content of the colorant (A) is preferably 10 to 90 mass%, more preferably 15 to 80 mass%, and even more preferably 20 to 70 mass%, based on 100 mass% of the total nonvolatile content of the colored composition. When an appropriate amount is contained, good color reproducibility is easily obtained. The content of the dye is preferably 1 to 800 parts by mass, and more preferably 5 to 400 parts by mass, relative to 100 parts by mass of the pigment. When an appropriate amount of the dye is used, the brightness and contrast ratio of the color filter are further improved.

[0013] Organic pigments Specific examples of organic pigments are given below. Red pigments include, for example, CI 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, 1 01, 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, 21 6, 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, 291, etc. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, preferred are CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, 269, and 291, and more preferred are CI Pigment Red 177, 209, 224, 242, 254, 269, and 291.

[0014] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferable, and CI Pigment Blue 15:6 is more preferable. It is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigments described in JP-A No. 2004-333817, Japanese Patent No. 4893859, and the like can also be used.

[0015] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred from the viewpoint of obtaining a high contrast ratio and high brightness.

[0016] Yellow pigments include, for example, CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 1 36, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, etc. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, or 231 is preferable, and CI Pigment Yellow 83, 138, 139, 150, 180, or 231 is more preferable.

[0017] Examples of the purple pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, CI Pigment Violet 19 or 23 is preferable, and CI Pigment Violet 23 is more preferable.

[0018] [Micronization of pigments] The organic pigment is preferably used in a finely divided state. Examples of the finely divided state include wet grinding, dry grinding, and solution deposition. In this specification, the salt milling treatment by the kneader method, which is one type of wet grinding, is preferred. The average primary particle diameter of the pigment is preferably 20 to 100 nm, more preferably 25 to 85 nm. If the pigment has an appropriate average primary particle diameter, the dispersibility is improved and the contrast ratio is also improved. Specifically, the minor axis diameter and major axis diameter of each pigment primary particle are measured, and the average is taken as the particle diameter of the pigment particle. Next, for 100 or more pigment particles, the volume of each particle is calculated by approximating the cube of the calculated particle diameter, and the volume average particle diameter is taken as the average primary particle diameter. The primary particle diameter of the pigment is measured by a method of directly measuring the size of the primary particles from an electron micrograph of the pigment taken with a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of each pigment primary particle are measured, and the average is taken as the particle diameter of the pigment particle. Next, for 100 or more pigment particles, the volume of each particle is calculated by approximating the cube of the calculated particle diameter, and the volume average particle diameter is taken as the average primary particle diameter.

[0019] The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during the salt milling process by utilizing the high hardness of the inorganic salt. By optimizing the conditions for the salt milling process of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0020] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate, etc. Among these, inexpensive sodium chloride (table salt) is preferable. From the viewpoints of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 mass%, more preferably 300 to 1000 mass%, relative to 100 mass% of the pigment.

[0021] The water-soluble organic solvent can wet the pigment and the water-soluble inorganic salt. The water-soluble organic solvent may be any solvent that dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. In this specification, the temperature rises during salt milling, and the solvent becomes prone to evaporate, so from the viewpoint of safety, a high-boiling point solvent having a boiling point of 120°C or more is preferred. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and more preferably 50 to 500% by mass, based on 100% by mass of the pigment.

[0022] When the pigment is subjected to salt milling, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature (25°C) and insoluble in water. In some embodiments, the resin is preferably partially soluble in an organic solvent. The amount of the resin used is preferably 5 to 200% by mass relative to 100% by mass of the pigment.

[0023] "dye" Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Furthermore, the dye may be a derivative of these dyes or a lake pigment obtained by converting a dye into a lake.

[0024] The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid. The direct dye is preferably an inorganic salt of an acid dye, or a salt-forming compound of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Also, a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye is also preferred. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive coloring composition having excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0025] Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it has excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion component that acts as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0026] Furthermore, when the dye has a polymerizable unsaturated group in the molecule, the dye becomes a dye with excellent durability.

[0027] The chemical structure of the dye may be, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azido dyes, azidophenylmethane ... Examples of the dye structure include dyes derived from dyes selected from the group consisting of tetrafluoroethylene dyes, ...

[0028] Among these dye structures, azo dyes are the most popular from the viewpoint of color properties such as hue, color separation, and color uniformity. A dye structure derived from a dye selected from the group consisting of xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from the group consisting of xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0029] [Xanthene dyes] In this specification, the dye is preferably a xanthene dye. The xanthene dye is a dye that exhibits a red or purple color, and is preferably in the form of an oil-soluble dye, an acid dye, a direct dye, or a basic dye. The dye may also be in the form of a lake pigment obtained by making these dyes into a lake. Among these, xanthene oil-soluble dyes and xanthene acid dyes are preferred in terms of improving the hue of the color filter.

[0030] Examples of xanthene dyes include oil-soluble dyes such as CI Solvent Red and CI Solvent Violet, basic dyes such as CI Basic Red and CI Basic Violet, acid dyes such as CI Acid Red and CI Acid Violet, and direct dyes such as CI Direct Red and CI Direct Violet. Direct dyes have a sulfonic acid group (e.g., -SO3H, -SO3Na) in their structure, and in the present invention, direct dyes are classified as acid dyes.

[0031] Among these, salt-forming compounds of xanthene acid dyes and / or sulfonamide compounds of xanthene acid dyes are particularly preferred because they have excellent hue and durability, and it is even more preferred to use compounds obtained by salting xanthene acid dyes with quaternary ammonium salt compounds, which are counter components that act as counter ions, and sulfonamide compounds obtained by sulfonamidating xanthene acid dyes.

[0032] Among xanthene dyes, rhodamine dyes are preferred because they are excellent in color development and durability.

[0033] The form of the xanthene acid dye used in the present invention will be specifically described below. [Xanthene acid dyes] As xanthene acid dyes, it is preferable to use CI Acid Red 51 (Erythrosine (Food Red No. 3)), CI Acid Red 52 (Acid Rhodamine), CI Acid Red 87 (Eosine G (Food Red No. 103)), CI Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), CI Acid Red 289, CI Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, and CI Acid Violet 9. Among these, in terms of heat resistance and light resistance, it is more preferable to use xanthene acid dyes such as CI Acid Red 87, CI Acid Red 92, and CI Acid Red 388, or rhodamine acid dyes such as CI Acid Red 52 (Acid Rhodamine), CI Acid Red 289, Acid Rhodamine G, and CI Acid Violet 9. Among these, it is most preferable to use rhodamine acid dyes such as CI Acid Red 52 and CI Acid Red 289, which are excellent in color development, heat resistance, and light resistance.

[0034] In addition, these acid dyes are preferably salt-forming compounds of acid dyes and nitrogen-containing compounds. Examples of the nitrogen-containing compounds include quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, and resins having functional groups thereof. By synthesizing xanthene acid dyes into salt-forming compounds, a coating film having high heat resistance, light resistance, and solvent resistance can be formed. The salt-forming compound of the acid dye may be a product with a compound having an onium salt group. For example, when the compound having an onium salt group is a resin having a cationic group in the side chain, the brightness and durability of the coating are further improved.

[0035] (Resin with cationic groups on the side chains) The resin having a cationic group in a side chain of the present invention is an acrylic resin containing a monomer unit represented by the following general formula (3), and preferably further has a thermal crosslinkable functional group. The cationic group of the resin having a cationic group in a side chain is preferably an onium base. Examples of the onium base include ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts. Among these, in terms of further improving storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are more preferred, and ammonium salts are more preferred. The cationic group in general formula (3) forms a salt with the anionic group of the xanthene acid dye, thereby obtaining a salt-forming compound.

[0036] General formula (3) [ka]

[0037] [In general formula (3), R 1 R represents a hydrogen atom or a substituted or unsubstituted alkyl group. 2 ~R 4 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group; R 2 ~R 4 Two of these may be bonded together to form a ring. Q is an alkylene group, an arylene group, -CONH-R 5 -,-COO-R 5 - represents R 5 represents an alkylene group. Y- represents an inorganic or organic anion.

[0038] Examples of the thermally crosslinkable functional group include a hydroxyl group, a carboxyl group, a carboxylic anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, an epoxy group, a mercapto group, an isocyanate group, an allyl group, and a (meth)acrylic group. Among these, from the viewpoint of storage stability in the application of a coloring composition for color filters and reactivity with other materials, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, or a (meth)acrylic group is preferred, and it is particularly preferred that the compound has a hydroxyl group. From the viewpoint of alkaline developability, it is preferable that the resin has a carboxyl group. The amount of ammonium base present in the resin having a cationic group in the side chain is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, more preferably 20 to 130 mgKOH / g. When the ammonium salt value is within the range of 10 to 200 mgKOH / g, the coloring power is improved, and the adhesion and solvent resistance of the coating are improved. The content of the monomer unit represented by general formula (3) is preferably 4 to 74% by weight, more preferably 8 to 48% by weight, based on 100% by weight of all monomer units constituting the resin having a cationic group in the side chain.

[0039] (Salt formation) The salt-forming compound of an acid dye and a nitrogen-containing compound can be synthesized by a known method, for example, as described in JP-A-11-72969. As an example of the synthesis method, the xanthene acid dye is dissolved in water, then a quaternary ammonium salt compound is added, and the dye is subjected to a salt-forming treatment while stirring. For example, a salt-forming compound is obtained in which the ammonium group (NH4+) of the quaternary ammonium salt compound is bonded to the sulfonic acid group (-SO3H) or sodium sulfonate group (-SO3Na) in the xanthene acid dye. In addition, methanol or ethanol can be used instead of water during the synthesis.

[0040] The synthesis of a salt-forming compound of an acid dye and a resin having a cationic group in the side chain can be performed, for example, by mixing an aqueous solution in which a xanthene acid dye and a resin having a cationic group in the side chain are dissolved by stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized and ionic bonded, and the ionic bonded portion becomes water-insoluble and precipitates. Conversely, the salt formed by the counter anion of the resin and the counter cation of the acid dye is water-soluble and can be removed by washing with water, etc.

[0041] The colorant (A) can be used alone or in combination of two or more kinds.

[0042] <Resin-type dispersant (B)> The resin-type dispersant (B) contains an aromatic carboxylic acid polyester portion (X1) and a vinyl polymer portion (X2). The vinyl polymer portion (X2) is a polymer having one or more thermally crosslinkable group-containing monomer units selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, a blocked isocyanate group, and a (meth)acryloyl group, and a monomer unit having an alicyclic hydrocarbon group.

[0043] (Resin-type dispersant (B)) In the resin-type dispersant (B), the aromatic carboxylic acid polyester moiety (X1) acts as a colorant adsorption site, and the vinyl polymer moiety (X2) acts as a relaxation site, so that it is possible to suppress aggregation of the colorant (A) and obtain a dispersion with excellent dispersion stability. Aromatic carboxylic acids have a skeleton more suitable for adsorbing colorants than aliphatic carboxylic acids, and the heat resistance of the coating is improved. Furthermore, when the vinyl polymer portion (X2) in this resin-type dispersant (B) has a thermally crosslinkable group, the solvent resistance of the coating film after curing is further improved when it is used in combination with an epoxy compound.

[0044] The content of the resin type dispersant (B) is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 60 parts by mass, and further preferably 5 to 40 parts by mass, based on 100 parts by mass of the colorant (A). When the resin type dispersant (B) is contained in an appropriate amount, the dispersibility and solvent resistance are further improved.

[0045] The weight average molecular weight of the resin type dispersant (B) is preferably from 2,000 to 100,000. If the resin type dispersant (B) has an appropriate weight average molecular weight, the dispersion stability is further improved. The acid value of the resin-type dispersant (B) is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and even more preferably 5 to 100 mgKOH / g. If the resin-type dispersant (B) has a suitable acid value, the dispersibility is further improved, and the viscosity of the photosensitive coloring composition can be easily adjusted.

[0046] [Method of synthesizing resin-type dispersant (B)] The resin-type dispersant (B) can be synthesized, for example, by the following synthesis methods (1) and (2). do.

[0047] [Synthesis method (1)] In the presence of a compound having two hydroxyl groups and one thiol group in the molecule (hereinafter referred to as a thiol compound), a monomer containing at least one selected from the group consisting of a monomer having an oxetane group, a monomer having a t-butyl group, and a monomer having a blocked isocyanate group, and a monomer having an aliphatic hydrocarbon group are radically polymerized to synthesize a vinyl polymer having two hydroxyl groups at one end region. Next, the hydroxyl group in the vinyl polymer is reacted with an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides to obtain a dispersant having an oxetane group, a t-butyl group, or a blocked isocyanate group as a crosslinkable group, and an aliphatic hydrocarbon group.

[0048] [Synthesis method (2)] In the presence of a compound produced by reacting a hydroxyl group in a hydroxyl group-containing compound (e.g., a thiol compound, but excluding vinyl polymers containing a hydroxyl group at one end) constituting the polyester portion (X1) with an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic anhydrides and tricarboxylic anhydrides containing an aromatic ring, a monomer containing at least one selected from the group consisting of a hydroxyl group-containing monomer, a monomer having an oxetane group, a monomer having a t-butyl group, and a monomer having a blocked isocyanate group, and a monomer having an aliphatic hydrocarbon group, are radically polymerized. This results in a dispersant having a hydroxyl group, an oxetane group, a t-butyl group, or a blocked isocyanate group as a crosslinkable group, and an aliphatic hydrocarbon group. The radical polymerization is preferably solution polymerization or bulk polymerization.

[0049] When radical polymerization is carried out using a hydroxyl group-containing monomer, it is preferable to synthesize the resin-type dispersant (B) by utilizing the synthesis method (2).

[0050] The content of the hydroxyl group-containing monomer, the monomer having an oxetane group, the monomer having a t-butyl group, the blocked isocyanate group, and the monomer having an aliphatic hydrocarbon group is preferably 5 to 90 mass %, more preferably 20 to 60 mass %, based on the total monomers. If it is 5 mass % or more, the solvent resistance is further improved. Also, if it is 90 mass % or less, the dispersion stability is further improved. Improve.

[0051] [Synthesis of polyester moiety (X1)] The synthesis of the aromatic carboxylic acid polyester moiety (X1) is a process of reacting an acid anhydride group in an acid anhydride containing at least one aromatic ring selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A catalyst can be used in the reaction. An organic solvent can be used in the reaction.

[0052] (catalyst) The catalyst may be, for example, triethylamine, triethylenediamine, N,N-dimethylbenzene tertiary amine compounds such as diamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene; mono-n-butyltin(IV) oxide, and the like.

[0053] (Organic solvent) Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, acetonitrile, hexane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0054] (Reaction temperature) The reaction temperature for the synthesis of the polyester moiety (X1) is preferably 50°C to 180°C, more preferably 80°C to 140°C. The reaction can be completed within an appropriate time by performing the reaction at an appropriate temperature. It is preferable to perform the reaction until the acid anhydride does not absorb any more in infrared absorption at the end of the reaction, but if the reaction is stopped when 97% or more of the acid anhydride is half-esterified as determined by acid value measurement, then the proper performance can be obtained.

[0055] Each component of the resin-type dispersant (B) will be described.

[0056] [Acid anhydride constituting the polyester moiety (X1) in the resin-type dispersant (B)] The acid anhydride constituting the aromatic carboxylic acid polyester moiety (X1) of the resin-type dispersant (B) preferably contains at least one selected from aromatic tetracarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides. The two anhydride groups of the tetracarboxylic dianhydride react with the hydroxyl groups of the above-mentioned hydroxyl group-containing compound, thereby enabling carboxyl groups, which serve as colorant-adsorbing groups, to be regularly arranged in the main chain of the resin-type dispersant (B), thereby improving dispersibility. Furthermore, when a tricarboxylic acid anhydride is used, it reacts with a hydroxyl group to form an ester bond, leaving a carboxyl group.

[0057] Furthermore, polycarboxylic acid anhydrides other than tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, such as dicarboxylic acid anhydrides and anhydrides of compounds having five or more carboxylic acids, can also be used in combination.

[0058] [Tetracarboxylic acid anhydride] Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride. Acid dianhydrides, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis (3,4-Dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid) Examples of the aromatic tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as 4,4'-diphenylmethane dianhydride (phenylphthalic acid), 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 succinic acid dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride. Among these, tetracarboxylic acid dianhydrides having two or more aromatic rings are more preferred in terms of excellent adsorption to colorants.

[0059] [Tricarboxylic acid anhydride] Examples of aromatic tricarboxylic acids include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride.

[0060] [Hydroxyl-containing compound constituting the polyester moiety (X1) in the resin-type dispersant (B)] Examples of the hydroxyl group-containing compound constituting the polyester moiety (X1) include compounds having two hydroxyl groups and one thiol group in the molecule, vinyl polymers having a hydroxyl group at one end, and other polyols. Among these, it is preferable to use at least one hydroxyl group-containing compound selected from the group consisting of compounds having two hydroxyl groups and one thiol group in the molecule and vinyl polymers having a hydroxyl group at one end.

[0061] [Compound with two hydroxyl groups and one thiol group in the molecule] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 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, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0062] [Vinyl polymer containing a hydroxyl group at one end] The details of the synthesis method of the resin-type dispersant (B) will be described later, but there are a method of synthesizing the polyester portion (X1) first and then the vinyl polymer portion (X2), and a method of synthesizing the vinyl polymer portion (X2) first and then the polyester portion (X1). When synthesizing the polyester portion (X1) first, a hydroxyl-containing compound containing at least the compound having two hydroxyl groups and one thiol group in the molecule described above is reacted with an acid anhydride. When synthesizing the vinyl polymer portion (X2) first, a monomer is polymerized in the presence of the compound having two hydroxyl groups and one thiol group in the molecule described above to obtain a vinyl polymer portion (X2) having a hydroxyl group derived from the compound having two hydroxyl groups and one thiol group in the molecule introduced at the terminal. Therefore, when synthesizing the next polyester portion (X1), it is the terminal hydroxyl group of the vinyl polymer portion (X2) that is reacted with an acid anhydride. That is, when the vinyl polymer portion (X2) is synthesized first, the hydroxyl-containing compound constituting the polyester portion (X1) also contains a vinyl polymer portion (X2) (vinyl polymer containing a hydroxyl group at one end) having a hydroxyl group derived from a compound having two hydroxyl groups and one thiol group in the molecule introduced at the end. This vinyl polymer portion (X2) functions as a relaxation portion, so that good dispersion stability is easily obtained even when a fine pigment or a dye is used. In addition, since it has a thermal crosslinking group, it is easy to obtain solvent resistance by reaction with an epoxy compound. It is preferable to use a polymerization initiator for the synthesis of the vinyl polymer portion (X2).

[0063] [Other polyols] Examples of other polyols include compounds belonging to the following groups (1) to (7). By using these polyol compounds in combination, it becomes easier to adjust the physical properties of the resin-type dispersant (B).

[0064] (1) Polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or hexanetriol;

[0065] (2) various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, and polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;

[0066] (3) Modified polyether polyols obtained by ring-opening polymerization of the above-mentioned various polyhydric alcohols with (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether;

[0067] (4) Polyester polyols obtained by co-condensation of one or more of the above-mentioned various polyhydric alcohols with polycarboxylic acids, in which the polycarboxylic acids are particularly represented by succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2,5,7-naphthalenetricarboxylic acid;

[0068] (5) Lactone-based polyester polyols obtained by polycondensation reaction of one or more of the above-mentioned various polyhydric alcohols with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone, or lactone-modified polyester polyols obtained by polycondensation reaction of the above-mentioned various polyhydric alcohols with polycarboxylic acids and various lactones;

[0069] (6) Epoxy-modified polyester polyols obtained by using, in combination with one or more epoxy compounds, such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic and / or polybasic acids, during the synthesis of polyester polyol;

[0070] (7) Other polyols such as polyester polyamide polyols, polycarbonate polyols, polybutadiene polyols, polypentadiene polyols, castor oil, castor oil derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, hydroxyl group-containing acrylic copolymers, hydroxyl group-containing fluorine-containing compounds, and hydroxyl group-containing silicone resins.

[0071] The other polyols can be used alone or in combination of two or more kinds.

[0072] The weight average molecular weight of the other polyol is preferably from 40 to 10,000, more preferably from 100 to 2,000, and even more preferably from 100 to 1,000. A suitable weight average molecular weight further improves dispersion stability.

[0073] Regarding the number of hydroxyl groups in the other polyol, a diol is preferred in terms of adjusting the molecular weight of the resin-type dispersant (B) and adjusting the viscosity of the photosensitive coloring composition.

[0074] [Monomer constituting the vinyl polymer portion (X2) in the resin-type dispersant (B)] The vinyl polymer portion (X2) is a radical polymer of a monomer (b1) having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth)acryloyl group, and a monomer (b2) having an alicyclic hydrocarbon group. Alternatively, a (meth)acryloyl group can be introduced into the vinyl polymer segment (X2) by reacting a hydroxyl group in a hydroxyl group-containing polymer obtained by radical polymerization of a hydroxyl group-containing monomer with an isocyanate group and an isocyanate group in a (meth)acryloyl group-containing monomer.

[0075] (Hydroxyl-containing monomer) The hydroxyl group-containing monomer is, for example, a (meth)acrylate monomer having a hydroxyl group, such as hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates, such as ethyl-α-hydroxymethyl acrylate; Examples of (meth)acrylamide monomers having a hydroxyl group include N-(hydroxyalkyl)(meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(2-hydroxybutyl)(meth)acrylamide; Examples of vinyl ether monomers having a hydroxyl group include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, and 2-(or 3- or 4-)hydroxybutyl vinyl ether; Examples of allyl ether monomers having a hydroxyl group include hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether.

[0076] In addition, a monomer obtained by adding an alkylene oxide and / or a lactone to the above-mentioned hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl) (meth)acrylamide, hydroxyalkyl vinyl ether, or hydroxyalkyl allyl ether can also be used as a hydroxyl group-containing monomer in this specification. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide. When two or more alkylene oxides are used in combination, the bond form may be either random and / or block. Examples of the lactone include δ-valerolactone, ε-caprolactone, and ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms. The alkylene oxide and the lactone can be used in combination.

[0077] (Monomer having an oxetane group) Examples of monomers having an oxetane group include (vinyloxyalkyl) alkyloxetane, (meth)acryloyloxyalkyloxetane, and (meth)acryloyloxyalkyl] alkyloxetane. Among these, (3-ethyloxetane-3-yl) methyl methacrylate is preferred. Examples of commercially available products include ETERNACOLLOXMA ((3-ethyloxetane-3-yl) methyl methacrylate) (manufactured by Ube Industries).

[0078] (Monomers with t-butyl groups) Examples of the monomer having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

[0079] (Monomer having a blocked isocyanate group) Examples of monomers having a blocked isocyanate group include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, etc. Examples of commercially available products include KarenzMOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko K.K.), KarenzMOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko K.K.), etc.

[0080] ((Meth)acryloyl group-containing monomer) The (meth)acryloyl group-containing monomer is an ethylenically unsaturated monomer having an isocyanate group and a (meth)acryloyl group, and examples thereof include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0081] The content of the monomer having an oxetane group, the monomer having a t-butyl group, the blocked isocyanate group, and the monomer having a (meth)acryloyl group-containing monomer is preferably 5 to 90 mass % of the total monomers, more preferably 20 to 60 mass %. If it is 5 mass % or more, it is possible to obtain a photosensitive coloring composition having excellent resistance due to the effect of crosslinking, and if it is 90 mass % or less, the stability of the photosensitive coloring composition is further improved.

[0082] (Monomer (b2) Having an Alicyclic Hydrocarbon Group) Examples of monomers having an alicyclic hydrocarbon group include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexane dimethanol monoacrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate. Among these, those containing one or more of a cyclohexyl group and a tert-butylcyclohexyl group are preferred. The tert-butylcyclohexyl group is a group having a carbon atom to which three cyclohexyl groups are bonded.

[0083] The content of the monomer having an alicyclic hydrocarbon group is preferably 10 to 95% by mass, more preferably 10 to 60% by mass, based on the total monomers. If it is 10% by mass or more, a photosensitive coloring composition having excellent hardness can be obtained, and if it is 90% by mass or less, the solubility in a developer is further improved.

[0084] [Other monomers] The vinyl polymer portion (X2) in the resin-type dispersant (B) can be radically polymerized with monomers other than the monomer (b1) having a thermally crosslinkable functional group and the monomer (b2) having an alicyclic hydrocarbon group. Other monomers include (meth)acrylic acid esters such as (meth)acrylic acid alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, and lauryl (meth)acrylate; Monomers having a carboxyl group, such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate; Methoxypolypropyleneglycol (meth)acrylate, ethoxypolyethyleneglycol Examples of the alkoxypolyalkylene glycol (meth)acrylates include alkoxypolyalkylene glycol (meth)acrylates such as chol (meth)acrylate.

[0085] Examples of the nitrogen-containing group monomer include N-substituted (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; and nitriles such as (meth)acrylonitrile.

[0086] Examples of the vinyl monomer include 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; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0087] The weight average molecular weight of the vinyl polymer portion (X2) is preferably 1000 to 20000, more preferably 2000 to 15000, further preferably 2000 to 12000, and particularly preferably 3000 to 8000. The vinyl polymer portion (X2) functions as a relaxation portion. A suitable weight average molecular weight improves dispersion stability and makes it easy to adjust the viscosity of the photosensitive coloring composition.

[0088] The content of the monomer is preferably 3 to 100 parts by mass, more preferably 8 to 25 parts by mass, and even more preferably 10 to 20 parts by mass, relative to 1 part by mass of the thiol compound. When an appropriate amount of the monomer is used, a relaxation site with appropriate steric repulsion is easily formed, and thus the pigment dispersibility is further improved.

[0089] The polymerization initiator may be an azo compound or an organic peroxide. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0090] The polymerization initiators can be used alone or in combination of two or more.

[0091] The content of the polymerization initiator is usually about 0.001 to 5 parts by mass based on 100 parts by mass of the monomer used in the synthesis of the polymer portion (X2).

[0092] In the case of solution polymerization, it is preferable to use the organic solvents already exemplified.

[0093] As the resin-type dispersant (B), dispersants described in JP-A-2009-155406 can also be used.

[0094] Other Dispersants The resin-type dispersant (B) can be used in combination with other dispersants other than those mentioned above. Other dispersants include, for example, polycarboxylates such as polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, and modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0095] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, and 2155 manufactured by BYK Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000 manufactured by Lubrizol Japan , 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Chiba Japan Co., Ltd. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 440 2, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0096] The resin-type dispersant (B) can be used alone or in combination of two or more kinds.

[0097] <Binder resin (C)> The binder resin (C) is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating film having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The binder resin (C) is preferably a thermoplastic resin or a photosensitive resin. In addition, the binder resin (C) is preferably alkali-soluble. This allows the coating film formed from the photosensitive coloring composition to be patterned by a photolithography method. The photosensitive resin not having alkali solubility and the alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

[0098] The binder resin (C) can be used alone or in combination of two or more kinds.

[0099] The content of the binder resin (C) 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 (A). When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0100] Examples of the alkali-soluble resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0101] <Thermoplastic resin> Thermoplastic resins are not alkali-soluble. Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylenes (HDPE, LDPE), polybutadiene, and polyimide resins.

[0102] <Alkali-soluble photosensitive resin> The alkali-soluble photosensitive resin has photosensitivity because it has a polymerizable unsaturated group. Any known resin can be used as the alkali-soluble photosensitive resin as long as it is alkali-soluble and photosensitive, but resins synthesized by the following methods (i) and (ii) are preferred. When the alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking by light irradiation, increasing the crosslink density, improving the chemical resistance of the coating.

[0103] [Method (i)] Method (i) is, for example, a method in which a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0104] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0105] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0106] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0107] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; 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; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0108] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-phenylenediamine benzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0109] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

[0110] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0111] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0112] Monomers that can be used other than the above-mentioned monomers include, in addition to the other monomers exemplified in the above method (i), phosphate ester group-containing monomers, etc.

[0113] The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0114] The above-mentioned raw materials for the binder resin (C) can be used alone or in combination of two or more kinds. The binder resin (C) can be used alone or in combination of two or more kinds.

[0115] The content of the binder resin (C) is preferably 20 to 1000 parts by mass based on 100 parts by mass of the colorant (A).

[0116] The weight average molecular weight (Mw) of the binder resin (C) is preferably 10,000 to 100,000, and more preferably 10,000 to 80,000. The number average molecular weight (Mn) is preferably 5,000 to 50,000. The value of Mw / Mn is preferably 10 or less.

[0117] The acid value of the alkali-soluble resin is preferably 20 to 300 mgKOH / g. A suitable acid value allows a high level of balance to be achieved among alkali solubility, adhesion, and residue suppression.

[0118] <Epoxy compound (F)> The coloring composition can contain an epoxy compound (F). This reacts with the carboxyl group of the resin-type dispersant (B) or the like after the coloring composition is thermally cured, improving the chemical resistance and solvent resistance of the coating. In terms of molecular weight, the epoxy compound can be a low molecular weight compound or a high molecular weight compound (resin). The epoxy compound (F) is preferably a multifunctional epoxy resin.

[0119] The weight average molecular weight of the epoxy compound (F) is preferably from 200 to 100,000, more preferably from 300 to 10,000, and further preferably from 500 to 5,000.

[0120] The content of the epoxy compound (F) is preferably 5 to 20% by weight based on 100% by weight of the nonvolatile content of the coloring composition. When the content is appropriate, the effect of improving the solvent resistance is high, and when the content is 20% by weight or less, the heat resistance is further improved and yellowing after heat treatment is easily suppressed, so that a coating film with high brightness can be formed.

[0121] The content of the epoxy compound (F) is preferably 25 to 150 parts by mass, more preferably 35 to 120 parts by mass, based on 100 parts by mass of the resin-type dispersant (B). When an appropriate amount is contained, a coloring composition excellent in not only brightness and contrast ratio but also heat resistance and chemical resistance can be obtained.

[0122] The epoxy resin that can be used in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, and the like. Preferred are novolac type epoxy resins and alicyclic epoxy resins, and particularly preferred are alicyclic epoxy resins. The number of functional groups is preferably two or more, and more preferably three or more, in view of excellent thermal crosslinking properties.

[0123] <Solvent (D)> The use of the solvent (D) makes it easy to adjust the viscosity of the colored composition, and therefore makes it easy to form a coating film with a smooth surface. The solvent may be appropriately selected depending on the purpose of use, and may be contained in an appropriate amount.

[0124] Examples of the solvent include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0125] Among these, in terms of coatability and drying property, solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferred. 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, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

[0126] The solvents can be used alone or in combination of two or more.

[0127] The content of the solvent is preferably from 100 to 10,000 parts by mass, and more preferably from 500 to 5,000 parts by mass, relative to 100 parts by mass of the colorant (A).

[0128] <Polymerizable compound (G)> The coloring composition of the present invention may contain a polymerizable compound (G). The polymerizable compound (G) is a monomer or oligomer containing a polymerizable unsaturated group.

[0129] Examples of the polymerizable compound (G) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl ether di(meth)acrylate. Examples of the acrylic acid esters and methacrylic acid esters include, but are not limited to, acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, 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-vinyl formamide, and acrylonitrile.

[0130] The photopolymerizable compounds can be used alone or in combination of two or more kinds.

[0131] The content of the polymerizable compound (G) is preferably 5 to 500 parts by mass, and more preferably 10 to 400 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, photocurability and developability are improved.

[0132] <Photopolymerization initiator (H)> The colored composition of the present invention may contain a photopolymerization initiator (H), which allows the colored composition to be subjected to a development treatment by a photolithography method to form a pattern.

[0133] The photopolymerization initiator (H) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-phenylpropanone. -Acetophenone compounds such as dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butyl)benzoate. benzophenone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(tri triazine-based compounds such as 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds;

[0134] The photopolymerization initiator (H) can be used alone or in combination of two or more kinds.

[0135] The content of the photopolymerization initiator (H) is preferably 1 to 500 parts by mass, and more preferably 5 to 400 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, photocurability and developability are improved.

[0136] <Sensitizer> The coloring composition may contain a sensitizer together with the photopolymerization initiator (H). Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. 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 are more preferred.

[0137] The sensitizers can be used alone or in combination of two or more kinds.

[0138] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the polymerization initiator (H). When an appropriate amount is contained, the photocurability and developability are further improved.

[0139] <Multifunctional thiol> The coloring composition can contain a polyfunctional thiol. The polyfunctional thiol is a compound having two or more thiol (SH) groups. When the polyfunctional thiol is used in combination with a photopolymerization initiator (H), a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, improving the sensitivity of the photosensitive coloring composition.

[0140] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane ... pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like.

[0141] The polyfunctional thiols can be used alone or in combination of two or more kinds.

[0142] The content of the polyfunctional thiol is preferably 0.05 to 10 parts by mass, more preferably 1.0 to 8.0 parts by mass, relative to 100 parts by mass of the colorant. By using 0.05 parts by mass or more of the polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such improvement in development resistance cannot be obtained.

[0143] <Leveling agent> The coloring composition may contain a leveling agent, which improves the wettability of the coating to the transparent substrate and the drying property of the coating when the coating is formed. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0144] The leveling agents can be used alone or in combination of two or more.

[0145] The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the colored composition. When an appropriate amount is contained, the balance between the coatability, pattern adhesion, and transmittance of the colored composition is further improved.

[0146] <UV absorbers, polymerization inhibitors> The coloring composition may contain an ultraviolet absorber and a polymerization inhibitor, which improves the shape and resolution of the pattern when the pattern is formed using a photolithography method.

[0147] Examples of the ultraviolet absorber include hydroxyphenyl triazines such as 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; benzotriazoles such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole; benzophenones such as dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone; salicylates such as phenyl salicylate and p-tert-butylphenyl salicylate; cyanoacrylates such as ethyl-2-cyano-3,3'-diphenylacrylate; and hindered amines such as 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetoneamine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, and poly[[6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino].

[0148] Examples of the polymerization inhibitor include hydroquinone derivatives and phenol compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; copper and manganese salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate; nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine, and the ammonium salts or aluminum salts thereof.

[0149] The ultraviolet absorbents and polymerization inhibitors may each be used alone or in combination of two or more kinds.

[0150] The content of each of the ultraviolet absorber and the polymerization inhibitor is preferably 0.01 to 20 parts by mass, and more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the colorant (A). When they are contained in appropriate amounts, a pattern with good resolution can be formed.

[0151] <Antioxidants (E)> The coloring composition can contain an antioxidant. The antioxidant can prevent the coating film formed from the coloring composition from yellowing due to oxidation caused by the thermal process during heat curing or ITO annealing, and can suppress a decrease in the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the content of the photopolymerizable compound is relatively reduced, so that the coating film is likely to yellow when the amount of the photopolymerization initiator (H) is increased or an epoxy compound (F) is added. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a decrease in the transmittance of the coating film can be suppressed.

[0152] The antioxidant is a compound having a radical scavenging function or a peroxide decomposition function. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. The antioxidant is preferably a compound that does not contain a halogen atom.

[0153] Examples of the hindered phenol antioxidant include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0154] Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate), poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6- tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine.

[0155] Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-ditert-butyl-6-methylphenyl)phosphite.

[0156] Examples of the sulfide antioxidant include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0157] The antioxidants can be used alone or in combination of two or more.

[0158] The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the colored composition, which leads to further improvements in transmittance, spectral characteristics, and sensitivity.

[0159] <Other additives> The coloring composition may contain other additives (e.g., silane coupling agents, amine compounds, etc.). When the coloring composition contains a silane coupling agent, the adhesion between the coating and the substrate is improved, and it becomes easier to form a narrow pattern by photolithography. In addition, when the coloring composition contains an amine compound, the oxygen dissolved in the composition can be reduced.

[0160] Examples of the silane coupling agent include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Examples of the epoxy silanes include triethoxysilane; aminosilanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

[0161] The amount of the silane coupling agent is preferably from 0.01 to 10 parts by mass, and more preferably from 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant (A) in the colored composition.

[0162] Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

[0163] <Method of producing colored composition> The coloring composition is prepared, for example, by dispersing the coloring agent (A), the resin-type dispersing agent (B), the solvent (D), and the like to prepare a coloring agent (A) dispersion. The coloring agent (A) dispersion and the binder resin (C) are then mixed to prepare a coloring composition. Other materials such as the antioxidant (E), the epoxy compound (F), the photopolymerizable compound, and the photopolymerizable initiator are blended as necessary. When the coloring agent (A) is an organic pigment, it is preferable to use it after previously performing a micronization treatment as described above. The timing of blending each material is arbitrary.

[0164] The dispersion treatment is preferably carried out using a dispersion device such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

[0165] (Dispersion aid) In the dispersion treatment, it is preferable to use a dispersion aid. Examples of the dispersion aid include a dye derivative and a surfactant. The dispersion aid has a large effect of preventing reagglomeration of the colorant (A) after dispersion, so that the viscosity stability of the colored composition is improved and the brightness of the coating is also improved.

[0166] Examples of the dye derivative include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. Examples of the dye derivative include compounds described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916, and Japanese Patent No. 4,585,781.

[0167] The dye derivatives can be used alone or in combination of two or more kinds.

[0168] The content of the dye derivative is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 3 to 30 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, dispersibility is further improved.

[0169] Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and amphoteric surfactants such as alkyl betaines such as alkyl dimethylaminoacetate betaines and alkyl imidazolines.

[0170] The dye derivatives can be used alone or in combination of two or more kinds.

[0171] The content of the surfactant is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, dispersibility is further improved.

[0172] <Removal of large particles> After blending, the coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust, for example, by means of centrifugation, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0173] <Color filters> The color filter of the present specification includes a substrate and a filter segment formed from a 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 (A) used. The color filter may further have a magenta filter segment, a cyan filter segment, and a yellow filter segment as the color filter segment. Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0174] <Manufacturing method for color filters> The color filter can be produced by a printing method or a photolithography method, with the photolithography method being preferred.

[0175] It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed.

[0176] In the photolithography method, for example, a coloring composition containing a colorant of 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 coating. The obtained coating (hereinafter referred to as the first coating) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the coating is developed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain a desired pattern. This process can be similarly carried out using a photosensitive coloring composition containing a colorant of another color tone to produce a color filter having filter segments of each color. In addition, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, and thus 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.

[0177] Examples of the coating device include a spray coater, a spin coater, a slit coater, and a roll coater. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0178] The developer may be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine. A defoaming agent or a surfactant may be added to the developer.

[0179] The dry film thickness of the filter segment and black matrix is ​​preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a reduced pressure dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

[0180] The transparent substrate may be a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or resin plate for driving the liquid crystal after the panel is formed.

[0181] In this specification, after forming the color filter segment, the color filter is laminated to the opposing substrate using a sealant, liquid crystal is injected through the injection port provided in the seal part, the injection port is sealed, and a polarizing film or a retardation film is laminated to the outside of the substrate as necessary, to produce a liquid crystal display device. Examples of such liquid crystal display devices include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0182] The display device of the present specification is preferably provided with a color filter. The display device can be used for applications such as liquid crystal display devices, organic EL display devices, solid-state imaging devices, quantum dot display devices, and electronic paper. EXAMPLES

[0183] The present invention will be described below based on examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". In addition, "PGMAc" means propylene glycol monomethyl ether acetate.

[0184] The weight average molecular weight (Mw) of the resin, the acid value of the resin-type dispersant (B), the ammonium salt value of the resin 1 having a cationic group on the side chain, and the average primary particle size of the pigment are measured as follows.

[0185] (Weight average molecular weight of resin (Mw)) The weight average molecular weight (Mw) of the resin is the polystyrene-equivalent weight average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as the developing solvent.

[0186] (Acid value of resin-type dispersant (B)) The resin acid value is the acid value (mgKOH / g) measured according to the potentiometric titration method of JIS K 0070 and converted into the non-volatile content.

[0187] (Ammonium salt value of resin having cationic groups on the side chain) The ammonium salt value of a resin having a cationic group on the side chain is determined by titration with 0.1N silver nitrate solution using 5% potassium chromate solution as an indicator, and then converted into the potassium hydroxide equivalent, and indicates the ammonium salt value of the non-volatile portion.

[0188] (Average primary particle size of pigment) The average primary particle size of the pigment was measured by a method that uses a transmission electron microscope (TEM) to directly measure the size of the primary particles from electron microscope photographs. Specifically, the minor axis diameter and major axis diameter of each pigment primary particle were measured, and the average was taken as the particle size of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to the cube of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

[0189] Next, the methods for producing the acrylic resin solution, dispersant, dye derivative, resin having a cationic group on the side chain, finely divided pigment, dye, pigment dispersion, dye solution, and green resist material used in the examples and comparative examples will be described.

[0190] <Method of manufacturing acrylic resin solution> (Preparation of Binder Resin (C)) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of PGMAc was charged into the reaction vessel, which was then heated to 80°C. The atmosphere in the reaction vessel was replaced with nitrogen, and a mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was dripped over 2 hours from the drip tube. After dripping was completed, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin with a weight average molecular weight (Mw) of 26,000. 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 resin solution previously synthesized so that the non-volatile content was 20% by weight to prepare the binder resin (C).

[0191] <Method for producing resin-type dispersant (B)> (Synthesis of Dispersant (BC-1)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.5 parts of pyromellitic anhydride, 4 parts of 3-mercapto-1,2-propanediol, 0.01 parts of monobutyltin oxide as a catalyst, and 59.6 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 7 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, 35 parts of methyl methacrylate, 25 parts of butyl methacrylate, 5 parts of methacrylic acid, 25 parts of cyclohexyl methacrylate (CHMA), and 51.1 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 80°C, 0.12 parts of AIBN were added, and the reaction was continued for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. PGMAc was added to adjust the nonvolatile content to 50%, and a dispersant (BC-1) with an acid value of 59.7 and a weight average molecular weight of 12,500 was obtained.

[0192] (Synthesis of Dispersants (B-1 to B-9)) Dispersants (B-1 to 9) were synthesized in the same manner as for dispersant BC-1, except that the raw materials were changed as shown in Table 1.

[0193] [Table 1]

[0194] The abbreviations in Table 1 are as follows: PMA: Pyromellitic anhydride TMA: Trimellitic anhydride MMA: Methyl methacrylate n-BA: Butyl methacrylate t-BA: tert-butyl acrylate MAA: Methacrylic acid OXMA: (3-ethyloxetan-3-yl)methyl methacrylate MOI-BM: 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate CHMA: Cyclohexyl methacrylate tBCHA: 4-tert-butylcyclohexyl acrylate AIBN: 2,2'-azobis(isobutyronitrile) PGMAc: Propylene glycol monomethyl ether acetate DBU: 1,8-diazabicyclo-s-[5.4.0]-7-undecene

[0195] <Method of producing dye derivative> (Dye derivative 1) 50 parts of copper phthalocyanine, a dye component, was chlorosulfonated and then reacted with 14 parts of N,N-dimethylaminopropylamine, an amine component, to obtain dye derivative 1 having a basic group. Dye derivative 1 [ka] CuPc represents a copper phthalocyanine residue.

[0196] (Dye derivative 2) Dye derivative 2 having a basic group was obtained by the same method as in the production of dye derivative 1, except that diphenyldiketopyrrolopyrrole was used as the dye component and N-aminopropylmorpholine was used as the amine component. Dye Derivative 2 [ka]

[0197] (Dye derivatives 3 and 4) As described in JP 2007-156395 A and JP 2007-79094 A The dye derivatives 3 and 4 were synthesized. Dye derivative 3 [ka] Dye derivative 4 [ka]

[0198] <Method for producing resin having cationic groups in its side chains> (Resin 1 having cationic groups on the side chains) In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone were charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropwise addition, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, resin 1 having cationic groups in the side chains with ammonium groups and a non-volatile content of 47% by weight was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

[0199] <Method of manufacturing fine pigments> (Micronized pigment (PB-1)) 100 parts of CI Pigment Blue 15:6 (PB15:6) ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70°C. This mixture was poured into 3000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove the salt and solvent, and then dried at 80°C overnight to obtain 98 parts of finely divided pigment (PB-1). The average primary particle size was 28.3 nm.

[0200] (Micronized pigment (PR-1)) 200 parts of CI Pigment Red 254 (BASF Japan "B-CF"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80°C. Next, this kneaded mixture was added to 8000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain 190 parts of finely divided pigment (PR-1). The average primary particle size was 27.6 nm.

[0201] (Micronized pigment (PR-2)) 100 parts of CI Pigment Red 177 (PR177) ("Cromophthal Red A2B" manufactured by BASF Japan Co., Ltd.), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded for 6 hours at 60°C, and subjected to salt milling treatment. The kneaded product obtained was poured into 3 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day and night to obtain 98 parts of a finely divided pigment (PR-2). The average primary particle size was 33 nm.

[0202] (Micronized pigment (PR-3)) 200 parts of CI Pigment Red 269 ("Toner Magenta F8B" manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80°C. Next, this kneaded material was added to 8000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain 190 parts of a finely divided pigment (PR-3). The average primary particle diameter was 39.6 nm.

[0203] (Micronized pigment (PG-1)) 120 parts of phthalocyanine green pigment CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyochem Co., Ltd.), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. This mixture was added to 5000 parts of warm water, heated to about 70°C and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove salt and solvent, and then dried at 80°C for a day and night to obtain 117 parts of finely divided pigment (PG-1). The average primary particle size was 32.6 nm.

[0204] (Micronized pigment (PG-2)) 100 parts of phthalocyanine green pigment CI Pigment Green 58 (DIC "FASTGENGREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded at 70°C for 6 hours. This kneaded mixture was added to 3000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for 24 hours to obtain 97 parts of fine pigment (PG-2). The average primary particle size was 28.2 nm.

[0205] (Micronized pigment (PY-1)) 100 parts of CI Pigment Yellow 138 (PY138) (BASF Japan "Paliotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80°C. This mixture was added to 2000 parts of warm water, heated to 80°C and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80°C overnight to obtain 95 parts of finely divided pigment (PY-1). The average primary particle size was 40.2 nm.

[0206] <Dye manufacturing method> (dye 1) Dye 1, which is a salt-forming compound consisting of CI Acid Red 52 and Resin 1 having a cationic group on the side chain, was produced according to the following procedure. 30 parts of resin 1 having a cationic group in the side chain was added to 2000 parts of water in terms of non-volatile content, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and the solution was gradually dropped into the resin solution. After the dropwise addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, the mixture was filtered by suction, washed with water, and the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture, and dye (1), which is a salt-forming compound of 32 parts of CI Acid Red 52 and resin 1 having a cationic group in the side chain, was obtained. At this time, the content of the active color component derived from CI Acid Red 52 in dye (1) was 25% by weight.

[0207] (dye 2) Dye 2, which is a salt-forming compound consisting of CI Acid Red 289 and Resin 1 having a cationic group on the side chain, was produced according to the following procedure. 30 parts of resin 1 having a cationic group in the side chain was added to 2000 parts of water in terms of non-volatile content, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 289 in 90 parts of water, and the solution was gradually added to the resin solution. After the addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, the mixture was filtered by suction, washed with water, and the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture, and dye 2, which is a salt-forming compound of 32 parts of CI Acid Red 289 and resin 1 having a cationic group in the side chain, was obtained. At this time, the content of the active color component derived from CI Acid Red 289 in dye 2 was 27% by weight.

[0208] (dye 3) Based on the description in Japanese Patent No. 6589305, dye 3 was prepared as a salt-forming compound consisting of CI Acid Red 52 and distearyl dimethyl ammonium chloride (Cortamine D86P) (molecular weight of the cationic portion is 550).

[0209] <Method of manufacturing pigment dispersion> [Comparative Example 1] (Pigment Dispersion (DP-1)) The mixture below was stirred and mixed until homogenous, then dispersed in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 5 hours, and then filtered through a 5.0 μm filter to obtain a blue pigment dispersion (DP-1). The pigment dispersion was adjusted with PGMAc to have a non-volatile content of 20% by weight. The masses shown below are calculated based on non-volatile content. Fine pigment (PB-1): 11.0 parts Pigment Blue 15:6 Dye derivative 1: 1.0 part Specific resin type dispersant: 8.0 parts The resin-type pigment dispersant is dispersant A used in Example 1 of JP2013-195854A.

[0210] [Examples 1 to 15, Comparative Examples 2 to 5] (Pigment Dispersion (DP-2~20)) Except for changing the composition as shown in Table 2, pigment dispersions (DP-2 to 20) were obtained in the same manner as pigment dispersion (DP-1).

[0211] [Table 2]

[0212] <Method of manufacturing dye solution> (Dye solution (DA-1)) The following mixture was stirred and mixed until homogeneous, and then filtered through a 5.0 μm filter to prepare a dye solution (DA-1). Dye 1: 16.0 parts PGMAc: 84.0 copies

[0213] Except for changing the dye to the composition shown in Table 3, dye solutions (DA-2, 3) were obtained in the same manner as the above dye solution (DA-1).

[0214] [Table 3]

[0215] <Method of manufacturing green resist material> (Alkaline developing type green resist material (E1)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") for 5 hours using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to obtain a green pigment dispersion (DPE-1). The pigment dispersion was adjusted with PGMAc so that the nonvolatile content was 20% by weight. The masses shown below are calculated based on non-volatile content. Fine pigment (PG-2): 6.0 parts Pigment Green 58 EFKA4300 (BASF Japan): 4.0 parts EFKA4300 is a basic block copolymer dispersant.

[0216] Next, the following raw materials were mixed and stirred so that the non-volatile content was the following blend amount (parts by mass), PGMAc was added to adjust the non-volatile content to 16% by weight, and the mixture was filtered through a 1.0 μm filter to obtain an alkaline development type green resist material (E1). Green pigment dispersion (DPE-1): 66.7 parts Acrylic resin 1: 13.3 parts Polymerizable compound (G) (Aronix M-402, manufactured by Toagosei Co., Ltd.): 10.0 parts Photopolymerization initiator (H) (Irgacure 907, manufactured by BASF Japan): 10.0 parts

[0217] [Example 16] Alkaline developing type blue resist material (RB-1) Using the pigment dispersion (DP-10) and dye solution (DA-1), the following raw materials were mixed and stirred, PGMAc was added to adjust the non-volatile content to 16% by weight, and the mixture was filtered through a 1.0 μm filter to obtain an alkaline development type blue resist material (RB-1). The masses shown below are calculated based on non-volatile content. Pigment dispersion (DP-10): 33.3 parts Dye 1: 5.0 parts Acrylic resin 1: 21.7 parts Polymerizable compound (G) (Aronix M-402, manufactured by Toagosei Co., Ltd.): 30.0 parts Photopolymerization initiator (H) (Omnirad 369, manufactured by IGM Resins BV): 10.0 parts

[0218] [Examples 17 to 29, Comparative Examples 6 and 7] (Alkaline developing type blue resist material (RB-2~19)) The components were mixed to obtain the compositions and blending amounts (non-volatile parts by mass) shown in Table 4, and the non-volatile content was adjusted to 16% by weight using PGMAc. Alkaline-developable blue resist materials (RB-2 to 19) were obtained in the same manner as for the alkaline-developable blue resist material (RB-1).

[0219] [Table 4]

[0220] The abbreviations in Table 4 are as follows: Antioxidant (E): Irganox 1010 manufactured by BASF Japan Epoxy compound (F): Daicel EHPE3150 Silane coupling agent: X-12-1048 manufactured by Shin-Etsu Chemical Co., Ltd. Photopolymerization initiator NCI-730: ADEKA ADEKA CRUISE NCI-730 Photopolymerization initiator PBG-3057: TR-PBG-3057 manufactured by Changzhou Strong Electronic New Materials Co., Ltd.

[0221] [Example 33] Alkaline developing type red resist material (RR-1) Pigment dispersion (DP-16) and (DP-1 8), the following raw materials were mixed and stirred, PGMAc was added to adjust the non-volatile content to 16% by weight, and the mixture was filtered through a 1.0 μm filter to obtain an alkaline development type red resist material (RR-1). The masses shown below are calculated based on non-volatile content. Pigment dispersion (DP-16): 35.0 parts Pigment dispersion (DP-18): 30.0 parts Acrylic resin 1: 21.7 parts Polymerizable compound (G) (Aronix M-402, manufactured by Toagosei Co., Ltd.): 20.0 parts Photopolymerization initiator (H) (Irgacure OXE-04 manufactured by BASF Japan): 1.0 part

[0222] [Examples 34 to 40, Comparative Examples 8 to 9] (Alkaline developing type red resist material (RR-2~10)) The components were mixed in the compositions and amounts (mass calculated as non-volatile content) shown in Table 5, and the non-volatile content was adjusted to 16 wt % using PGMAc. In the same manner as for the alkaline development type red resist material (RR-1), alkaline development type red resist materials (RR-2 to RR-10) were obtained.

[0223] [Table 5]

[0224] <Evaluation of pigment dispersion> The resulting pigment dispersions (DP-1 to DP-20) were evaluated by the following methods. The results are shown in Table 6.

[0225] (viscosity stability) The initial viscosity of the obtained pigment dispersion at 25° C. was measured using an E-type viscometer (ELD-type viscometer manufactured by Toki Sangyo Co., Ltd.) Separately, the pigment dispersion was left to stand in a sealed glass container at 40° C. for 24 hours, and then the viscosity was measured in the same manner as above to obtain the viscosity over time. ○: Viscosity change rate was less than ±10%, and no sediment was formed (good). △: Viscosity change rate was between ±10% and 20%, and no sediment was produced. (Practical) ×: The viscosity change rate was ±20% or more, or sediment was generated even when the viscosity change rate was less than ±20% (not practical).

[0226] (Pencil hardness) The obtained colored composition was applied to a glass substrate (Corning Glass Eagle 2000) having a length of 100 mm x width of 100 mm and a thickness of 0.7 mm using a spin coater so that the finished film thickness after heating at 100 ° C for 60 minutes was 2.0 μm. Next, after holding for 2 minutes on a hot plate heated to 80 ° C, the substrate was exposed to ultraviolet light at an illuminance of 20 mW / cm2 and an exposure amount of 100 mJ / cm2 using an ultra-high pressure mercury lamp, heated at 100 ° C for 60 minutes, and cooled to obtain a coated substrate. The coated substrate was measured for the pencil surface hardness of the protective film by the pencil scratch test of 8.4.1 of JIS K5400-1990, and evaluated according to the following criteria. ○: Pencil surface hardness is 2H or more (good) △: Pencil surface hardness is H (practical) ×: Pencil surface hardness is F or less (not practical)

[0227] <Evaluation of photosensitive coloring composition for color filters> The obtained photosensitive coloring compositions (RB1 to RB19, RR1 to 10) were evaluated by the following methods. The results are shown in Table 7.

[0228] (viscosity stability) The initial viscosity of the obtained photosensitive coloring composition was measured at 25°C using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) Separately, the photosensitive coloring composition was left to stand in a sealed glass container at 40°C for 24 hours, and then the viscosity was measured in the same manner as above, and the viscosity was determined as the viscosity over time. ◯: The viscosity change rate was less than ±10%, and no sediment was formed. Δ: The viscosity change rate was ±10% or more and less than ±20%, and no sediment was formed. ×: The viscosity change rate was ±20% or more, or sediment was generated even when the viscosity change rate was less than ±20%.

[0229] (Developer solubility) The obtained photosensitive coloring composition was applied to a glass substrate of 100 mm length x 100 mm width, 0.7 mm thickness using a spin coater so that the thickness after drying was 2.5 μm, and dried under reduced pressure to obtain a substrate. Next, the obtained substrate was held on a hot plate heated to 90 ° C for 2 minutes, and then exposed to ultraviolet light using an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm2 and an exposure dose of 50 mJ / cm2 through a photomask having a predetermined stripe pattern. The filter segments were spray-developed using an alkaline developer consisting of 0.15% by mass of sodium carbonate, 0.05% by mass of sodium bicarbonate, 0.1% by mass of anionic surfactant ("Pelex NBL" manufactured by Kao Corporation) and 99.7% by mass of water, and the developer waste after 50 seconds was checked to see whether any solids remained. The evaluation was done on the following three levels: ○: There is no solid in the liquid, and the solution is not suspended. (Good) △: No solids, but the entire liquid is suspended. (Practical) ×: Solids precipitated and aggregated (not practical).

[0230] [Table 6]

[0231] [Table 7]

[0232] <Manufacturing of color filters> A red resist material (RR-1) was applied to a glass substrate of 100 mm length x 100 mm width and 0.7 mm thickness by a die coater so that the dry film thickness was about 2.5 μm, and the solvent was removed in an oven at 70 ° C for 20 minutes and dried. Then, a stripe pattern exposure was performed with ultraviolet light using an exposure device. The exposure dose was 100 mJ / cm2. Furthermore, the unexposed portion was removed by spray development using a developer consisting of an aqueous sodium carbonate solution, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red filter segment with a line width of about 50 μm. Next, a green filter segment was formed next to the red filter segment using the resist material E1, and then a blue filter segment was formed using the blue resist material (RB-1) by the same procedure, and a color filter having three color filter segments on the same glass substrate was obtained.

[0233] By using the color filter resist material of the present invention, a color filter having good solvent resistance over a wide chromaticity range, high brightness and a high contrast ratio could be obtained.

Claims

1. The composition includes a colorant (A), a resin-type dispersant (B), a binder resin (C), and a solvent (D), The resin type dispersant (B) has a main chain containing an aromatic carboxylic acid polyester moiety (X1) and a side chain containing a vinyl polymer moiety (X2), the aromatic carboxylic acid polyester moiety (X1) has a carboxyl group, the vinyl polymer moiety (X2) is a polymer having one or more types of thermally crosslinkable group-containing monomer units selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, a blocked isocyanate group, and a (meth)acryloyl group, and a monomer unit having an alicyclic hydrocarbon group, and the total monomer units of the vinyl polymer moiety (X2) contain 5 to 90 mass% of thermally crosslinkable group-containing monomer units and 10 to 95 mass% of monomer units having an alicyclic hydrocarbon group.

2. 2. The coloring composition for color filters according to claim 1, wherein the monomer unit having an alicyclic hydrocarbon group is a monomer unit containing at least one of a cyclohexyl group and a tert-butylcyclohexyl group.

3. 3. The coloring composition for color filters according to claim 1, wherein the weight average molecular weight of the vinyl polymer portion is from 2,000 to 100,000.

4. The coloring composition for color filters according to any one of claims 1 to 3, further comprising an antioxidant (E).

5. The coloring composition for color filters according to any one of claims 1 to 4, further comprising an epoxy compound (F).

6. A photosensitive coloring composition for color filters, comprising the coloring composition for color filters according to any one of claims 1 to 5, a polymerizable compound (G), and a photopolymerization initiator (H).

7. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition for color filters according to claim 6.

8. A display device comprising the color filter according to claim 7.

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