Red coloring composition, film, color filter, solid-state image sensor, and image display device

Abstract

The present invention aims to provide a red coloring composition suitable for forming a film that is highly bright, highly colored, low reflectivity, and has excellent light resistance. Furthermore, it aims to provide a film, a color filter, a solid-state image sensor, and an image display device formed from the red coloring composition. [Solution] The above problem is solved by a red coloring composition comprising a coloring agent (A) and a resin (B), wherein the coloring agent (A) comprises CI violet 19, a red pigment, and two or more pigment derivatives with different structures.

Description

[Technical Field]

[0001] The present invention relates to a red coloring composition, a film, a color filter, a solid-state image sensor, and an image display device. [Background technology]

[0002] In color filters used in solid-state image sensors and image display devices, CI pigment red 254 and CI pigment red 177 are widely used as colorants in coloring compositions for forming red pixels. In recent years, there has been a demand for even higher brightness and coloring power, and in response to these demands, the use of CI pigment violet 19 has been proposed (Patent Documents 1 and 2).

[0003] Furthermore, solid-state image sensors and image display devices are increasingly being used in a variety of environments, leading to higher demands for various types of resistance. In particular, there is a strong demand for high light resistance, especially considering outdoor use, and ongoing research is underway to address this issue.

[0004] While liquid crystal displays (LCDs) have been the dominant technology for image display devices, organic EL (Electro-Luminescence) displays are gaining popularity due to their low power consumption, lack of backlight requirements, and ability to be made thinner and more flexible. Furthermore, to achieve even thinner displays, development is underway to eliminate the polarizing plates used to prevent light reflection in organic EL displays and replace them by adding an anti-reflective function to color filters. Such color filters are desirable to have low reflectivity, but Patent Documents 1 and 2 do not mention reflectivity. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-147977 [Patent Document 2] Japanese Patent Publication No. 2021-103295 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a red coloring composition suitable for forming a film that is highly bright, highly colored, low reflectivity, and has excellent lightfastness. Furthermore, it aims to provide a film, a color filter, a solid-state image sensor, and an image display device formed from the red coloring composition. [Means for solving the problem]

[0007] As a result of diligent research, the inventors of the present invention discovered that a red coloring composition suitable for forming a film with high brightness, high coloring power, and low reflectivity can be obtained by including CI violet 19, a red pigment, and two or more pigment derivatives with different structures, leading to the present invention.

[0008] In other words, the present invention is a red coloring composition comprising a coloring agent (A) and a resin (B). The present invention relates to a red coloring composition in which the coloring agent (A) comprises CI violet 19, a red pigment, and two or more pigment derivatives having different structures.

[0009] Furthermore, the present invention relates to the red coloring composition wherein the red pigment comprises at least one selected from the group consisting of C.I. Pigment Red 179, C.I. Pigment Red 264, C.I. Pigment Red 269, and C.I. Pigment Red 122.

[0010] Furthermore, the present invention relates to the red coloring composition in which CI violet 19 is β-type unsubstituted quinacridone.

[0011] The present invention also relates to the red coloring composition, wherein the pigment derivative is a compound having at least one selected from the group consisting of an acidic group, a basic group, a group having a salt structure, and a phthalimide group in addition to an organic pigment structure or a triazine structure.

[0012] Furthermore, the present invention relates to the red coloring composition in which at least two of the two or more pigment derivatives having different structures are compounds containing different organic pigment structures.

[0013] Furthermore, the present invention relates to the red coloring composition in which at least two of the two or more pigment derivatives having different structures are compound compounds containing a diketopyrrolopyrrole pigment structure, a quinophthalone pigment structure, an azo pigment structure, an anthraquinone pigment structure, or a triazine structure.

[0014] Furthermore, the present invention relates to the red coloring composition wherein resin (B) comprises resin (B1) having aromatic carboxyl groups.

[0015] Furthermore, the present invention relates to the red coloring composition wherein the coloring agent (A) further comprises an isoindoline pigment.

[0016] The present invention further relates to the red coloring composition comprising a photopolymerizable compound (C) and / or a photopolymerizable initiator (D).

[0017] Furthermore, the present invention relates to a film formed from the aforementioned red coloring composition.

[0018] Furthermore, the present invention relates to a color filter having the aforementioned film.

[0019] Furthermore, the present invention relates to a solid-state image sensor having the aforementioned color filter.

[0020] Furthermore, the present invention relates to an image display device having the aforementioned color filter. [Effects of the Invention]

[0021] According to the present invention, a red coloring composition suitable for forming a film with high brightness, high coloring power, low reflectivity, and excellent light resistance can be provided. Furthermore, a film, a color filter, a solid-state image sensor, and an image display device formed from the red coloring composition can be provided. [Brief explanation of the drawing]

[0022] [Figure 1] This is the X-ray diffraction pattern of CuKα in CI Violet 19. [Modes for carrying out the invention]

[0023] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments and can be modified and implemented within the scope of solving the problem.

[0024] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," "(meth)acryloyloxy," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," "acryloyloxy and / or methacryloyloxy," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; published by The Society of Dyers and Colourists).

[0025] <Coloring agent (A)> The red coloring composition of the present invention comprises, as a coloring agent (A), CI violet 19, a red pigment, and two or more pigment derivatives having different structures.

[0026] (CI Violet 19) In the present invention, CI violet 19 is preferably β-type unsubstituted quinacridone from the viewpoint of brightness, coloring power, and reflectance. Unsubstituted quinacridone mainly has three types of crystal structures: α, β, and γ. β and γ types are stable crystal forms (crystal transformation between them is difficult), while α type is a metastable crystal form. Figure 1 shows the CuKα X-ray diffraction patterns of β-type and γ-type unsubstituted quinacridone. It is preferable to include CI violet 19 having the β-type diffraction peak shown in Figure 1.

[0027] In the red coloring composition of the present invention, CI violet 19 is preferably present in an amount of 5 to 40% by mass, and more preferably in an amount of 10 to 30% by mass, of the coloring agent (A).

[0028] (Red pigment) Examples of red pigments include 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, 6 3:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 2 Red pigments such as 63, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, or 296, pigments described in Japanese Patent Publication No. 2014-134712, and pigments described in Japanese Patent Publication No. 6368844 can be used. In particular, from the viewpoint of brightness and coloring power, it is preferable to include at least one selected from the group consisting of CI. Pigment Red 179, C.I. Pigment Red 264, C.I. Pigment Red 269, and C.I. Pigment Red 122.

[0029] In the red coloring composition of the present invention, the red pigment is preferably 50 to 80% by mass, and more preferably 60 to 75% by mass, of the coloring agent (A).

[0030] (Pigment derivatives) The red colored composition of the present invention contains two or more pigment derivatives with different structures. By including pigment derivatives with different structures, the pigment derivatives in the composition are less likely to interact with each other, such as agglomerating, and when adsorbed onto the pigment, the adsorption state differs due to the structural differences. As a result, the particles formed by the pigment and the adsorbed pigment derivatives are also less likely to interact with each other, such as agglomerating, and the particle size of the various particles in the composition becomes finer, which is presumed to result in a low reflectivity. Examples of pigment derivatives include compounds having an acidic group, a basic group, a neutral group, etc., in addition to the pigment structure or triazine structure. The pigment structure or triazine structure and the acidic group, basic group, neutral group, etc., may be directly bonded or bonded via a linking group.

[0031] Examples of pigment structures include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, benzimidazolon pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, and naphtholazo.

[0032] Examples of acidic groups include sulfo groups, carboxyl groups, and phosphate groups. Examples of basic groups include sulfonamide groups and tertiary amino groups. Examples of neutral groups include salts of the above-mentioned acidic groups, salts of basic groups, phenyl groups, and phthalimide groups.

[0033] In the present invention, it is preferable that the pigment derivative is a compound having an organic pigment structure or a triazine structure, and at least one selected from the group consisting of an acidic group, a basic group, a group having a salt structure, and a phthalimide group.

[0034] Furthermore, it is preferable that at least two of the two or more different structural pigment derivatives are compounds containing different organic pigment structures. It is presumed that having different organic pigment structures reduces the interaction between the pigment derivatives themselves, and between the pigment and the particles formed by the adsorbed pigment derivatives, resulting in lower reflectivity.

[0035] Preferably, at least two of the two or more pigment derivatives with different structures are compounds that include a diketopyrrolopyrrole pigment structure, a quinophthalone pigment structure, an azo pigment structure, an anthraquinone pigment structure, or a triazine structure as an organic pigment structure. This structure readily adsorbs to CI violet 19 or red pigments, and can be used to create a red colored composition with low reflectivity and excellent lightfastness.

[0036] As for pigment derivatives with two or more different structures, the following combinations of (1) to (3) are preferred, with (3) being the most preferred. (1) Pigment derivatives containing a quinophthalone pigment structure + Pigment derivatives containing organic pigment structures other than the quinophthalone pigment structure (2) Pigment derivatives containing an azo pigment structure + Pigment derivatives containing an organic pigment structure other than an azo pigment structure (3) Pigment derivatives containing a quinophthalone pigment structure + pigment derivatives containing an azo pigment structure + pigment derivatives containing organic pigment structures other than quinophthalone and azo pigment structures

[0037] Specific examples of pigment derivatives are shown below, but the invention is not limited to these.

[0038] [Diketopyrrolopyrrole pigment derivatives] [ka] General formula (101) General formula (102)

[0039] [Phthalocyanine-based pigment derivatives] [ka] General formula (103)

[0040] [Anthraquinone-based pigment derivatives] [ka] General formula (104) General formula (105) JPEG0007896242000004.jpg41170 General formula (106) General formula (107)

[0041] [Quinacridone-based pigment derivatives] [ka] General formula (108)

[0042] [Dioxazine-based pigment derivatives] [ka] General formula (109) JPEG0007896242000007.jpg47170 General formula (110)

[0043] [Thiazine indigo pigment derivatives] [ka] General formula (111)

[0044] [Triaidine-based pigment derivatives] [ka] General formula (112)

[0045] [Benzoisoindole-based pigment derivatives] [ka] General formula (113)

[0046] [Quinophthalone-based pigment derivatives] [ka] General formula (114) General formula (115) JPEG0007896242000012.jpg46170 General formula (116) General formula (117) JPEG0007896242000013.jpg46170 General formula (118) General formula (119) JPEG0007896242000014.jpg45170 General formula (120) General formula (121) JPEG0007896242000015.jpg48170 General formula (122) General formula (123) JPEG0007896242000016.jpg51170 General formula (124) General formula (125) JPEG0007896242000017.jpg50170 General formula (126) General formula (127) General formula (128)

[0047] [Naphthol-based pigment derivatives] [ka] General formula (129)

[0048] [Azo pigment derivatives] [ka] General formula (130) JPEG0007896242000020.jpg33170 General formula (131) JPEG0007896242000021.jpg39170 General formula (132) JPEG0007896242000022.jpg41170 General formula (133)

[0049] In general formulas (101) to (112), (114) to (128), (130) to (133), R 101 ~R 117 , R 129 , R 130 , R 141 ~R 145Each is independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a phthalimidoalkyl group which may have a substituent, an acyl group which may have a substituent, an amino group, a sulfo group, a carboxyl group, a phosphate group, a halogen group, a group represented by general formulas (150) to (155), (158), or (159). m and n each independently represent a positive integer. However, when a molecule has a plurality of substituents, one or more of them are substituents other than a hydrogen atom. Also, when there is only one substituent in a molecule, it is a substituent other than a hydrogen atom.

[0050] In general formula (I13), R 118 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, -SO2R 177 , or -NR 178 R 179 . However, R 177 is a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom, and R 178 and R 179 each independently represent a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, or a heterocyclic ring which may further contain additional nitrogen, oxygen or sulfur atoms formed integrally by R 178 and R 179 . R 119 represents a hydrogen atom, an alkyl group which may have a substituent, or an acyl group which may have a substituent. R 120 , R 121 , R 123 to R 128 each independently represent a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, a halogen atom, a cyano group, an alkoxy group which may have a substituent, or NR 180 R 181 . However, R 180 and R 181 are each independently a hydrogen atom, an alkyl group which may have a substituent, or a heterocyclic ring which may further contain additional nitrogen, oxygen or sulfur atoms formed integrally by R 180 and R 181 . R 122 This represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted acyl group, or a group represented by general formulas (150) to (155).

[0051] In general formula (129), R 131 ~R 140 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, or a group represented by general formula (150), (153), or (159). 131 ~R 140 The adjacent groups may be bonded by -NHCONH- groups to form a benzimidazolon ring. 131 ~R 140 At least one of these is a group represented by general formula (150), (153), or (159).

[0052] [ka] General formula (150) JPEG0007896242000024.jpg29170 General formula (151) JPEG0007896242000025.jpg46170 General formula (152) JPEG0007896242000026.jpg46170 General formula (153) JPEG0007896242000027.jpg16170 General formula (154) JPEG0007896242000028.jpg55170 General formula (155)

[0053] In general formulas (150) to (155), X1 represents a direct bond, -SO2-, -CO-, -CH2-, -CH2NHCOCH2-, -CONHC6H4CO-, or -CONHC6H4-. Y1 is directly coupled, -NR 170 SO2-, -SO2NR 170 -, -CONR 170 -, -NR 170 CO- or -CH2NR 170 COCH2NR 170 - represents Y2 represents a direct bond, an optionally substituted arylene group, or an optionally substituted heteroaromatic ring, and these groups are -NR 170 They may be linked to each other by divalent linking groups selected from -, -O-, -SO2-, or CO-. Y3 is directly bonded, -NR 170 - or -O- represents. 'o' represents an integer between 0 and 20. M1 represents hydrogen, copper, zinc, manganese, nickel, cobalt, and iron atoms. M2 represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom, or aluminum atom. i represents the valence of M2. R 150 and R 151 Each of these can independently be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 150 and R 151 Together, they represent a heterocycle that may have substituents, further containing nitrogen, oxygen, or sulfur atoms. R 152 ~R 156 , R 159 ~R 162 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a polyoxyalkylene group. R 157 and R 158 These are, independently, groups represented by the following general formulas (156) or (157), -O-(CH2) o -R 171 , -OR 172 , -NR 173 R 174 , represents -Cl, -F or Y3-Y2-Y1-Q, R 157 and R 158 Either one of them is a group represented by the following general formula (156) or (157), -O-(CH2) o -R 171 , -OR 172 , or NR 173 R 174 That is the case. R 170 This represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. R 171 R represents a heterocyclic residue which may have substituents. 172 ~R 174 Each of the following independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group, and Q represents an organic dye residue.

[0054] [ka] General formula (156)

[0055] In the general formula (156), Z1 is -NR 170 - represents -CONH- or -O-, and Z2 represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted arylene group, and these groups are -NR 170 They may be linked together by divalent linking groups selected from -, -O-, -SO2-, or CO-. However, R 170 This is R in general formulas (150) to (155). 170 It is synonymous with [the above]. R150 and R 151 Each of these can independently be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 150 and R 151 Together, they represent a heterocycle that may have substituents, further containing nitrogen, oxygen, or sulfur atoms.

[0056] [ka] General formula (157)

[0057] In general formula (157), Z3 is a single bond connecting the triazine ring and the nitrogen atom, -NR 175 -, -NR 175 -Z4-CO-, -NR 175 -Z4-CONR 176 -, -NR 175 -Z4-SO2-, -NR 175 -Z4-SO2NR 176 -, -O-Z4-CO-, -O-Z4-CONR 175 -, -O-Z4-SO2-, or O-Z4-SO2NR 175 - represents R 175 and R 176 Each of the following independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group, while Z4 represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted arylene group. R 152 ~R 156 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a polyoxyalkylene group.

[0058] [ka] General formula (158)

[0059]

Chem.

[0060] In general formula (159), X2 represents -SO₂-, -CO-, -NH-, -SO₂NH-, -NHSO₂-, -CONH- or -NHCO-, and R 163 ~R 167 are each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphate group or a group represented by general formulas (150) to (155).

[0061] The alkyl group which may have a substituent is preferably a linear alkyl group having 1 to 20 carbon atoms as the alkyl group, and the substituent which may be present is preferably hydrogen or a halogen group. The phthalimidoalkyl group which may have a substituent is preferably an alkyl group having 1 to 3 carbon atoms as the alkyl group, and the substituent which may be present is preferably hydrogen or a halogen group. The acyl group which may have a substituent is preferably an acyl group having 1 to 10 carbon atoms as the alkyl group, and the substituent which may be present is preferably hydrogen or a halogen group. The alkoxy group which may have a substituent is preferably a linear alkoxy group having 1 to 5 carbon atoms as the alkyl group, and the substituent which may be present is preferably hydrogen or a halogen group. The alkenyl group or alkenylene group which may have a substituent preferably has, as the substituent which may be present, hydrogen or a linear alkyl group having from 1 to 10 carbon atoms. The phenyl group which may have a substituent preferably has, as the substituent which may be present, hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group. The arylene group which may have a substituent preferably has, as the substituent which may be present, hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group. The heterocycles that may have substituents are preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and tetrahydrothiopyran, and the substituents that may be present are preferably hydrogen, halogen groups, linear alkyl groups having 1 to 10 carbon atoms, and alkoxy groups. The heteroaromatic ring, which may have substituents, is preferably pyrrole, pyridine, furan, or thiophene, and the substituents that may be present are preferably hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group.

[0062] In the red colored composition of the present invention, the pigment derivative is preferably in a total amount of 1 to 50% by mass, and more preferably 3 to 30% by mass, in the colorant (A).

[0063] (Other colorants) The red colored composition of the present invention may contain colorants other than CI violet 19, red pigment, and pigment derivatives. Other colorants can be arbitrarily selected from various conventionally known pigments other than red pigments and dyes. As pigments, organic or inorganic pigments can be used individually or in mixtures of two or more. Pigments with high color development and high heat resistance, particularly those with high heat decomposition resistance, are preferred, and organic pigments are usually used. Specific examples of other colorants usable in the red colored composition of the present invention are shown below by color index numbers.

[0064] [Pigments] As the orange pigment, you can use orange pigments such as CI Pigment Orange 34, 36, 38, 43, 51, 55, 59, 61, 62, 64, 71, or 73.

[0065] As for yellow pigments, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, Yellow pigments such as 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, 233, or 234 can be used. Yellow dyes such as quinoline-based, azo-based, disazo-based, and methine-based dyes can also be used. In particular, isoindoline pigments are preferred in terms of brightness and coloring power, and CI Pigment Yellow 139 and 185 are even more preferred.

[0066] As green pigments, for example, zinc phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, Japanese Patent Publication No. 2008-19383, Japanese Patent Publication No. 2007-320986, Japanese Patent Publication No. 2004-70342, International Publication No. 2015 / 118720, etc., and aluminum talocyanine pigments described in Japanese Patent No. 4893859, etc. can be used.

[0067] As blue pigments, for example, CI Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64, etc., can be used.

[0068] As purple pigments, for example, CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50 can be used.

[0069] In addition, inorganic pigments such as titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black can be used. Inorganic pigments are used in combination with organic pigments to ensure good coating properties, sensitivity, and developability while maintaining a balance between saturation and brightness.

[0070] [Pigment miniaturization] When using organic pigments as colorants, it is preferable to mix them with other raw materials after micronization. Examples of micronization methods include wet grinding, dry grinding, and dissolution extraction. Among these, salt milling by the kneader method, a type of wet grinding, is preferred. The average primary particle size of the organic pigment after micronization is preferably 10 to 60 nm, and more preferably 15 to 45 nm. Having the average primary particle size within this range results in lower reflectivity and improved brightness. The average primary particle size is the average value of approximately 200 particles arbitrarily selected from magnified images obtained using a TEM (transmission electron microscope). If the particles have a long axis and a short axis, the length of the long axis is used.

[0071] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using batch or continuous kneading machines such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, and planetary mixers, and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0072] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the standpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0073] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (miscible) in water but substantially does not dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling point solvent with a boiling point of 120°C or higher, as it does not easily volatilize due to the temperature rise during salt milling. Examples of water-soluble organic solvents 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, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0074] During the salt milling process, a resin may be added as needed. Examples of resins include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of pigment.

[0075] [dye] Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Also included are derivatives of dyes and lake pigments, which are dyes that have been transformed into lakes.

[0076] Furthermore, examples of dyes include acidic dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acidic dyes; salt-forming compounds of acidic dyes with quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds; and salt-forming compounds such as acidic dyes with resin components having amino groups. Salt-forming compounds of acidic dyes with compounds having an onium base are also preferred due to their excellent fastness. In addition, the compounds having an onium base are preferably resins having cationic groups in their side chains.

[0077] Basic dyes include salt-forming compounds made from organic acids, perchloric acid, or metal salts thereof. Among salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various substances and compatibility with pigments.

[0078] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), and quinoneimine dyes (oxazine dyes). Examples include dyes such as thiazine dyes, azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred from the viewpoint of color characteristics such as hue, color separation, and color unevenness, with xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes being more preferred. The specific structures of the dyes are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0079] <Resin (B)> The red coloring composition of the present invention contains resin (B). Resin (B) is incorporated for the purpose of dispersing particles such as pigments in the red coloring composition, or as a binder. Resins used primarily to disperse particles such as pigments are also called dispersants. However, these uses of the resin are just examples, and it can also be used for purposes other than those described above.

[0080] (Aromatic carboxyl group-containing resin (B1)) The red coloring composition of the present invention preferably contains a resin (B1) having aromatic carboxyl groups. The resin (B1) having aromatic carboxyl groups is particularly effective in preventing the re-aggregation of colorants, and therefore is preferably incorporated for applications that disperse particles such as pigments.

[0081] In the resin (B1) having aromatic carboxyl groups, the aromatic carboxyl groups may be included in the main chain of the repeating unit or in the side chain of the repeating unit. From the viewpoint of more significantly exhibiting the effects of the present invention, it is preferable that the aromatic carboxyl groups are included in the main chain of the repeating unit. In this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In an aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.

[0082] Resins having aromatic carboxyl groups in the main chain of repeating units can be manufactured by known methods such as those described in WO2008 / 007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, and JP 1996-143651.

[0083] A particularly preferred example of a resin having aromatic carboxyl groups in the repeating main chain is one having a main chain containing an aromatic carboxylic acid ester moiety having an ester bond obtained by esterifying an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety. The ratio of acid anhydride groups to 1 mole of hydroxyl groups is 0.9 to 1.5 moles, preferably 1.0 to 1.3 moles. Furthermore, the main chain containing the aromatic carboxylic acid ester moiety may have a structure having a encapsulation site derived from a monoalcohol, as described later. That is, the acid anhydride group remaining in the main chain is ring-opened with a monoalcohol, resulting in the presence of an alcohol ester group and a carboxyl group. By using such resins, the filterability of the red coloring composition is improved, foreign matter on the coating film formed by applying the red coloring composition is suppressed, and furthermore, when applying the red coloring composition, the resolubility of the solidified material derived from the red coloring composition formed in the coating apparatus in propylene glycol monomethyl ether acetate is improved. In this specification, side chains based on vinyl polymer moieties are formed by polymerization of ethylenically unsaturated monomers. The total monomer units constituting the vinyl polymer moiety refer to the substructures derived from each ethylenically unsaturated monomer after vinyl polymerization.

[0084] [Aromatic compounds having two or more acid anhydride groups] Aromatic compounds having two or more acid anhydride groups include, for example, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid 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'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid 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 Examples include dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride.

[0085] [Compounds having two or more hydroxyl groups] As described above, compounds having two or more hydroxyl groups are preferably compounds having a hydroxyl group and a thiol group in the molecule, and more preferably compounds having two hydroxyl groups and one thiol group in the molecule.

[0086] Examples of compounds having two hydroxyl groups and one thiol group in their 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, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0087] [Monoalcohol] Monoalcohols include, for example, methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, and other monoalcohols. Monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, etc. Examples include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. These can be used individually or in combination of two or more.

[0088] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The resin can have an ether group or a carbonyl group at the end of the main chain, improving the resolubility of the resin in propylene glycol monomethyl ether acetate. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0089] The main chain, which is an aromatic carboxylic acid ester moiety, may have encapsulation sites derived from monoalcohols, as well as encapsulation sites formed by reaction with water.

[0090] Regarding the synthesis of the encapsulation site, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 molar equivalents, and more preferably 1.5 to 20 molar equivalents, per equivalent of acid anhydride group remaining in the main chain. If the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability. If the amount is 30 molar equivalents or less, transesterification reactions due to ester bonding between the monoalcohol and the dispersant are less likely to occur, and a decrease in molecular weight is less likely to occur.

[0091] [Side chains, which are vinyl polymer parts] The side chains of a resin having aromatic carboxyl groups in the repeating main chain are obtained by polymerizing a vinyl polymerizable polymerizable compound in the presence of a compound having thiol groups. When a compound having two hydroxyl groups and one thiol group in its molecule is used as the compound having the thiol group, the main chain is formed after the side chain is formed. Furthermore, if the compound having the thiol group is the main chain after the esterification reaction (which has multiple thiol groups derived from a compound having two hydroxyl groups and one thiol group in its molecule), then side chains are formed after the main chain is formed.

[0092] (Other resins) The red coloring composition of the present invention may include resins other than the resin having aromatic carboxyl groups (B1) described above (hereinafter also referred to as "other resins"). The other resins are resins that do not contain aromatic carboxyl groups.

[0093] The weight-average molecular weight (Mw) of the other resins is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0094] Other resins include (meth)acrylic resin, (meth)acrylamide resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.

[0095] As other resins, it is also preferable to use resins having acidic groups other than aromatic carboxyl groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups. Resins having acidic groups can also be used as alkali-soluble resins or dispersants. The acid value of the resin having acidic groups is preferably 30 to 500 mg KOH / g. The lower limit is more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. The upper limit is more preferably 400 mg KOH / g or less, even more preferably 200 mg KOH / g or less, particularly preferably 150 mg KOH / g or less, and most preferably 120 mg KOH / g or less.

[0096] As other resins, it is also preferable to use resins having basic groups. The resin having basic groups is preferably a resin containing repeating units having basic groups in their side chains, more preferably a copolymer having repeating units having basic groups in their side chains and repeating units not having basic groups, and even more preferably a block copolymer having repeating units having basic groups in their side chains and repeating units not having basic groups. The resin having basic groups can also be used as a dispersant. The amine value of the resin having basic groups is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, and more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, and more preferably 100 mg KOH / g or less.

[0097] Preferred resins having basic groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers, and urethane polymers having functional groups in their side chains such as tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles.

[0098] Other resins may also preferably include resins used as dispersants. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. Similarly, a basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acidic groups.

[0099] As the acidic dispersant (acidic resin), a resin in which the amount of acidic groups is 70 mol% or more when the total amount of acidic groups and basic groups is set to 100 mol% is preferred. The acidic groups of the acidic dispersant (acidic resin) are preferably carboxyl groups. The acid value of the acidic dispersant (acidic resin) is preferably 5 to 200 mg KOH / g. The upper limit is preferably 150 mg KOH / g or less, more preferably 100 mg KOH / g or less, and even more preferably 80 mg KOH / g or less. The lower limit is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, and even more preferably 20 mg KOH / g or more.

[0100] As a basic dispersant (basic resin), a resin is preferred in which the amount of basic groups is 60 mol% or more when the total amount of acidic groups and basic groups is set to 100 mol%. The basic group of the basic dispersant is preferably an amino group. The amine value of the basic dispersant (basic resin) is preferably 5 to 100 mg KOH / g. The upper limit is preferably 80 mg KOH / g or less, more preferably 60 mg KOH / g or less, and even more preferably 45 mg KOH / g or less. The lower limit is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, and even more preferably 20 mg KOH / g or more.

[0101] The resin (B) content in the total solids of the red coloring composition of the present invention is preferably 0.1 to 70% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is preferably less than 50% by mass, more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0102] The content of the resin (B1) having aromatic carboxyl groups in the total solid content of the red coloring composition of the present invention is preferably 5 to 40% by mass. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

[0103] Furthermore, the content of the resin (B1) having aromatic carboxyl groups in the resin (B) contained in the red coloring composition is preferably 50 to 100% by mass. The upper limit is preferably 100% by mass or less, and more preferably 95% by mass or less. The lower limit is preferably 60% by mass or more, and more preferably 70% by mass or more.

[0104] <Photopolymerizable compound (C)> The red coloring composition of the present invention can be made into a photosensitive red coloring composition by including a photopolymerizable compound (C) and / or a photopolymerization initiator (D). The photopolymerizable compound (C) includes monomers or oligomers that harden upon exposure to ultraviolet light or the like to produce a transparent resin.

[0105] Photopolymerizable compound (C) is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate. Examples include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid esters of methylolated 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-vinylformamide, and acrylonitrile.

[0106] (Photopolymerizable compound containing an acid group) The photopolymerizable compound (C) may contain a photopolymerizable compound having an acidic group. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0107] Examples of photopolymerizable compounds having acidic groups include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups with dicarboxylic acids; and esters of polyhydric acids with monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups between monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and oligoesterified compounds containing free carboxyl groups between tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0108] (Photopolymerizable compound containing urethane bonds) The photopolymerizable compound (C) may contain a photopolymerizable compound having a urethane bond. Examples of the photopolymerizable compound include a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a (meth)acrylate having a hydroxyl group.

[0109] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0110] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0111] Photopolymerizable compound (C) can be used alone or in combination of two or more types.

[0112] The amount of photopolymerizable compound (C) is preferably 1 to 50% by mass, and more preferably 2 to 40 parts by mass, based on 100% by mass of the nonvolatile content of the red coloring composition. Adding an appropriate amount further improves curability and developability.

[0113] <Photopolymerizable initiator (D)> The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4 Acetophenone compounds such as -methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t Benzophenone compounds such as butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 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( Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0114] Photopolymerization initiator (D) can be used alone or in combination of two or more types.

[0115] In the present invention, it is preferable that the photopolymerization initiator (D) contains an oxime ester-based photopolymerization initiator.

[0116] (Oxime ester-based photopolymerization initiator) Oxime ester-based photopolymerization initiators undergo cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly reactive radicals, resulting in improved photocurability by allowing pattern formation with less exposure compared to using other photopolymerization initiators.

[0117] Examples of oxime ester-based photopolymerization initiators include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Compounds described in Technology (1995, pp. 202-232), compounds described in JP 2000-66385, compounds described in JP 2000-80068, compounds described in JP 2004-534797, compounds described in JP 2006-342166, compounds described in JP 2017-19766, compounds described in Japanese Patent No. 6065596, International Publication WO2015 / 152153 Examples include compounds described in the publication, compounds described in International Publication WO2017 / 051680, compounds described in Japanese Patent Publication No. 2007-210991, compounds described in Japanese Patent Publication No. 2009-179619, compounds described in Japanese Patent Publication No. 2010-037223, compounds described in Japanese Patent Publication No. 2010-215575, compounds described in Japanese Patent Publication No. 2011-020998, and compounds described in International Publication WO2021 / 175855.

[0118] Examples of oxime ester-based photopolymerization initiators include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF Japan), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Optomer N-1919, Adeka Arclus NCI-730, NCI-831, NCI-930 (manufactured by ADEKA Corporation). Furthermore, it is preferable to use oxime ester-based photopolymerization initiators that are colorless or highly transparent and do not easily discolor other components.

[0119] Specifically, when classified by the skeleton contained in the compound, examples include carbazole skeletons, fluorene skeletons, diphenyl skeletons, and dioxime systems having two oxime ester groups. Furthermore, as for specific structures contained in the compound, those having a hydroxyl group, a nitro group, a carbonyl group, a fluorinated carbon group, or a benzofuran are preferably used.

[0120] [Oxime ester-based photopolymerization initiator with a diphenyl skeleton] [ka]

[0121] [Oxime ester-based photopolymerization initiator with a carbazole skeleton] [ka]

[0122] [Oxime ester-based photopolymerization initiators with a fluorene skeleton] [ka]

[0123] [Oxime ester-based photopolymerizable initiator having two oxime ester groups] Examples of oxime ester-based photopolymerizable initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0124] Among these, oxime ester-based photopolymerization initiators having a carbazole structure, oxime ester-based photopolymerization initiators having a diphenyl skeleton, and oxime ester-based photopolymerization initiators having two oxime ester groups (including those having a carbazole skeleton) are preferred, with oxime ester-based photopolymerization initiators having a carbazole structure being the most preferred.

[0125] The content of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the red coloring composition. When an appropriate amount is added, the photocurability and developer resistance are improved and the surface condition is improved.

[0126] <Sensitizer> Furthermore, the red coloring composition of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0127] Among the sensitizers mentioned above, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitizing. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc., can be used.

[0128] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0129] Sensitizers can be used alone or in combination of two or more types.

[0130] The sensitizer content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (D). Including an appropriate amount further improves curability and developability.

[0131] <Thiol-based chain transfer agents> The red coloring composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerizable initiator (D), thiyl radicals are generated in the radical polymerization process after photoirradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive red coloring composition.

[0132] Furthermore, polyfunctional aliphatic thiols with two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups are preferred. More preferably, polyfunctional aliphatic thiols with four or more thiol groups are preferred. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0133] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. Examples include 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are used.

[0134] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0135] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass, based on 100% by mass of the nonvolatile content of the red coloring composition. When an appropriate amount is included, the light sensitivity and tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating.

[0136] <Polymerization inhibitor> The red coloring composition of the present invention may contain a polymerization inhibitor. This suppresses photosensitivity due to diffracted light on the mask during exposure in photolithography, making it easier to obtain patterns of the desired shape.

[0137] Examples of polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n- Examples include alkylresorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0138] The polymerization inhibitor content is preferably 0.01 to 0.4 parts by mass per 100% by mass of the non-volatile content of the red coloring composition. Within this range, the effect of the polymerization inhibitor is enhanced, resulting in improved linearity of the taper, reduced wrinkles in the coating film, and better pattern resolution.

[0139] <UV absorber> The red coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having ultraviolet absorption function, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0140] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator (D) and UV absorber. Including an appropriate amount further improves resolution after development.

[0141] Furthermore, the total content of the photopolymerization initiator (D) and the ultraviolet absorber is preferably 1 to 20% by mass of the nonvolatile content of the red coloring composition. Including an appropriate amount further improves the adhesion between the substrate and the film, resulting in good resolution.

[0142] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0143] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction between 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomeric and polymer-type compounds having a triazine structure can also be used.

[0144] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0145] Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomeric and polymeric compounds having a salicylic acid ester structure can also be used.

[0146] <Antioxidant> The red coloring composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator (D) and thermosetting compound contained in the red coloring composition from oxidizing and yellowing due to the heat process during thermosetting and ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the red coloring composition is high, the amount of coating film crosslinking component decreases, so countermeasures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator (D) are taken, which can lead to a phenomenon intensifying yellowing during the heat process. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0147] Examples of antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. In this specification, antioxidants that do not contain halogen atoms are preferred.

[0148] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

[0149] Antioxidants can be used alone or in combination of two or more types.

[0150] Furthermore, an antioxidant content of 0.5 to 5.0% by mass per 100% by mass of the solid content of the red coloring composition is more preferable because it results in good transmittance, spectral characteristics, and sensitivity.

[0151] <Leveling agent> In order to improve the coatability of the composition on a transparent substrate and the drying properties of the colored film, it is preferable to add a leveling agent to the red colored composition of the present invention. Various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used as leveling agents.

[0152] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0153] More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from BIC Chemie, and FZ-7002, 2110 from Toray Dow Corning Co., Ltd. Examples include 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0154] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0155] More specifically, examples include Surflon S-242, S-243, S-420, S-611, S-651, S-386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 from DIC Corporation, FC-4430, FC-4432 from Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Co., Ltd.

[0156] Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tripenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0157] More specifically, examples include Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amiet 102, 105, 105A, 302, 320, Aminon PK-02S, L-02, Homogenol L-95, ADEKA Corporation's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd.'s (meth)acrylic acid-based (co)polymers Polyflow No. 75, No. 90, No. 95, etc.

[0158] Examples of cationic surfactants include alkylamine salts and alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof.

[0159] More specifically, examples include Kao Corporation's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0160] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, and the like.

[0161] More specifically, examples include Futagent 100 and 150 manufactured by Neos Co., Ltd., ADEKA Hope YES-25, ADEKA Cole TS-230E, PS-440E, EC-8600 manufactured by ADEKA Corporation, and the like.

[0162] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocoamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0163] More specifically, examples include Amhitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation, and the like.

[0164] When the red coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the red coloring composition of the present invention. By being within this range, the balance of the coating property, pattern adhesion, and transmittance of the red coloring composition becomes good. The red coloring composition of the present invention may contain only one type of surfactant or may contain two or more types. When containing two or more types, it is preferable that the total amount thereof is within the above range.

[0165] <Storage stabilizer> The red colored composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass, based on the total amount of the coloring agent (A) (100% by mass).

[0166] <Adhesion enhancer> The red coloring composition of the present invention may contain adhesion-enhancing agents such as silane coupling agents to improve adhesion to the substrate. Improved adhesion due to the adhesion-enhancing agents results in better reproduction of fine lines and improved resolution.

[0167] Adhesion enhancers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of silane coupling agents include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent (A) in the red coloring composition. This range is preferable because it provides a greater effect and a good balance of adhesion, resolution, and sensitivity.

[0168] <Solvent> The red coloring composition of the present invention may contain a solvent to facilitate the formation of a colored film by coating it onto a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected considering not only the good coatability of the red coloring composition, but also the solubility of each component of the red coloring composition, as well as safety.

[0169] As the solvent, solvents commonly used in the field can be used, and their properties such as boiling point, SP value, evaporation rate, and viscosity are taken into consideration, and they are used individually or in mixtures as appropriate according to the application conditions (speed, drying conditions, etc.).

[0170] Examples of solvents that can be used 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 both -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 but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0171] Of the above solvents, it is preferable to include an organic solvent whose boiling point at 1 atm is 120°C or higher and 180°C or lower, from the viewpoint of applicability and drying properties. Among these, 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 preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0172] <Method for producing a red colored composition> The red colored composition of the present invention can be manufactured by finely dispersing a colorant (A) in a colorant carrier such as a resin (B) and / or a solvent, preferably together with a dispersion aid (pigment derivative or surfactant), using various dispersion methods 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 (colorant dispersion). At this time, two or more colorants may be dispersed simultaneously in the colorant carrier, or they may be dispersed separately in the colorant carrier and then mixed. If the colorant, such as a dye, has high solubility, specifically if it has high solubility in the solvent used, dissolves upon stirring, and no foreign matter is detected, then it is not necessary to manufacture it by fine dispersion as described above.

[0173] Furthermore, when used as a photosensitive red colored composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable red colored composition. The solvent-developable or alkali-developable red colored composition can be prepared by mixing the colorant dispersion with a photopolymerizable compound (C) and / or a photopolymerizable initiator (D), and optionally a solvent, other dispersing aids, and additives. The photopolymerizable initiator (D) may be added during the preparation of the red colored composition, or it may be added later to the prepared red colored composition.

[0174] <Removal of coarse particles> The red colored composition of the present invention is preferably subjected to centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration using a sintered filter or membrane filter to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, as well as any mixed dust. Thus, the red colored composition is preferably substantially free of particles of 0.5 μm or larger. More preferably, it is 0.3 μm or smaller.

[0175] <Moisture content in the red coloring composition> The red coloring composition of the present invention preferably contains 2% by mass or less of water.

[0176] When the red coloring composition has a water content within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0177] The water content in the red coloring composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less. With such a sufficiently small amount of water within this range, problems with dispersion stability and sensitivity are less likely to occur even after storage over time.

[0178] The method for controlling the water content is not particularly limited, and known methods can be used. For example, methods such as manufacturing the red coloring composition while blowing in a dried inert gas, or adding molecular sieves for dehydration after manufacturing can be mentioned. Among them, the method of manufacturing while blowing in a dried inert gas is preferred.

[0179] The water content can be measured by a known method such as the Karl Fischer method.

[0180] <Amount of toluene in the red coloring composition> The red coloring composition of the present invention may contain toluene. When it contains toluene, the toluene content is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0181] <Film> The film of the present invention is formed using the above-described red coloring composition. The film may be used in a state laminated on a substrate, or the film may be peeled off from the substrate. Also, the film may be either a flat film or a film having a pattern formed thereon, but a film having a pattern formed thereon is preferred.

[0182] (Method for manufacturing the film) The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured by a process of coating the red coloring composition of the present invention onto a substrate.

[0183] Examples of substrates include those made of materials such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. An image sensor such as a CCD or CMOS may also be formed on the substrate. Furthermore, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface.

[0184] A known coating method can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0185] The film thickness can be adjusted as appropriate depending on the purpose. A film thickness of 0.05 to 20.0 μm is preferred, and 0.3 to 10.0 μm is more preferred.

[0186] Next, a pattern is formed. Methods for forming the pattern include photolithography and dry etching. Note that when used as a flat film, the pattern formation step is unnecessary; the coating is then dried as needed.

[0187] The following describes in detail how to form the patterns.

[0188] [When forming a pattern using photolithography] When forming a pattern using photolithography, the layer formed by coating the substrate with the red coloring composition of the present invention is dried as needed (pre-bake), then exposed in a patterned manner through a mask (exposure step), the unexposed areas are removed by alkaline development (development step), and then the pattern is heat-treated as needed (post-bake step).

[0189] [Exposure process] The exposure process involves exposing a layer formed by coating to a specific pattern via a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulsed exposure).

[0190] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline aqueous solution, leaving only the hardened parts and obtaining a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0191] [Post-baking process] After development, heat treatment (post-baking) can be performed as needed. Post-baking improves the durability of the film. The temperature is preferably between 80 and 300°C. The duration is preferably between 2 minutes and 1 hour. When a material with low heat resistance is used as the substrate, or when an organic electroluminescent element is used as the light source, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0192] [When forming a pattern using the dry etching method] When forming a pattern by dry etching, for example, a layer formed by coating a substrate with the red coloring composition of the present invention is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then dry etching is performed on the cured film using an etching gas, with the patterned photoresist layer as a mask. For pattern formation by dry etching, the method described in Japanese Patent Application Publication No. 2013-064993 can be referenced.

[0193] <Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention has a film formed using the red coloring composition of the present invention. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment. It is preferable to use the red coloring composition of the present invention for the red filter segment.

[0194] (How to manufacture color filters) In color filters, it is preferable to first form a black matrix on the substrate, and then form the filter segments. Alternatively, thin-film transistors (TFTs) can be formed on the substrate beforehand, and then the black matrix can be formed. Examples of black matrices include multilayer films of chromium or chromium / chromium oxide, inorganic films such as titanium nitride, and resin films in which light-shielding agents are dispersed.

[0195] The color filter of the present invention can be bonded to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealed portion, the injection port is sealed, and a polarizing film or phase difference film is bonded to the outside of the substrate as needed to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that perform colorization using color filters such as twisted nematic (TN), super-twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convened bend (OCB).

[0196] In this specification, color filters can be used in applications other than liquid crystal displays, such as solid-state image sensors, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays.

[0197] <Solid-state image sensor> The solid-state image sensor of the present invention has the color filter of the present invention. The form used for the solid-state image sensor is not particularly limited, but for example, it may have a substrate on which a plurality of photodiodes constituting the light-receiving area of ​​the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like are provided, a light-shielding film with an opening only for the light-receiving portion of the photodiode is provided on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a filter on the device protection film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens; the same applies hereinafter) is provided on the device protection film below the filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the filter. In addition, the filter may have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, it is preferable that the partition walls have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and optical sensors.

[0198] <Image display device> The image display device of the present invention has the color filter of the present invention. Examples of image display devices include liquid crystal displays and organic EL displays. The form used for an image display device is not particularly limited, as long as it functions as an image display device. For example, the configurations described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994) are examples. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989). [Examples]

[0199] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively.

[0200] Prior to the examples, each measurement method will be described.

[0201] The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of resin (B) are as follows.

[0202] (Average molecular weight of resins containing acidic groups) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resins containing acid groups were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the instrument, with two separation columns connected in series and two TSK-GEL SUPER HZM-N packing materials connected in series for both columns. The measurements were performed at an oven temperature of 40°C, using THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalents.

[0203] (Average molecular weight of resins containing basic groups) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resins containing basic groups were measured using an HLC-8320GPC instrument (manufactured by Tosoh Corporation), a SUPER-AW3000 column, and a 30 mM triethylamine and 10 mM LiBr N,N-dimethylformamide solution as the eluent. All molecular weights are polystyrene equivalents.

[0204] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g). The acid value per unit solid content of the resin was then calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

[0205] (Amine value of resin) The amine value of the resin is calculated by converting the total amine value (mgKOH / g), which was measured according to the ASTM D 2074 method, into a solid content equivalent.

[0206] (Quaternary ammonium salt value of resins) The quaternary ammonium salt value of the resin was determined by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent amount of potassium hydroxide. The quaternary ammonium salt value of the resin represents the quaternary ammonium salt value of the non-volatile portion.

[0207] <Manufacturing of resin (B)> (Resin (B1)) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 90 parts methyl methacrylate, 50 parts ethyl acrylate, 50 parts tert-butyl acrylate, and 50 parts propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted. Nineteen parts of pyromellitic dianhydride, fifty parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to dilute the solution to a solid content of 50% by measuring the solid content, yielding a resin (B1) solution with an acid value of 70.1 mg KOH / g and a weight-average molecular weight of 8,500.

[0208] (Resin (B2)) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40 parts methyl methacrylate, 10 parts n-butyl methacrylate, and 13.2 parts tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, purging the system with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate as an initiator, 5.6 parts cuprous chloride as a catalyst, and 133 parts methoxypropyl acetate were charged, and the temperature was raised to 110°C under a nitrogen atmosphere to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher, calculated from the non-volatile content. Next, 61 parts methoxypropyl acetate, 25 parts dimethylaminoethyl methacrylate and 25 parts methacryloyloxyethyltrimethylammonium chloride as monomers for the second block (block A) were added to this reactor, and the reaction was continued while stirring was maintained at 110°C and a nitrogen atmosphere. Two hours after adding dimethylaminoethyl methacrylate, the polymerization solution was sampled and its solid content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher. The reaction solution was then cooled to room temperature to stop the polymerization. GPC measurement revealed that the polymer had a Mw of 16000, a molecular weight distribution Mw / Mn of 1.4, and a reaction conversion rate of 98.5%. In this way, resin (B2) with an amine value of 62.5 mg KOH / g per solid was obtained. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution to a non-volatile content of 50% by mass to prepare resin (B2) solution.

[0209] (Resin (B3)) 370 parts of cyclohexanone were placed in a separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C, and the flask was purged with nitrogen. A mixture of 30 parts dicyclopentanyl methacrylate, 10 parts styrene, 31.2 parts glycidyl methacrylate, and 2.0 parts 2,2'-azobisisobutyronitrile was then added dropwise over 2 hours via the dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours. Then, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for another hour. Next, the container was replaced with an air-purging system, and 9.3 parts of acrylic acid (100% of the glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the solids acid value reached 0.5, at which point the reaction was terminated to obtain a resin solution. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 3.5 hours to obtain a resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to prepare resin (B3) solution so that the non-volatile content was 50% by mass. The weight-average molecular weight (Mw) was 19000.

[0210] (Resin (B4)) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 25.1 parts benzyl methacrylate, 23.0 parts n-butyl methacrylate, 14.3 parts 2-hydroxyethyl methacrylate, 13.4 parts methacrylic acid, 24.1 parts paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 3 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to achieve a non-volatile content of 50% by mass to prepare resin (B4) solution. Resin (B4) had an acid value of 87 mgKOH / g, a weight-average molecular weight of 25,000, and a composition ratio (mol%) of benzyl methacrylate / methacrylic acid / n-butyl methacrylate / 2-hydroxyethyl methacrylate / paracumylphenol ethylene oxide modified acrylate = 22 / 24 / 25 / 17 / 12.

[0211] <Manufacturing of red coloring composition> [Example 1] (Red colored composition 1) After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250MKII"), and then filtered through a 5.0 μm pore size filter to produce red colored composition 1 with 20% by mass of nonvolatile components. Details of the raw materials used will be described later. PV19 β type-2: 2.2 parts PR264: 7.3 copies PY139: 1.7 parts Pigment derivative 1 : 1.4 parts Pigment derivative 2: 1.4 parts Resin (B1) solution (50% solids): 12.0 parts Propylene glycol monomethyl ether acetate: 74.0 parts

[0212] [Examples 2-58, 201-223, 225-273, 275-304, Comparative Examples 1-4] (Red coloring composition 2~62, 201~223, 225~273, 275~304) Red coloring compositions 2-62, 201-223, 225-273, and 275-304 were manufactured in the same manner as in the manufacture of red coloring composition 1, except that the coloring agent and resin were changed to the raw materials and proportions listed in Tables 1-1 to 1-7. Regarding the colorants, the amount of colorants other than pigment derivatives was adjusted so that x=0.697 and y=0.301 with a C light source. However, the total amount of colorants other than pigment derivatives was 11.2 parts.

[0213] [Example 224] (Red colored composition 224) After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250MKII"). The mixture was then filtered through a 5.0 μm pore size filter to produce a red colored composition 224 with 20% by mass of nonvolatile components. Details of the raw materials used will be described later. PV19 β type-2: 1.0 part PR177: 7.3 copies PY139: 1.7 parts PV32: 1.0 copies PV29: Part 0.2 Pigment derivative 1:0.9 parts Pigment derivative 9:0.9 parts Pigment derivative 12:1.0 parts Resin (B1) solution (50% solids): 12.0 parts Propylene glycol monomethyl ether acetate: 74.0 parts

[0214] [Example 274] (Red colored composition 274) Red colored composition 274 was manufactured in the same manner as the manufacture of red colored composition 224, except that PV19 β-2 was changed to PV19 β-3.

[0215] <Evaluation of red-colored compositions> The red coloring compositions were evaluated using the following procedure. The results are shown in Tables 1-1 to 1-7.

[0216] (brightness) The obtained red colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater. Then, it was dried at 70°C for 20 minutes, followed by heating at 230°C for another 20 minutes, and then allowed to cool to produce a coated substrate. The brightness of the obtained coated substrates was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200") and evaluated according to the following criteria. The coated substrate was heat-treated at 230°C and then adjusted to a chromaticity of x=0.697 and y=0.301 using a C light source. ◎: Brightness level 8.3 or higher ○: Brightness is 8.0 or higher, but less than 8.3. △: Brightness is 7.5 or higher, but less than 8.0. ×: Brightness is less than 7.5

[0217] (coloring power) Using the same coated substrate as used for brightness evaluation, the film thickness was measured using the surface shape measuring device "Dektak8 (manufactured by Veeco)" and evaluated according to the following criteria. The thinner the film thickness, the higher the coloring power. ◎: Film thickness less than 2.0 μm ○: Film thickness of 2.0 μm or more, and less than 2.2 μm. △: Film thickness is 2.2 μm or more, but less than 2.4 μm. ×: Film thickness is 2.4 μm or more

[0218] (reflectance) Using the same coated substrate as used for luminance evaluation, the reflectance of the coating was measured using the spectrophotometric system "CM-26D (manufactured by Konica Minolta)" and evaluated according to the following criteria. In the measurement, a black film tape (manufactured by Chukyo Chemical Industries Co., Ltd.) was attached to the coated surface of the coating film substrate, with the tape-attached surface facing down and the glass surface facing up, and light was applied from the glass surface for measurement. The lower the SC, the lower the reflectivity. ◎: SC is less than 5.5 〇: SC is 5.5 or more and less than 5.7 △: SC is 5.7 or more and less than 6.0 ×: SC is 6.0 or more

[0219] (Light resistance) The obtained red coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 °C for 20 minutes, further heated at 230 °C for 20 minutes, and allowed to cool to prepare a coating film substrate. The coating film substrate was applied so that the film thickness became 3.5 μm after heat treatment at 230 °C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film was measured using a micro spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Subsequently, an ultraviolet cut filter ("COLORED OPTICAL GLASS L38" manufactured by Hoya Corporation) was attached onto the substrate, and after irradiating with ultraviolet rays for 150 hours using a xenon lamp of 300 W / m 2 , the chromaticity ([L * (2), a * (2), b * (2)]) was measured, and the color difference ΔEab * was obtained according to the following calculation formula and evaluated based on the following criteria. ΔEab * = √((L * (2) - L * (1)) 2 + (a * (2) - a * (1)) 2 + (b * (2) - b * (1)) 2 ) ◎: ΔEab* is less than 1.0 〇:ΔEab * The value is between 1.0 and 1.5. △:ΔEab * The value is between 1.5 and 3.0. ×:ΔEab * 3.0 or higher

[0220] <Ingredients listed in the table> The raw materials listed in Tables 1-1 to 1-7 below are as follows:

[0221] (CI Violet 19) PV19 α-type: CI Violet 19 crystal structure α-type Average primary particle diameter 78nm PV19 β-type: CI Violet 19 crystal structure β-type Average primary particle diameter 60nm PV19 γ-type: CI Violet 19 crystal structure γ-type Average primary particle diameter 72nm PV19 β-type-2: 95 parts of the above-mentioned CI Violet 19 β-type crystal structure were mixed with 5 parts of the pigment derivative 1 below, 800 parts of pulverized salt, and 100 parts of diethylene glycol in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 70°C for 12 hours. This mixture was added to 3000 parts of warm water and stirred in a high-speed mixer for about 1 hour while being heated to about 70°C to form a slurry. After removing the salt and solvent by repeated filtration and washing with water, it was dried at 80°C for 24 hours to obtain 98 parts of PV19 β-type-2. Average primary particle diameter 23nm PV19 β-type-3: PV19 β-type-3 was obtained in the same manner as the production of PV19 β-type-2, except that pigment derivative 1 was replaced with pigment derivative 9 described below. Average primary particle diameter 19nm

[0222] (Red pigment) PR264: CI Pigment Red 264 PR179: CI Pigment Red 179 PR269: CI Pigment Red 269 PR177: CI Pigment Red 177 PR254: CI Pigment Red 254 PR122: CI Pigment Red 122

[0223] (Other colorants) PY139: CI Pigment Yellow 139 PY185: CI Pigment Yellow 185 PY150: CI Pigment Yellow 150 PY138: CI Pigment Yellow 138 PV32: CI Pigment Violet 32 PV29: CI Pigment Violet 29

[0224] (Pigment derivatives) Pigment derivatives 1-12: Compounds 1-12 with the following structures [ka] JPEG0007896242000038.jpg147170

[0225] [Table 1-1]

[0226] [Table 1-2]

[0227] [Table 1-3]

[0228] [Table 1-4]

[0229] [Table 1-5]

[0230] [Table 1-6]

[0231] [Table 1-7]

[0232] As shown in the table above, the red coloring compositions of the examples were able to form films with high brightness, high coloring power, low reflectivity, and excellent lightfastness.

[0233] <Manufacturing of a photosensitive red colored composition> [Example 101] (Photosensitive red colored composition 1) A mixture of the following compositions was stirred and mixed until homogeneous, and then filtered through a pore size 1 μm to produce photosensitive red colored composition 1. Red coloring composition 1 (solid content 20%): 37.50 parts Resin (B3) solution (50% solids): 6.85 parts Photopolymerizable compound (Aronix M-402, manufactured by Toagosei Co., Ltd.): 3.75 parts Photopolymerization initiator (ADEKA "ADEKA Cruise NCI-831"): 0.23 parts Leveling agent (2% solid content, see below): 5.00 parts Propylene glycol monomethyl ether acetate: 46.68 parts

[0234] The leveling agent mentioned above is as follows: A leveling agent was prepared by mixing 1 part each of BYK-330 (manufactured by Big Chemie) and Megafac F-551 (manufactured by DIC), dissolving them in 98 parts of PGMAc to create a mixed solution.

[0235] [Examples 102-158, 401-504, Comparative Examples 101-104] (Photosensitive red coloring composition 2-62, 401-504) Photosensitive red coloring compositions 2-62 and 401-504 were manufactured in the same manner as in the manufacture of photosensitive red coloring composition 1, except that red coloring composition 1 was replaced with one of the red coloring compositions listed in Tables 2-1 to 2-7.

[0236] [Example 505] (Photosensitive red coloring composition 505) A mixture of the following compositions was stirred and mixed until homogeneous, and then filtered through a 1 μm pore size filter to produce photosensitive red colored composition 505. Red coloring composition 224 (solid content 20%): 37.50 parts Resin (B3) solution (50% solids): 6.85 parts Photopolymerizable compound A: 3.75 parts Photopolymerization initiator (ADEKA "ADEKA Cruise NCI-831"): 0.23 parts Leveling agent (2% solid content, see below): 5.00 parts Propylene glycol monomethyl ether acetate: 46.68 parts

[0237] The above photopolymerizable compound A is as follows: A mixture of equal amounts of Arronix M-402 (manufactured by Toagosei Co., Ltd.), Arronix M-306 (manufactured by Toagosei Co., Ltd.), and NK ester ABE-300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) was prepared as photopolymerizable compound A.

[0238] [Example 506] (Photosensitive red coloring composition 506) Photosensitive red colored composition 506 was manufactured in the same manner as in the manufacture of photosensitive red colored composition 505, except that red colored composition 224 was replaced with red colored composition 274.

[0239] <Evaluation of photosensitive red colored compositions> The photosensitive red colored compositions were evaluated using the following procedure. The results are shown in Tables 2-1 to 2-7.

[0240] (brightness) The obtained photosensitive red colored composition was applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70°C for 20 minutes, exposed to ultraviolet light at an integrated light intensity of 100 mJ / cm2 using an ultra-high pressure mercury lamp, and developed with an alkaline developer at 23°C to obtain a coated substrate. Then, it was heated at 230°C for 20 minutes, allowed to cool, and the brightness of the obtained coated substrate was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200") and evaluated according to the following criteria. The coated substrate was heat-treated at 230°C and adjusted to a chromaticity of x=0.697 and y=0.301 using a C light source. The alkaline developer used consisted of 1.5% by mass of sodium carbonate, 0.5% by mass of sodium bicarbonate, 8.0% by mass of anionic surfactant (Kao Corporation's "Perilex NBL"), and 90% by mass of water. ◎: Brightness level 8.3 or higher ○: Brightness is 8.0 or higher, but less than 8.3. △: Brightness is 7.5 or higher, but less than 8.0. ×: Brightness is less than 7.5

[0241] (coloring power) Using the same coated substrate as used for brightness evaluation, the film thickness was measured using the surface shape measuring device "Dektak8 (manufactured by Veeco)" and evaluated according to the following criteria. The thinner the film thickness, the higher the coloring power. ◎: Film thickness less than 3.5 μm ○: Film thickness of 3.5 μm or more, and less than 3.8 μm. △: Film thickness is 3.8 μm or more, but less than 4.0 μm. ×: Film thickness is 4.0 μm or more

[0242] (reflectance) Using the same coated substrate as used for luminance evaluation, the reflectance of the coating was measured using the spectrophotometric system "CM-26D (manufactured by Konica Minolta)" and evaluated according to the following criteria. For the measurement, a black film tape (manufactured by Chuko Kasei Kogyo Co., Ltd.) was attached to the coated surface of the coated substrate, with the tape-attached side facing down and the glass side facing up, and the measurement was performed by shining light from the glass side. The lower the SC (Sensitivity), the lower the reflectivity. ◎: SC is less than 5.5 ○: SC is 5.5 or higher, but less than 5.7 △: SC is 5.7 or higher, but less than 6.0 ×: SC is 6.0 or higher

[0243] (Lightfastness) The obtained photosensitive red colored composition was applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70°C for 20 minutes, exposed to ultraviolet light at an integrated light intensity of 100 mJ / cm² using an ultra-high pressure mercury lamp, and developed with an alkaline developer at 23°C to prepare a coated substrate. The coated substrate was coated to a film thickness of 3.5 μm after heat treatment at 230°C. Subsequently, the color difference ΔEab was evaluated using the same procedure as for evaluating the lightfastness of the red colored composition. * We sought and evaluated the following criteria. ◎:ΔEab * is less than 1.0 〇:ΔEab * The value is between 1.0 and 1.5. △:ΔEab * The value is between 1.5 and 3.0. ×:ΔEab * 3.0 or higher

[0244] [Table 2-1]

[0245] [Table 2-2]

[0246] [Table 2-3]

[0247] [Table 2-4]

[0248] [Table 2-5]

[0249] [Table 2-6]

[0250] [Table 2-7]

[0251] As shown in the table above, the photosensitive red coloring compositions of the examples were able to form films with high brightness, high coloring power, low reflectivity, and excellent lightfastness.

[0252] In the photosensitive red colored composition of each example, the same effects as in each example can be obtained even if the compound described in <Photopolymerizable Compound (C)> above is included in an amount of 1 to 50% by mass of 100% by mass of the nonvolatile content of the photosensitive red colored composition, and the compound described in <Photopolymerization Initiator (D)> above is included in an amount of 0.1 to 20% by mass of 100% by mass of the nonvolatile content of the photosensitive red colored composition.

[0253] In the photosensitive red colored compositions of each example, the same effects as in each example can be obtained even if two or more types of photopolymerizable compounds and photopolymerization initiators are used in combination.

[0254] As described above, the red coloring composition of the present invention has high brightness, high coloring power, and low reflectivity, and can form a film with excellent light resistance, making it suitable for manufacturing color filters for solid-state image sensors, image display devices, and the like.

Claims

1. A red coloring composition comprising a coloring agent (A) and a resin (B), A red coloring composition in which the coloring agent (A) comprises C.I. Violet 19, a red pigment, and two or more pigment derivatives having different structures, The pigment derivatives are pigment structures selected from the group consisting of diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, benzimidazolon pigments, indole pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments. A compound having at least one selected from the group consisting of an acidic group, a basic group, a group having a salt structure, and a phthalimide group. A red coloring composition comprising two or more pigment derivatives with different structures, including a pigment derivative containing a quinophthalone pigment structure and a pigment derivative containing a pigment structure other than the quinophthalone pigment structure.

2. The red coloring composition according to claim 1, wherein the red pigment comprises at least one selected from the group consisting of C.I. Pigment Red 179, C.I. Pigment Red 264, C.I. Pigment Red 269, and C.I. Pigment Red 122.

3. The red coloring composition according to claim 1, wherein C.I. Violet 19 is β-type unsubstituted quinacridone.

4. The red coloring composition according to claim 1, wherein resin (B) comprises resin (B1) having an aromatic carboxyl group.

5. The red coloring composition according to claim 1, wherein the coloring agent (A) further comprises an isoindoline pigment.

6. The red coloring composition according to claim 1, further comprising a photopolymerizable compound (C) and / or a photopolymerizable initiator (D).

7. A film formed from the red coloring composition according to claim 1 or 6.

8. A color filter having the film described in claim 7.

9. A solid-state image sensor having a color filter as described in claim 8.

10. An image display device having a color filter as described in claim 8.

Images