Coloring composition for color filters, color filters, and solid-state image sensors

Abstract

To provide a colored composition, a color filter, and a solid-state image sensor that have high coloring power and transmittance, and good dispersion stability. [Solution] A coloring composition for color filters containing a phthalocyanine compound represented by general formula (1), and a color filter using the same. General formula (1) JPEG2026113406000037.jpg6375

Description

[Technical Field]

[0001] This invention relates to a coloring composition for color filters, a color filter, and a solid-state image sensor. [Background technology]

[0002] Color filters, which make up liquid crystal display devices (LCDs), solid-state image sensors, etc., are formed by coating a photosensitive colored composition onto a substrate or by creating a pattern using photolithography.

[0003] Generally, color filters used in solid-state image sensors have smaller pixel sizes and are thinner than those used in LCDs. Furthermore, solid-state image sensors themselves are becoming smaller. While color filters are becoming thinner, the chromaticity of the pixels must be maintained, meaning the concentration of the colorant in the coating cannot be reduced. Therefore, the colorant content in the photosensitive coloring composition must be increased, while other components (resin, polymerizable compound, photopolymerization initiator, etc.) must be relatively reduced. As a result, a problem arose where residue would form between patterns after the development process. To address this problem, there is a need for highly coloring pigments that exhibit sufficient color characteristics even in small quantities. Furthermore, these pigments must also possess high transmittance to allow for greater light reception and heat resistance to withstand the manufacturing process of color filters.

[0004] The green pigments used as the main color in the manufacture of green filter segments are phthalocyanine-based pigments, particularly PG36 and PG58. However, their coloring power has not been satisfactory in response to the strong demand for thin films in recent years. There are also studies that use aluminum phthalocyanine as the central metal, but its dispersibility at high concentrations is poor, and its spectral characteristics are bluer than those of PG36 and PG58, making it difficult to use as a green color filter. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2002-131521 [Patent Document 2] Japanese Patent Publication No. 2002-250812 [Patent Document 3] Patent No. 5779833 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a colored composition, a color filter, and a solid-state image sensor that have high coloring power and transmittance, and good dispersion stability. [Means for solving the problem]

[0007] As a result of diligent research to solve the aforementioned problems, the present inventors have discovered that a coloring composition for color filters containing a phthalocyanine compound having a specific structure exhibits high coloring power, excellent transmittance, and high dispersion stability. Based on this finding, the present invention was made.

[0008] [1] A coloring composition for color filters comprising a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine compound represented by the following general formula (1).

[0009] General formula (1) [ka] In the formula, R1 to R8 each independently represent a hydrogen atom, an optionally substituted alkoxyl group, or an optionally substituted aryloxy group, and at least one of R1 to R8 is an optionally substituted alkoxyl group or an optionally substituted aryloxy group. M represents Al, and Z represents a monovalent ligand.

[0010] [2] In R1 to R8, the total number of an alkoxyl group which may have a substituent and an aryloxy group which may have a substituent is 1 to 4, and in R1 and R2, R3 and R4, R5 and R6, R7 and R8, at least one of each is a hydrogen atom. The colorant composition for a color filter according to [1].

[0011] [3] In R1 to R8, the total number of an alkoxyl group which may have a substituent and an aryloxy group which may have a substituent is 1 to 2. The colorant composition for a color filter according to [2].

[0012] [4] When the phthalocyanine compound is heated at 230 °C for 20 minutes with a colorant composition comprising 20% by mass of the phthalocyanine compound in the total solid content and a resin having a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm, and a coating film is prepared by adjusting the thickness to 1 μm, the maximum value of the absorbance at 630 to 680 nm is 1.1 or more. The colorant composition for a color filter according to any one of [1] to [3].

[0013] [5] The colorant composition for a color filter according to any one of [1] to [4], further comprising a resin type dispersant.

[0014] [6] The colorant composition for a color filter according to any one of [1] to [5], further comprising a yellow pigment.

[0015] [7] The colorant composition for a color filter according to any one of [1] to [6], further comprising a photoinitiator.

[0016] [8] The colorant composition for a color filter according to any one of [1] to [7], further comprising a polymerizable compound.

[0017] [9] A color filter having a film formed of the colorant composition for a color filter according to any one of [1] to [8] on a substrate.

[0018] A solid-state image sensor comprising the color filters described in

[10] [9]. [Effects of the Invention]

[0019] The present invention provides a coloring composition for color filters, a color filter, and a solid-state image sensor that have high coloring power and transmittance and good dispersion stability. [Modes for carrying out the invention]

[0020] The following definitions are used in this specification. When "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" are used, unless otherwise specified, they refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. "CI" as used herein means Color Index (CI). A phthalocyanine compound represented by general formula (1) may be referred to as phthalocyanine compound (1). Colorants include pigments and dyes. A coloring composition for color filters is referred to as a coloring composition.

[0021] <Coloring agent> The colored composition of the present invention contains a pigment or dye as a coloring agent. As the pigment, organic or inorganic pigments can be used individually or in combination of two or more. The pigment is preferably one with high color development and high heat resistance, particularly pigment with high heat decomposition resistance; organic pigments are usually used. Specific examples of organic pigments usable in colored compositions for color filters are shown below by their color index numbers.

[0022] <Phthalocyanine compound (1)> The present invention relates to a colored composition for color filters comprising a colorant, a binder resin, and an organic solvent, wherein the colorant contains a phthalocyanine compound represented by the following general formula (1). The phthalocyanine compound (1) has high coloring power and transmittance, and can therefore be suitably used as a colorant for color filters, and is particularly suitable for use as a colorant for color filters used in solid-state image sensors.

[0023] General formula (1) [ka] In the formula, R1 to R8 each independently represent a hydrogen atom, an optionally substituted alkoxyl group, or an optionally substituted aryloxy group, and at least one of R1 to R8 is an optionally substituted alkoxyl group or an optionally substituted aryloxy group. M represents Al, and Z represents a monovalent ligand.

[0024] Examples of "alkoxyl groups" that may have substituents include linear or branched alkoxyl groups and cyclic alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy. Examples of "alkoxyl groups with substituents" include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

[0025] Examples of "aryloxy groups" that may have substituents include phenoxy groups, naphthoxy groups, and anthuryloxy groups, while examples of "substituted aryloxy groups" include p-methylphenoxy groups, p-nitrophenoxy groups, p-methoxyphenoxy groups, 2,4-dichlorophenoxy groups, pentafluorophenoxy groups, and 2-methyl-4-chlorophenoxy groups.

[0026] The phthalocyanine compound (1) has high coloring power and transmittance, and good dispersion stability, as at least one of R1 to R8 is an optionally substituted alkoxyl group or an optionally substituted aryloxy group, and the other R1 to R8 are hydrogen atoms, i.e., at least one of the α-positions is an optionally substituted alkoxyl group or an optionally substituted aryloxy group.

[0027] When at least one of R1 to R8 is an optionally substituted alkoxyl group or an optionally substituted aryloxy group, the entire transmission spectrum of the phthalocyanine compound shifts to longer wavelengths and produces a good green color, compared to when all of R1 to R8 are hydrogen atoms. Here, the transmission spectrum of the phthalocyanine compound is the transmission spectrum of the coating obtained when a coating film of a colored composition consisting of 20% by mass of the phthalocyanine compound in the total solid content and a resin with a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm is formed and then heat-treated at 230°C for 20 minutes. If R1 to R8 are all hydrogen, the transmission spectrum of the coating film prepared under the above conditions is not sufficiently long-wavelength, resulting in a bluish tint and failing to produce a good green color. A good green color can be evaluated by applying the above coloring composition using a spin coater, drying it at 70°C for 20 minutes, and then heating it at 230°C for 20 minutes to adjust the film thickness so that the transmittance at 650 nm is 10%, and then checking the transmittance at 600 nm. When 650 nm, which is the bottom region of the transmission spectrum when green color is produced, is set to a constant value, a higher transmittance at 600 nm indicates a better green color, while a lower transmittance indicates a bluish tint and insufficient green color.

[0028] The optionally substituted alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, as it exhibits high coloring power and transmittance, and good dispersion stability. The optionally substituted aryloxy group is preferably a phenoxy group, as it exhibits high coloring power and transmittance, and good dispersion stability.

[0029] In R1 to R8, it is preferable that the total number of optionally substituted alkoxyl groups and optionally substituted aryloxy groups is 1 to 4, and that at least one of each of R1 and R2, R3 and R4, R5 and R6, and R7 and R8 is a hydrogen atom. That is, it is preferable that 1 to 4 of the four phthalonitrile skeletons are phthalonitriles having only one optionally substituted alkoxyl group or optionally substituted aryloxy group. Furthermore, it is more preferable that the total number of optionally substituted alkoxyl groups and optionally substituted aryloxy groups in R1 to R8 is 1 to 3, and even more preferable that it is 1 to 2. With the above configuration, dispersibility and color characteristics are good.

[0030] Compared to the case where both of any combination of R1 and R2, R3 and R4, R5 and R6, or R7 and R8 are optionally substituted alkoxy groups or optionally substituted aryloxy groups, it is preferable that only one of any combination of the above is an optionally substituted alkoxy group or optionally substituted aryloxy group, as this results in a higher maximum transmittance around 520-540 nm in the transmission spectrum of the coating film prepared under the above conditions.

[0031] Furthermore, when the total number of optionally substituted alkoxyl groups and optionally substituted aryloxy groups in R1 to R8 is 1 to 3, the transmission spectrum of the coating film produced under the above conditions is in a more preferable wavelength range, and when it is 1 to 2, it is in an even more preferable wavelength range. This is because, compared to the case where all of R1 to R8 are hydrogen, and compared to the case where the total number of optionally substituted alkoxyl groups and optionally substituted aryloxy groups is 4, the case where it is 1 to 3 results in a slightly less pronounced shift to longer wavelengths, thus producing a wavelength range that exhibits a better green color.

[0032] As described above, the degree of wavelength shift can be evaluated by applying the above-mentioned colored composition using a spin coater, drying it at 70°C for 20 minutes, and then heating it at 230°C for 20 minutes to adjust the film thickness so that the transmittance at 650 nm is 10%, and then confirming the wavelength at which the transmittance becomes 40% in the 550-650 nm range. In this case, when the wavelength at which the transmittance becomes 40% is between 603 nm and 610 nm, it can be confirmed that the material has developed a good green color.

[0033] Z is not particularly limited as long as it is a monovalent ligand, but can be a halogen atom, -OH, -OR9, or -OP(=O)R 10 R 11 -OC(=O)R 12 -OS(=O)2R 13 It is preferable. Here, R9 represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. R 10and R 11 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R 12 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. R 13 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. Z is preferably -OP(=O)R 10 R 11 , -OC(=O)R 12 , -OS(=O)2R 13 It is preferable that it is, and the coloring power and the transmittance are good. Also, -OP(=O)R 10 R 11 is more preferable, and the balance of the coloring power, the transmittance, and the dispersion stability is good, and the heat resistance is good. R9 to R 13 is preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and the dispersibility and the color characteristics are good.

[0034] Here, R9 to R 13Examples of alkyl groups in this context include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and adamantyl groups. When the alkyl group is a substituent-containing alkyl group, examples of substituents include halogen atoms such as chlorine, fluorine, and bromine, alkoxyl groups such as methoxy, aromatic groups such as phenyl and tolyl, hydroxyl, amino, and nitro groups. There may also be multiple substituents. Examples of alkyl groups having substituents include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, 2,5-dimethylcyclopentyl, and 4-tert-butylcyclohexyl.

[0035] R9~R 13 Examples of aryl groups in this context include phenyl, naphthyl, and anthuryl groups. Substituents for aryl groups include halogen atoms such as chlorine, fluorine, and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups, and nitro groups. Multiple substituents are also possible. Examples of substituted aryl groups include p-tolyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-dimethylaminophenyl, 2-methyl-4-chlorophenyl, 4-methoxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, and anthraquinonyl groups.

[0036] R9~R 13Examples of heterocyclic groups in this context include pyridyl, pyrazyl, piperidino, pyranyl, morpholino, and acridinyl groups. Substituents in heterocyclic groups include halogen atoms such as chlorine, fluorine, and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups, and nitro groups. Multiple substituents are also permitted. Examples of heterocyclic groups with substituents include 3-methylpyridyl, N-methylpiperidyl, and N-methylpyrrolyl groups.

[0037] R9 and R 13 Examples of alkoxyl groups and optionally substituted aryloxy groups in the above are the same as those for R1 to R8.

[0038] In particular, Z is -OP(=O)R 10 R 11 This is preferable because it results in better light resistance.

[0039] Furthermore, R 10 and R 11 However, when the substituent is a hydrogen atom, hydroxyl group, alkyl group, alkoxyl group, or aryloxy group that does not contain aromatic rings or heterocycles, the dispersibility is remarkably good, making it preferable.

[0040] Preferably, the phthalocyanine compound (1) is a colored composition consisting of 20% by mass of the phthalocyanine compound (1) in the solid content and a resin with a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm. When this colored composition forms a film with a thickness of 1 μm and is heat-treated at 230°C for 20 minutes, the maximum absorbance at 630 to 680 nm is 1.1 or more. Within this range, the coloring power is high, and the dispersibility and color characteristics are also good.

[0041] Typical examples of phthalocyanine compounds (1) in the present invention include the phthalocyanine compounds listed below, but the present invention is not limited to these.

[0042] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0043] The colored composition for color filters of the present invention preferably contains 20 to 80% by mass of phthalocyanine compound (1) in 100% by mass of solids, and more preferably 25 to 75% by mass. Within this range, good dispersibility and color characteristics are obtained.

[0044] The colored composition for color filters of the present invention may further contain a yellow coloring agent to adjust the chromaticity, etc., to the extent that it does not impair the effects of the present invention. There are no particular restrictions on the yellow coloring agent, but generally, yellow dyes or yellow pigments are used.

[0045] Examples of yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, and oxazine dyes.

[0046] Therefore, specific examples of yellow dyes include CI Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, Examples include 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

[0047] Also, CI Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. can also be mentioned.

[0048] Other examples include CI Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, and 106.

[0049] Also, CI Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 10 Other examples include 4, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195, etc.

[0050] Other examples include CI Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64, 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184:1, 202, 211, 229, 231, 232, 233, 241, 245, 246, 247, 248, 249, 250, 251, etc.

[0051] As the yellow pigment, organic or inorganic pigments can be used individually or in combination of two or more types. Pigments with high color development and high heat resistance, especially those with high heat decomposition resistance, are preferred, and organic pigments are usually used. As organic pigments, commercially available ones can be used.

[0052] For yellow pigments, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 Examples include pigments described in Japanese Patent Publication No. 2012-226110, as well as those listed in 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and Japanese Patent Publication No. 2012-226110. Preferably, the pigments are CI Pigment Yellow 138, 139, 150, 185, 231, 233, or the pigments described in Japanese Patent Publication No. 2012-226110.

[0053] Furthermore, a green pigment can be added for the purpose of adjusting the hue. Examples of green pigments include, but are not limited to, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and the pigments described in Japanese Patent Publication No. 2017-111398. Among these, from the viewpoint of transmittance, CI Pigment Green 36, 58, 59, 62, 63, and the pigments described in Japanese Patent Publication No. 2017-111398 are preferred.

[0054] When using a yellow coloring agent, the mass ratio of the yellow coloring agent to the phthalocyanine compound (1) is preferably in the range of 50 / 50 to 10 / 90. Within this range, the transmittance of the green color filter is improved, and the desired hue can be obtained.

[0055] (Other organic pigments) 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 ,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260 Examples include pigments described in JP 262, 263, 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, 296, pigments described in JP 2014-134712, pigments described in JP 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, the preferred pigments are CI pigment red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844. More preferably, the preferred pigments are CI pigment red 177, 254, 291, 295, 296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844.

[0056] Furthermore, the red coloring composition may also contain orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, and / or yellow pigments as described below.

[0057] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, and CI Pigment Blue 15:6 is more preferred. In addition, purple pigments, as described later, may be used in combination with the blue coloring composition.

[0058] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 or 23 is preferred from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, and CI Pigment Violet 23 is more preferred.

[0059] For forming cyan colored filter segments, blue pigments such as CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, and 81 can be used alone or in mixtures in the cyan colored composition.

[0060] For forming a magenta colored filter segment, a magenta colored composition can be used that contains purple pigments and red pigments, such as CI Pigment Violet 1, 19 and CI Pigment Red 144, 146, 177, 169, 81, either individually or in combination. A yellow pigment may also be used in combination with the magenta colored composition.

[0061] In addition, inorganic pigments include titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, and cobalt. Examples include green, amber, and synthetic iron black. Inorganic pigments are used in combination with organic pigments to ensure good applicability, sensitivity, and developability while maintaining a balance between saturation and brightness.

[0062] <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 80 nm, and more preferably 15 to 70 nm. An appropriate particle size further improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of approximately 20 particles arbitrarily selected from a magnified image obtained using a TEM (transmission electron microscope). If the particle has both a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] <Metal Removal> If specific metal elements are present in large quantities as impurities other than the pigment components in a photosensitive colored composition, it can impair the dispersion stability over time, and may also reduce heat resistance or sensitivity. Furthermore, color filters made using such compositions may develop foreign matter, which can easily lead to a decrease in brightness. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in the photosensitive colored composition is 500 ppm by mass or less.

[0068] The total amount of specific metal elements contained in the photosensitive colored composition is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. Furthermore, while there is no particular lower limit to the total amount of specific metal elements, it is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, a photosensitive colored composition can be obtained that suppresses costs, has excellent storage stability, and can form a color filter with minimal generation of foreign matter and reduction in brightness.

[0069] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0070] Furthermore, it is preferable that the metals that make up the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, contain fewer impurities that do not function effectively, and these can be removed in the same way as specific metal elements by the following methods. In addition, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc., that have been introduced due to materials used in the manufacturing process of the various raw materials of the photosensitive colored composition (for example, catalysts) be low.

[0071] Methods for removing colorants or metals introduced from equipment during the manufacturing process include washing with water as described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in Japanese Patent Publication No. 2011-48736. One or more of these methods may be used as appropriate.

[0072] The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0073] <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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] <Dye derivatives> Dye derivatives may be used in the colored composition as needed. Dye derivatives are compounds having acidic groups, basic groups, neutral groups, etc., in organic dye residues. Examples of dye derivatives include compounds having acidic substituents such as sulfo groups, carboxyl groups, or phosphate groups, as well as compounds having basic substituents such as amine salts thereof, sulfonamide groups, or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0078] Specifically, diketopyrrolopyrrole dye derivatives are described in Japanese Patent Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Publication No. 2017-156397; phthalocyanine dye derivatives are described in Japanese Patent Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Publication No. 2017-165820, and Japanese Patent No. 5753266; and anthraquinone dye derivatives are described in Japanese Patent Publication No. Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, Brochure WO2009 / 025325, Quinacridone-based dye derivatives are Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, Dioxazine-based dye derivatives are Japanese Patent Publication No. 2011-162662, Thiazine-indigo-based dye derivatives are Japanese Patent Publication No. 2007-3147 Japanese Patent Publication No. 85, Triazine-based dye derivatives are described in Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, Japanese Patent Publication No. 2007-314681, Benzoisoindole-based dye derivatives are described in Japanese Patent Publication No. 2009-57478, Quinophthalone-based dye derivatives are described in Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2 Examples of dye derivatives include those described in Japanese Patent Publication No. 012-226110, those described in Japanese Patent Publication Nos. 2012-208329 and 2014-5439 for naphthol-based dye derivatives, those described in Japanese Patent Publication Nos. 2001-172520 and 2012-172092 for azo-based dye derivatives, those described in Japanese Patent Publication Nos. 2004-307854 for acidic substituents, and those described in Japanese Patent Publication Nos. 2002-201377, 2003-171594, 2005-181383 and 2005-213404 for basic substituents. In addition, these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but compounds having substituents such as acidic groups, basic groups, or neutral groups on the aforementioned organic dye residues are synonymous with dye derivatives.

[0079] These dye derivatives can be used individually or in combination of two or more types.

[0080] The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of pigment.

[0081] By adding a pigment derivative to a pigment and performing pigmentation treatments such as acid basting, acid slurry, dry milling, salt milling, or solvent-salt milling, the pigment derivative is adsorbed onto the pigment surface, making the primary particles of the pigment finer compared to when no pigment derivative is added.

[0082] By adding a dye derivative to the pigment and performing dispersion treatments such as wet dispersion using two-roll, three-roll, or bead-based processes, the dye derivative is adsorbed onto the pigment surface, giving the pigment surface polarity and promoting the adsorption of resin-type dispersants. This improves compatibility with the pigment, dye derivative, resin-type dispersant, solvent, and other additives, resulting in improved dispersion stability and viscosity stability over time when used in colored compositions and colored curable compositions. Furthermore, the improved compatibility leads to excellent film stability over time when colored curable compositions are coated onto glass substrates, etc., resulting in good stability and property dependence of pattern shape, etc., on the waiting time from coating to exposure (PCD: Post-Coating Delay) and the waiting time from exposure to heat treatment (PED: Post-Exposure Delay), as well as good line width sensitivity stability. In addition, the adsorption and coating of the pigment surface with the dye derivative and resin-type dispersant suppresses pigment aggregation and crystal precipitation due to sublimation when the coating film is heated and fired. Furthermore, variations in development time and development residue are also suppressed.

[0083] <Resin-type dispersant> The colored composition of the present invention preferably contains a resin-type dispersant. The resin-type dispersant should have a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and should function to stabilize the dispersion on the colorant carrier by adsorbing to the added colorant. Specifically, this includes urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof. Oily dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based materials can be used, and these can be used individually or in combination of two or more.

[0084] Preferred examples of resin-type dispersants having acidic functional groups include resin-type dispersants having aromatic carboxylic acid structures, which 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.

[0085] Particularly preferred examples of resin-type dispersants having acidic functional groups include those 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. Particularly preferred are those having a side chain containing a vinyl polymer moiety from the viewpoint of heat resistance, light resistance, and dispersion stability. 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 has a structure having a encapsulation site derived from a monoalcohol, which will be 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 a resin-type dispersant, the filterability of the colored composition is improved, foreign matter on the coating film formed by coating the colored composition is suppressed, and furthermore, when coating as a photosensitive colored composition, the resolubility of solidified material derived from the photosensitive colored composition formed in the coating apparatus in propylene glycol monomethyl ether acetate is improved. In this invention, the side chains based on the vinyl polymer moiety 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.

[0086] (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 Water, 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 A Examples include ter 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.

[0087] (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.

[0088] 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.

[0089] (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.

[0090] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The dispersant may have an ether group or a carbonyl group at the end of its main chain, improving the resolubility of the dispersant in PGMAc. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0091] 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.

[0092] 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.

[0093] (Side chains, which are vinyl polymer components) The side chains of the resin-type dispersant are obtained by polymerizing a vinyl polymerizable compound in the presence of a compound having a thiol group. 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.

[0094] Preferred examples of resin-type dispersants having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers, and urethane polymer dispersants having functional groups in their side chains that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

[0095] Furthermore, as disclosed in Japanese Patent Publication No. 2009-185277, a preferred example is the combined use of a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (which functions as a resin-type dispersant).

[0096] The resin-type dispersant is preferably used in an amount of 3 to 200% by mass relative to the total amount of colorant, and more preferably in an amount of 5 to 100% by mass from the viewpoint of film formation.

[0097] Resin-type dispersants having side chains containing vinyl polymer moieties are preferably used in an amount of about 30 to 100% by mass relative to the total amount of resin-type dispersants, and more preferably in an amount of about 50 to 90% by mass from the viewpoint of heat resistance, light resistance, developability and dispersion stability.

[0098] <Binder resin> The coloring compositions of this specification may include a binder resin. The binder resin is a resin with a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. A transmittance of 95% or more is preferred. In terms of curability, examples of binder resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins. The active energy ray curable resin may be a thermoplastic resin or thermosetting resin having an active energy ray reactive functional group. Furthermore, in terms of physical properties, an alkali-soluble resin is preferred for the binder resin from the viewpoint of developability. Alkali solubility is necessary to provide developability in the alkali development process during the production of color filters, and an acidic group is required.

[0099] Binder resins can be used alone or in combination of two or more types.

[0100] The binder resin content is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of colorant. Including an appropriate amount allows for easy film formation and facilitates obtaining good color characteristics.

[0101] <Thermoplastic resin> Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclic rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of alkali-soluble thermoplastic resins include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred in terms of improved developability, heat resistance, and transparency.

[0102] <Activated energy ray-curable alkali-soluble resin> Active energy ray-curable alkali-soluble resins preferably have ethylenically unsaturated double bonds. Ethyleneenly unsaturated double bonds can be introduced, for example, by the methods (i) and (ii) shown below. The resin undergoes three-dimensional crosslinking due to the effect of active energy rays, increasing the crosslinking density and improving chemical resistance.

[0103] [Method (i)] Method (i) involves, for example, adding a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. Then, the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0104] Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0105] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

[0106] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Furthermore, if necessary, such as increasing the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

[0107] Other monomers include the following: For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol Examples include (meth)acrylates such as methyl(meth)acrylate or ethoxypolyethylene glycol (meth)acrylate, or (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate.

[0108] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples include imidobenzoates, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimideacridine, and other N-substituted maleimides; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0109] A method similar to method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, to which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of the copolymer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0110] [Method (ii)] Method (ii) involves reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the isocyanate group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0111] Examples of ethylenically unsaturated monomers having hydroxyl groups include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferable to use a material having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0112] Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0113] Other monomers that can constitute alkali-soluble resins include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate ester group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, etc. Examples of N-substituted maleimides include cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( Examples include 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimidacridine. Examples of alkylene oxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0114] For carboxyl group-containing ethylenically unsaturated monomers, the monomers already described can be used.

[0115] Phosphate ester group-containing ethylenically unsaturated monomers are, for example, compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0116] <Alkali-soluble resin without ethylenically unsaturated double bonds> The coloring compositions of this specification may contain alkali-soluble resins that do not have ethylenically unsaturated double bonds in order to adjust the degree of curing of the coating.

[0117] In this invention, the weight-average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, and more preferably 4,000 to 20,000, in order to impart alkali-developable solubility. Furthermore, the Mw / Mn value is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, adhesion to the substrate decreases, and the exposure pattern becomes less likely to remain. If it exceeds 40,000, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. In this invention, the acid value of the alkali-soluble resin is 50 to 200 (KOH mg / g), preferably in the range of 70 to 180, and more preferably in the range of 90 to 170, in order to impart alkali-developable solubility. If the acid value is less than 50, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. If it exceeds 200, adhesion to the substrate decreases, and the exposure pattern becomes less likely to remain.

[0118] Each raw material used in the synthesis of the binder resin can be used individually or in combination of two or more types.

[0119] <Thermosetting compounds> In the present invention, a thermosetting compound can be further included in combination with a thermoplastic resin as the binder resin. When producing a color filter using the coloring composition for color filters of the present invention, the inclusion of a thermosetting compound reacts during the firing of the filter segment, increasing the crosslinking density of the coating film. This improves the heat resistance of the filter segment, suppresses pigment aggregation during the firing of the filter segment, and improves the contrast ratio.

[0120] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto. In the coloring composition for color filters of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0121] <Polymerizable compound> The colored composition of the present invention may include a polymerizable compound and a photopolymerization initiator as a photosensitive colored composition. The polymerizable compound may include monomers or oligomers that harden upon exposure to ultraviolet light or heat to produce a transparent resin.

[0122] Polymerizable compounds include, 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, and Examples include tetraerythritol 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 methylolated melamine (meth)acrylate, epoxy(meth)acrylate, and urethane acrylate, as well as (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.

[0123] (Polymerizable compounds containing acidic groups) Polymerizable compounds may contain photopolymerizable monomers having acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0124] Examples of photopolymerizable monomers 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.

[0125] (Polymerizable compound containing urethane bonds) Polymerizable compounds may contain monomers having ethylenically unsaturated bonds and urethane bonds. Examples of such monomers include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0126] 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.

[0127] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0128] Polymerizable compounds can be used alone or in combination of two or more types.

[0129] The amount of polymerizable compound 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 photosensitive colored composition. Adding an appropriate amount further improves curability and developability.

[0130] <Photopolymerization initiator> Examples of photopolymerization initiators include 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-methylthio)phenyl] Acetophenone compounds such as [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 thioxanthone ((p-p-p-p((p-p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p(((p-p(((p-p(((p-p((((p-p(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((( Triazine compounds such as lichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-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.

[0131] Photopolymerization initiators can be used alone or in combination of two or more types.

[0132] In the present invention, it is preferable that the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator.

[0133] (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 as patterns can be formed with less exposure compared to using other photopolymerization initiators.

[0134] Examples of oxime compounds include those described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2006-342166, Japanese Patent Publication No. 1653-1660, Japanese Patent Publication No. 156-162, Japanese Patent Publication No. 1653-1660, Japanese Patent Publication No. 2000-66385, Japanese Patent Publication No. 2000-80068, and Japanese Patent Publication No. 2004-534797. Examples include the compounds described in [Japanese Patent Publication No.], the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in Japanese Patent Publication No. 2017-19766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. WO2015 / 152153, the compounds described in International Publication No. WO2017 / 051680, the compounds described in Japanese Patent Publication No. 2007-210991, the compounds described in Japanese Patent Publication No. 2009-179619, the compounds described in Japanese Patent Publication No. 2010-037223, the compounds described in Japanese Patent Publication No. 2010-215575, the compounds described in Japanese Patent Publication No. 2011-020998, and the compounds described in International Publication No. WO2021 / 175855.

[0135] Examples of oxime compounds 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 compounds that are colorless or highly transparent and do not easily discolor other components.

[0136] 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.

[0137] (Oxime ester-based photopolymerization initiators having a diphenyl skeleton) [ka]

[0138] (Oxime ester photopolymerization initiator with a carbazole skeleton) [ka]

[0139] (Oxime ester photopolymerization initiator having a fluorene skeleton) [ka]

[0140] (Photopolymerization initiator having two oxime ester groups) Examples of photopolymerization initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0141] 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.

[0142] The amount of photopolymerization initiator 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 photosensitive composition. When an appropriate amount is added, the photocurability and developer resistance are improved and the surface condition is improved.

[0143] <Sensitizer> Furthermore, the photosensitive colored 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.

[0144] 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.

[0145] 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.

[0146] Sensitizers can be used alone or in combination of two or more types.

[0147] 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. Including an appropriate amount further improves curability and developability.

[0148] <Thiol-based chain transfer agents> The photosensitive colored composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive photosensitive colored composition.

[0149] 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.

[0150] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, and pen Examples include tetraerythritol 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, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0151] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0152] 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 photosensitive coloring composition. When an appropriate amount is included, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating.

[0153] <Polymerization inhibitors> The photosensitive colored composition 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.

[0154] 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.

[0155] The polymerization inhibitor content is preferably 0.01 to 0.4 parts by mass per 100% by mass of the nonvolatile content of the photosensitive 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.

[0156] <UV absorber> The photosensitive colored composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0157] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator and UV absorber. Including an appropriate amount further improves resolution after development.

[0158] Furthermore, the total content of the photopolymerization initiator and ultraviolet absorber is preferably 1 to 20% by mass of the nonvolatile content of the photosensitive colored composition. Including an appropriate amount further improves the adhesion between the substrate and the coating, resulting in good resolution.

[0159] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 5% 2-methoxy-1-methylphenyl A mixture of tyl acetate and 95% benzenepropanoic acid, 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, methyl3-(3-(2H-benzotriazole2-yl) Reaction product of (-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-4-methylpheno Examples include 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.

[0160] 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.

[0161] 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.

[0162] Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

[0163] <Antioxidant> The photosensitive colored composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive colored 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 photosensitive colored 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 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.

[0164] 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.

[0165] 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.

[0166] Antioxidants can be used alone or in combination of two or more types.

[0167] Furthermore, an antioxidant content of 0.5 to 5.0% by mass per 100% by mass of the solid content of the photosensitive colored composition is more preferable because it results in good transmittance, spectral characteristics, and sensitivity.

[0168] <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 photosensitive 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.

[0169] 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.

[0170] 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.

[0171] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0172] 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.

[0173] 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.

[0174] More specifically, 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, L S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor 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-L1 06, 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), Amito 102, 105, Examples include 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0175] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0176] More specifically, examples include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0177] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0178] More specifically, examples include Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc.

[0179] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0180] More specifically, examples include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0181] When the photosensitive colored composition of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition of the present invention. Within this range, a good balance is achieved between the applicability, pattern adhesion, and transmittance of the colored composition. The photosensitive coloring composition of the present invention may contain only one type of surfactant or two or more types. If two or more types are included, it is preferable that their total amount be within the above range.

[0182] <Storage stabilizer> The 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 colorant (100% by mass).

[0183] <Adhesion enhancer> The photosensitive colored 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 agent results in better reproduction of fine lines and improved resolution.

[0184] 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 in the coloring composition. Within this range, the effect is greater, and the balance between adhesion, resolution, and sensitivity is good, making it more preferable.

[0185] <Solvent> The colored composition of the present invention contains 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 colored composition, but also the solubility of each component of the colored composition, as well as safety.

[0186] 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 should be taken into consideration, and they should be used individually or in mixtures as appropriate according to the application conditions (speed, drying conditions, etc.).

[0187] 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.

[0188] 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.

[0189] Of the above organic solvents, for coating applications, it is preferable to include an organic solvent with a boiling point of 120°C or higher and 180°C or lower at 1 atm, 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.

[0190] <Method for producing a photosensitive composition> The photosensitive colored compositions included in the present invention can be manufactured by finely dispersing a colorant in a colorant carrier such as a dispersant and binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), using various dispersion methods such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or 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.

[0191] Furthermore, when used as a photosensitive colored composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable colored composition can be prepared by mixing the colorant dispersion with a photopolymerizable monomer and / or a photopolymerization initiator, and optionally with a solvent, other dispersion aids, and additives. The photopolymerization initiator may be added during the preparation of the colored composition, or it may be added to the prepared colored composition afterward.

[0192] <Removal of coarse particles> The photosensitive colored composition of the present invention is subjected to centrifugal separation and sintering at a gravitational acceleration of 3000 to 25000 G. It is preferable 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, by means of filtration using a filter or membrane filter. Thus, it is preferable that the colored composition substantially does not contain particles of 0.5 μm or larger. More preferably, it is preferable that the particles are 0.3 μm or smaller.

[0193] <Moisture content in colored composition> The photosensitive colored composition of the present invention preferably contains 2% by mass or less of water.

[0194] If the water content of the photosensitive coloring composition is within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0195] The water content in the photosensitive coloring composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0196] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the photosensitive colored composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate the mixture. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0197] The water content can be measured by known methods such as the Karl Fischer method.

[0198] <Amount of toluene in the colored composition> The coloring composition of the present invention may contain toluene, and if so, 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.

[0199] <Membrane> The film of the present invention is formed using the resin composition described above. The film may be used in a laminated state on a substrate, or the film may be peeled off from the substrate. The film may be a flat film or a film with a pattern, but a film with a pattern is preferred.

[0200] [Membrane manufacturing method] 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 colored composition of the present invention onto a substrate.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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 simply dried as needed.

[0205] The following describes in detail how to form the patterns.

[0206] (When forming a pattern using photolithography) When forming a pattern using photolithography, the photosensitive coloring composition of the present invention is coated onto a substrate to form a layer, which is then dried as necessary (pre-bake), exposed in a patterned manner through a mask (exposure step), the unexposed areas are removed by alkaline development (development step), and the pattern is then heat-treated as necessary (post-bake step).

[0207] [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).

[0208] [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.

[0209] [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.

[0210] (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 colored 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.

[0211] <Optical filters> The film of the present invention can be used in optical filters. For example, it can be used as a color filter, a component of a color filter in a solid-state image sensor or an organic EL display device.

[0212] <Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment. The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0213] <How to manufacture color filters>

[0214] In this specification, color filters can be used in applications such as solid-state image sensors, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays.

[0215] <Solid-state image sensor> The film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, a substrate has a plurality of photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), a light-shielding film has openings only for the light-receiving portion of the photodiodes on the photodiodes and transfer electrodes, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes, and a filter has been placed on the device protection film. Furthermore, there may be a configuration in which a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) is placed on the device protection film below the filter (closer to the substrate), or a configuration in which the light-collecting means is placed on the filter. In addition, the filter may have a structure in which a hardened film that forms each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions 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. [Examples]

[0216] The present invention will be described below based on examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" means "parts by weight".

[0217] The following examples relate to the aluminum phthalocyanine of the present invention. The phthalocyanine was identified as follows.

[0218] (Identification of phthalocyanine) The determination was made by comparing the molecular ion peaks of the mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), Bruker Daltonics) with the calculated mass numbers, and by comparing the ratios of carbon, hydrogen, and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, Perkin-Elmer) with theoretical values.

[0219] <Manufacturing of aluminum phthalocyanine> (Synthesis example 1: Phthalocyanine (P-1)) In a reaction vessel, 1250 parts n-amyl alcohol, 225 parts 3-ethoxyphthalonitrile, and 78 parts anhydrous aluminum chloride were mixed and stirred. 266 parts DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added, the mixture was heated, and refluxed at 180°C for 5 hours. The reaction solution, cooled to 30°C while stirring, was poured into a mixed solvent of 5000 parts methanol and 10000 parts water with stirring to obtain a green slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts methanol and 4000 parts water, and dried to obtain 135 parts of phthalocyanine (p1a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p1a) revealed measured values ​​of (C) 64.1%, (H) 4.4%, and (N) 15.3%, compared to the calculated values ​​of (C) 63.96%, (H) 4.29%, and (N) 14.92%, thus identifying it as the target compound. [ka]

[0220] Next, 100 parts of phthalocyanine (p1a) were added to 1200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. After stirring at 40°C for 3 hours, this sulfuric acid solution was injected into 24000 parts of cold water at 3°C. The resulting green precipitate was filtered, washed with water, and dried to obtain 92 parts of phthalocyanine (p1b) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p1b) revealed measured values ​​of (C) 65.3%, (H) 5.1%, and (N) 15.4%, compared to the calculated values ​​of (C) 65.30%, (H) 4.93%, and (N) 15.23%, thus identifying it as the target compound. [ka]

[0221] Next, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above phthalocyanine (p1b), and 60.6 parts of diphenyl phosphate were added to the reaction vessel. After reacting at 100°C for 3 hours, the solution was poured into 10,000 parts of water. The reaction product was filtered, washed with 20,000 parts of water, and dried under reduced pressure at 60°C overnight to obtain 108 parts of phthalocyanine (P-1). The obtained phthalocyanine (P-1) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0222] (Synthesis Example 2: Phthalocyanine (P-2)) The same procedure as in Synthesis Example 1 was followed, except that 190 parts of 3-ethoxyphthalonitrile and 35.0 parts of phthalodinitrile were replaced to obtain 145 parts of phthalocyanine (p2a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p2a) confirmed that it was the target compound. [ka]

[0223] Next, in a reaction vessel, 112 parts of phthalocyanine (P-2) were obtained in the same manner as in Synthesis Example 1, except that phthalocyanine (p1a) was replaced with phthalocyanine (p2a). The obtained phthalocyanine (P-2) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0224] (Synthesis example 3: Phthalocyanine (P-3)) The synthesis was carried out in the same manner as in Synthesis Example 1, except that 179 parts of 3-ethoxyphthalonitrile and 45.8 parts of phthalodinitrile were replaced, to obtain 152 parts of phthalocyanine (p3a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p3a) confirmed that it was the target compound. [ka]

[0225] Next, in a reaction vessel, 120 parts of phthalocyanine (P-3) were obtained in the same manner except that phthalocyanine (p1a) of Synthesis Example 1 was changed to phthalocyanine (p3a). For the obtained phthalocyanine (P-3), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0226] (Synthesis Example 4: Phthalocyanine (P-4)) In Synthesis Example 1, 141 parts of phthalocyanine (p4a) represented by the following chemical formula were obtained in the same manner except that 112 parts of 3-ethoxyphthalonitrile and 112 parts of phthalodinitrile were changed. For the obtained phthalocyanine (p4a), it was confirmed to be the target compound by elemental analysis. [Chemical Formula]

[0227] Next, in a reaction vessel, 120 parts of phthalocyanine (P-4) were obtained in the same manner except that phthalocyanine (p1a) of Synthesis Example 1 was changed to phthalocyanine (p4a). For the obtained phthalocyanine (P-4), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0228] (Synthesis Example 5: Phthalocyanine (P-5)) In Synthesis Example 3, 110 parts of phthalocyanine (P-5) were obtained in the same manner except that diphenyl phosphate was replaced with phenylphosphonic acid. For the obtained phthalocyanine (P-5), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0229] (Synthesis Example 6: Phthalocyanine (P-6)) In Synthesis Example 3, 115 parts of phthalocyanine (P-6) were obtained in the same manner except that diphenyl phosphate was replaced with pyridine sulfonic acid. For the obtained phthalocyanine (P-6), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0230] (Synthesis example 7: Phthalocyanine (P-7)) In Synthesis Example 3, 132 parts of phthalocyanine (P-7) were obtained in the same manner except that diphenyl phosphate was replaced with benzoic acid. The obtained phthalocyanine (P-7) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0231] (Synthesis example 8: Phthalocyanine (P-8)) In Synthesis Example 3, the procedure was carried out similarly except that 3-ethoxyphthalonitrile was replaced with 225 parts of phenoxydiphthalonitrile to obtain 115 parts of phthalocyanine (p8a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p8a) confirmed that it was the target compound. [ka]

[0232] Next, in a reaction vessel, 120 parts of phthalocyanine (P-8) were obtained in the same manner as in Synthesis Example 3, except that phthalocyanine (p3a) was replaced with phthalocyanine (p8a). The obtained phthalocyanine (P-8) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0233] (Synthesis example 9: Phthalocyanine (P-9)) In Synthesis Example 3, the procedure was the same except that 3-ethoxyphthalonitrile was replaced with 225 parts of butoxydiphthalonitrile to obtain 120 parts of phthalocyanine (p9a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p9a) confirmed that it was the target compound. [ka]

[0234] Next, in a reaction vessel, 125 parts of phthalocyanine (P-9) were obtained in the same manner as in Synthesis Example 3, except that phthalocyanine (p3a) was replaced with phthalocyanine (p9a). The obtained phthalocyanine (P-9) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0235] (Synthesis Example 10: Phthalocyanine (P-10)) The same procedure as in Synthesis Example 3 was followed, except that 3-ethoxyphthalonitrile was replaced with 225 parts of 4-ethoxyphthalonitrile to obtain 115 parts of phthalocyanine (p10a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p10a) confirmed that it was the target compound.

[0236] [ka]

[0237] Next, in a reaction vessel, 125 parts of phthalocyanine (P-10) were obtained in the same manner as in Synthesis Example 3, except that phthalocyanine (p3a) was replaced with phthalocyanine (p10a). The obtained phthalocyanine (P-10) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0238] (Synthesis Example 11: Phthalocyanine (P-11)) In Synthesis Example 3, the procedure was carried out similarly except that 3-ethoxyphthalonitrile was replaced with 225 parts of 3-hydroxydiphthalonitrile to obtain 120 parts of phthalocyanine (p11a) represented by the following chemical formula. Elemental analysis of the obtained phthalocyanine (p11a) confirmed that it was the target compound. [ka]

[0239] Next, in a reaction vessel, 125 parts of phthalocyanine (P-11) was obtained in the same manner as in Synthesis Example 3, except that phthalocyanine (p3a) was changed to phthalocyanine (p11a). For the obtained phthalocyanine (P-11), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0240] (Synthesis Example 12: Phthalocyanine (P-12)) In Synthesis Example 1, diphenyl phosphate was replaced with phenyl phosphate, and after reacting phenyl phosphate at 100 °C for 3 hours, instead of injecting this solution into 10,000 parts of water, 1,000 parts of water was slowly injected into the reaction solution over 30 minutes, and further transferred to another container and 9,000 parts of water was slowly injected over 30 minutes. In the same manner as in Synthesis Example 1, 103 parts of phthalocyanine (P-12) was obtained. For the obtained phthalocyanine (P-12), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0241] (Synthesis Example 13: Phthalocyanine (P-13)) In Synthesis Example 12, 104 parts of phthalocyanine (P-13) was obtained in the same manner except that phenyl phosphate was replaced with benzylphosphonic acid. For the obtained phthalocyanine (P-13), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0242] (Synthesis Example 14: Phthalocyanine (P-14)) In Synthesis Example 12, 107 parts of phthalocyanine (P-14) was obtained in the same manner except that phenyl phosphate was replaced with naphthyl phosphate. For the obtained phthalocyanine (P-14), a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it was identified as the target compound.

[0243] (Synthesis Example 15: Phthalocyanine (P-15)) In Synthesis Example 1, 100 parts of phthalocyanine (P-15) were obtained in the same manner except that diphenyl phosphate was replaced with p-toluenesulfonic acid. The obtained phthalocyanine (P-15) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0244] (Synthesis Example 16: Phthalocyanine (P-16)) In Synthesis Example 1, 111 parts of phthalocyanine (P-16) were obtained in the same manner except that diphenyl phosphate was replaced with 2-naphthalenesulfonic acid. The obtained phthalocyanine (P-16) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0245] (Synthesis example 17: Phthalocyanine (P-17)) In Synthesis Example 1, 99 parts of phthalocyanine (P-17) were obtained in the same manner except that diphenyl phosphate was replaced with methylphosphonic acid. The obtained phthalocyanine (P-17) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0246] (Synthesis example 18: Phthalocyanine (P-18)) In Synthesis Example 1, 97 parts of phthalocyanine (P-18) were obtained in the same manner except that diphenyl phosphate was replaced with ethylphosphonic acid. The obtained phthalocyanine (P-18) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0247] (Synthesis example 19: Phthalocyanine (P-19)) In Synthesis Example 1, 96 parts of phthalocyanine (P-19) were obtained in the same manner except that diphenyl phosphate was replaced with methyl phosphate. The obtained phthalocyanine (P-19) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0248] (Synthesis example 20: Phthalocyanine (P-20)) In Synthesis Example 1, 99 parts of phthalocyanine (P-20) were obtained in the same manner except that diphenyl phosphate was replaced with dimethyl phosphate. The obtained phthalocyanine (P-20) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0249] (Synthesis example 21: Phthalocyanine (P-21)) In Synthesis Example 1, 10¹ parts of phthalocyanine (P-21) were obtained in the same manner except that diphenyl phosphate was replaced with vinylphosphonic acid. The obtained phthalocyanine (P-21) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0250] (Synthesis example 22: Phthalocyanine (P-22)) In Synthesis Example 1, 100 parts of phthalocyanine (P-22) were obtained in the same manner except that diphenyl phosphate was replaced with phosphonic acid. The obtained phthalocyanine (P-22) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0251] (Synthesis example 23: Phthalocyanine (P-23)) In Synthesis Example 1, 92 parts of phthalocyanine (P-23) were obtained in the same manner except that diphenyl phosphate was replaced with phosphate. The obtained phthalocyanine (P-23) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0252] (Synthesis example 24: Phthalocyanine (P-24)) In Synthesis Example 1, 97 parts of phthalocyanine (P-24) were obtained in the same manner except that diphenyl phosphate was replaced with dimethylphosphinic acid. The obtained phthalocyanine (P-24) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0253] (Synthesis example 25: Phthalocyanine (P-25)) In Synthesis Example 1, 10¹ parts of phthalocyanine (P-25) were obtained in the same manner except that diphenyl phosphate was replaced with diethylphosphinic acid. The obtained phthalocyanine (P-25) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0254] (Synthesis example 26: Phthalocyanine (P-26)) In Synthesis Example 1, 103 parts of phthalocyanine (P-26) were obtained in the same manner except that diphenyl phosphate was replaced with dibutyl phosphate. The obtained phthalocyanine (P-26) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0255] (Synthesis example 27: Phthalocyanine (P-27)) In Synthesis Example 3, 10¹ parts of phthalocyanine (P-27) were obtained in the same manner except that diphenyl phosphate was replaced with phosphonic acid. The obtained phthalocyanine (P-27) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0256] (Synthesis example 28: Phthalocyanine (P-28)) In Synthesis Example 3, 103 parts of phthalocyanine (P-28) were obtained in the same manner except that diphenyl phosphate was replaced with diethylphosphinic acid. The obtained phthalocyanine (P-28) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0257] (Synthesis example 29: Phthalocyanine (P-29)) In Synthesis Example 3, 102 parts of phthalocyanine (P-29) were obtained in the same manner except that diphenyl phosphate was replaced with methylphosphonic acid. The obtained phthalocyanine (P-29) was identified as the target compound by confirming the peak corresponding to the same molecular weight from the mass spectrum.

[0258] The chemical formulas for phthalocyanines (P-1) to (P-29) are shown below.

[0259] [ka] [ka] [ka] [ka] [ka]

[0260] [Dye derivative 1] [ka]

[0261] <Manufacturing of resin-type dispersants> (Resin-type dispersant (B-1)) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 70 parts methyl methacrylate, 20 parts t-butyl methacrylate, and 10 parts methacrylic acid were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, 6.0 parts 1-thioglycerol were added, and the mixture was reacted for 12 hours. Solid content measurement confirmed that 95% of the mixture had reacted. Next, 8.5 parts pyromellitic anhydride, 115 parts propylene glycol monomethyl ether acetate (PGMAc), and 0.20 parts 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. The mixture was then diluted with propylene glycol monomethyl ether acetate to a non-volatile content of 40% to obtain a resin-type dispersant (B-1) with an acid value of 100 mg KOH / g and a weight-average molecular weight of 9000.

[0262] (Resin-type dispersant (B-2)) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged, and the vessel was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that 95% of the mixture had reacted. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 120°C for 5 hours. Subsequently, 12.1 g of 3-methoxybutanol was added and the mixture was reacted at 120°C for 3 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was complete, propylene glycol monomethyl ether acetate was added to adjust the non-volatile content to 40% by mass, yielding a resin-type dispersant (B-2) with an acid value of 110 mg KOH / g and a weight-average molecular weight of 9000.

[0263] (Resin-type dispersant (B-3)) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step (on a non-volatile content basis), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). Non-volatile content measurement confirmed that 95% of the compound had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out by IR until the disappearance of the 2270 cm-1 peak based on the isocyanate group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a resin-type dispersant (B-3) containing a side chain with a vinyl polymer moiety that is an ultraviolet crosslinking group, with a non-volatile content of 40%. The acid value of the obtained resin-type dispersant (B-3) was 68 mgKOH / g, the unsaturated double bond equivalent was 1593, and the weight-average molecular weight was 13000.

[0264] <Manufacturing of binder resin> (Binder resin) 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 the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 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 an acrylic 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. Methoxypropyl acetate was added to the previously synthesized resin solution to prepare a binder resin with a non-volatile content of 20%. The mass-average molecular weight (Mw) was 26,000.

[0265] <Evaluation of resins> (Average molecular weight (Mw) of the resin during polymerization) This is the weight-average molecular weight (Mw) in polystyrene equivalent, measured using a TSKgel column (Tosoh Corporation) and a GPC (Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, with THF as the developing solvent.

[0266] (Acid value of resin) To 0.5 to 1.0 parts of the resin solution, 80 ml of acetone and 10 ml of water were added 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 of the resin solution. 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.

[0267] <Manufacturing of coloring compositions> [Example 1] (Coloring composition (GP-1)) After stirring and mixing the mixture with the following composition 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 resulting mixture was then filtered through a 5.0 μm pore size filter to prepare a green colored composition (GP-1) with 20% by mass of nonvolatile components. Phthalocyanine (P-1): 24.0 parts Resin-type dispersant (B-1): 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 136.0 parts

[0268] [Examples 2-27, Comparative Examples 1-5] (Coloring composition (GP-2)~(GP-32)) Green colored compositions (GP-2) to (GP-32) were prepared in the same manner as in Example 1, except that phthalocyanine (P-1) was replaced with the phthalocyanine shown in Table 1. The phthalocyanines listed in the table are shown below. • PG62: Pigment Green 62, manufactured by Toyo Color Co., Ltd. • PG36: Pigment Green 36, manufactured by Toyo Color Co., Ltd. • PG58: Pigment Green 58, manufactured by DIC Corporation.

[0269] [Example 28] (Coloring composition (GP-33)) After stirring and mixing the mixture with the following composition 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"). Subsequently, the resulting mixture was filtered through a 5.0 μm pore size filter to prepare a green colored composition (GP-33) with 20% by mass of nonvolatile components. Phthalocyanine (P-13): 21.6 parts Dye derivative 1:2.4 parts Resin-type dispersant (B-1): 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 136.0 parts

[0270] [Examples 29-30] (Coloring composition (GP-34)~(GP-35)) Green colored compositions (GP-34) to (GP-35) were prepared in the same manner as in Example 28, except that the resin-type dispersant (B-1) was replaced with the resin-type dispersant shown in Table 1.

[0271] [Table 1]

[0272] A coating solution was prepared by diluting the colored compositions (GP-1) to (GP-35) with a binder resin as described below. The proportion of phthalocyanine pigment in the total solid content of the coating solution was 20% by mass. Coloring composition 33.3 parts Binder resin 66.7 parts

[0273] (Evaluation of coloring power) A coating solution obtained by diluting coloring compositions (GP-1) to (GP-35) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater. The substrate was then dried at 70°C for 20 minutes, and further heated at 230°C for 20 minutes to adjust the film thickness to 1 μm, thereby producing a coating film. In this manner, a coated substrate was obtained. The absorbance of the obtained substrate was measured using a spectrophotometer (Hitachi "U-4100") to determine its absorption spectrum, and the coloring power was evaluated from the maximum absorbance value in the 630-680 nm range. The evaluation criteria are as follows. 1.6 or higher: ◎ 1.3 or higher and less than 1.6: ○ 1.1 or higher and less than 1.3: △ Less than 1.1: ×

[0274] (Evaluation of transmittance 1) Next, the coating solution obtained by diluting the coloring compositions (GP-1) to (GP-35) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70°C for 20 minutes, and then heated at 230°C for 20 minutes to adjust the film thickness so that the transmittance at 650 nm was 10%. The transmission spectrum of this coating was measured using a spectrophotometer (Hitachi U-4100), and the transmittance at 600 nm was determined. The criteria for evaluation are as follows. This allows us to confirm whether the coloring composition has produced a good green color. 50% or more: ◎ 40% or more but less than 50%: ○ Less than 40%: ×

[0275] (spectral wavelength position) For the substrate formed in the transmittance evaluation 1 described above, the wavelength at which the transmittance was 40% in the 550-650 nm range was determined. This allows us to confirm whether a better green color is being produced. 603nm to less than 610nm: ◎ 600nm to less than 603nm, 610nm to less than 616nm: ○ Below 600nm, above 616nm: ×

[0276] (Evaluation of transmittance 2) For the substrate formed in the transmittance evaluation 1 described above, the maximum transmittance in the 520-540 nm range was determined. 93% or higher: ◎ 90% or more but less than 93%: ○ Less than 90%: ×

[0277] [Lightfastness] The substrates formed in the above-mentioned transmittance evaluation 1 were subjected to a lightfastness test by exposing them to a xenon weather meter at an illuminance of 60 W / m2 at 300-400 nm for 20 hours. The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was determined according to the following criteria. ◎: The decrease in absorbance at the maximum absorption wavelength is less than 3%. ○: The rate of decrease in absorbance at the maximum absorption wavelength is 3% or more, but less than 5%. △: The decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30%. ×: The decrease in absorbance at the maximum absorption wavelength is 30% or more.

[0278] [Heat resistance] The substrate formed in the transmittance evaluation 1 described above was heated at 250°C for 1 hour to perform a heat resistance test. The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was determined according to the following criteria. ◎: The decrease in absorbance at the maximum absorption wavelength is less than 3%. ○: The rate of decrease in absorbance at the maximum absorption wavelength is 3% or more, but less than 5%. △: The decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30%. ×: The decrease in absorbance at the maximum absorption wavelength is 30% or more.

[0279] (Dispersion stability assessment) The viscosity of the colored composition was measured on the day of preparation using an E-type viscometer (ELD-type viscometer manufactured by Toki Sangyo Co., Ltd.) at 25°C. After allowing the colored composition to stand at 40°C for 7 days from the day of preparation, the sample temperature was returned to 25°C, and the viscosity over time was measured according to the viscosity measurement method described above. The viscosity increase over time was calculated using the following formula and evaluated according to the following criteria. Viscosity increase over time = (Viscosity over time) / (Initial viscosity) × 100 (%)

[0280] Note that ◎, ○, and △ are within the range of practical usability. If it is ×, it becomes a production problem because the colored composition cannot be applied to the glass substrate under the same application conditions. Thickness increase over time: 95% or more and less than 105%: ◎ Thickening rate over time: 90% or more and less than 110%: ○ Over time, the viscosity increases by 80% or more but less than 90%, or by 110% or more but less than 120%: △ Over time, viscosity increase rate is less than 80% or more than 120%: ×

[0281] [Table 2]

[0282] [Example 31] (Coloring composition (GP-36)) After stirring and mixing the mixture with the following composition 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 resulting mixture was then filtered through a 5.0 μm pore size filter to prepare a green colored composition (GP-36) with 20% by mass of nonvolatile components. Phthalocyanine (P-1): 28.0 parts Resin-type dispersant (B-1): 30.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 142.0 parts

[0283] [Examples 32-57, Comparative Examples 6-10] (Coloring composition (GP-37)~(GP-67)) Green colored compositions (GP-37) to (GP-67) were prepared in the same manner as in Example 1, except that phthalocyanine (P-1) was replaced with the phthalocyanines shown in Table 3.

[0284] [Example 58] (Coloring composition (GP-68)) After stirring and mixing the mixture with the following composition 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 resulting mixture was then filtered through a 5.0 μm pore size filter to prepare a green colored composition (GP-68) with 20% by mass of nonvolatile components. Phthalocyanine (P-13): 25.2 parts Dye derivative 1:2.8 parts Resin-type dispersant (B-2): 15.0 parts Resin-type dispersant (B-3): 15.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 142.0 parts

[0285] [Examples 59-63] (Coloring composition (GP-69)~(GP-73)) Green colored compositions (GP-69) to (GP-73) were prepared in the same manner as in Example 58, except that phthalocyanine (P-13) was replaced with the phthalocyanine and resin-type dispersant shown in Table 3.

[0286] [Example 64] (Coloring composition (GP-74)) After stirring and mixing the mixture with the following composition 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 resulting mixture was then filtered through a 5.0 μm pore size filter to prepare a green colored composition (GP-74) with 20% by mass of nonvolatile components. Phthalocyanine (P-13): 25.2 parts Dye derivative 1:2.8 parts Resin-type dispersant (B-2): 15.0 parts Resin-type dispersant (B-3): 15.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 114.0 parts 3-Methoxy-1-butanol (3 MB): 28.0 parts

[0287] (Dispersion stability assessment) The dispersion stability of green colored compositions (GP-36) to (GP-74) was evaluated in the same manner as for green colored compositions (GP-1) to (GP-35). Thickness increase over time: 95% or more and less than 105%: ◎ Thickening rate over time: 90% or more and less than 110%: ○ Over time, the viscosity increases by 80% or more but less than 90%, or by 110% or more but less than 120%: △ Over time, viscosity increase rate is less than 80% or more than 120%: ×

[0288] [Table 3]

[0289] <Manufacturing of yellow coloring composition> (Yellow finely milled pigment (PY-1)) 200 parts of isoindoline-based yellow pigment CI Pigment Yellow 185 (BASF's "Paliotol Yellow D1155"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this mixture was added to 8 liters of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After filtering and repeatedly washing with water to remove sodium chloride and diethylene glycol, the slurry was dried at 85°C overnight to obtain finely milled yellow pigment (PY-1).

[0290] <Manufacturing of green coloring composition> [Example 65] A mixture of the following compositions was stirred and mixed until homogeneous. Then, using 0.5 mm diameter zirconia beads, the mixture was dispersed for 5 hours 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 prepare a green colored composition (GP-75). The pigment concentration in the solid content of the green colored composition (GP-75) was 60% by mass. Phthalocyanine pigment (P-1) 16.8 parts Yellow finely milled pigment (PY-1) 7.2 parts Resin-type dispersant (B-1): 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 136.0 parts

[0291] [Examples 66-91, Comparative Examples 11-15] Green colored compositions (GP-76) to (GP-106) were obtained in the same manner as in Example 65, as shown in Table 4. The pigment concentration in the solid content of the green colored compositions (GP-75) to (GP-105) was 60% by mass.

[0292] [Example 92] A mixture of the following compositions was stirred and mixed until homogeneous. Then, using 0.5 mm diameter zirconia beads, the mixture was dispersed for 5 hours 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 prepare a green colored composition (GP-107). The pigment concentration in the solid content of the green colored composition (GP-107) was 70% by mass. Phthalocyanine pigment (P-1) 19.6 parts Yellow finely milled pigment (PY-1) 5.6 parts Dye derivative 1:2.8 parts Resin-type dispersant (B-3): 30.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 142.0 parts

[0293] [Table 4]

[0294] A coating solution was prepared by diluting the colored compositions (GP-75) to (GP-106) with a binder resin as described below. The proportion of phthalocyanine pigment in the total solid content of the coating solution was 20% by mass. Coloring composition 33.3 parts Binder resin 66.7 parts

[0295] A coating solution was prepared by diluting the colored composition (GP-107) with a binder resin as described below. The proportion of phthalocyanine pigment in the total solid content of the coating solution was 20% by mass. 28.6 parts of coloring composition Binder resin 71.4 parts

[0296] (Evaluation of coloring power) A coating solution obtained by diluting coloring compositions (GP-75) to (GP-107) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater. The substrate was then dried at 70°C for 20 minutes, and further heated at 230°C for 20 minutes to adjust the film thickness to 1 μm, thereby producing a coating film. In this manner, a coated substrate was obtained. The absorbance of the obtained substrate was measured using a spectrophotometer (Hitachi "U-4100") to determine its absorption spectrum, and the coloring power was evaluated from the maximum absorbance value in the 630-680 nm range. The evaluation criteria are as follows. 1.4 or higher: ◎ 1.1 or higher and less than 1.4: ○ 0.8 or higher and less than 1.1: △ Less than 0.8: ×

[0297] (Evaluation of transmittance 1) Next, the coating solution obtained by diluting the coloring compositions (GP-75) to (GP-107) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70°C for 20 minutes, and then heated at 230°C for 20 minutes to adjust the film thickness so that the transmittance at 650 nm was 10%. The transmission spectrum of this coating was measured using a spectrophotometer (Hitachi "U-4100"), and the transmittance at 600 nm was determined. The criteria for evaluation are as follows. 50% or more: ◎ 40% or more but less than 50%: ○ Less than 40%: ×

[0298] (Evaluation of transmittance 2) For the substrate formed in the transmittance evaluation 1 described above, the maximum transmittance in the 520-540 nm range was determined. 90% or more: ◎ 80% or more but less than 90%: ○ Less than 80%: ×

[0299] [Lightfastness] The substrates formed in the above-mentioned transmittance evaluation 1 were subjected to a lightfastness test by exposing them to a xenon weather meter at an illuminance of 60 W / m2 at 300-400 nm for 20 hours. The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was determined according to the following criteria. ◎: The decrease in absorbance at the maximum absorption wavelength is less than 3%. ○: The rate of decrease in absorbance at the maximum absorption wavelength is 3% or more, but less than 5%. △: The decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30%. ×: The decrease in absorbance at the maximum absorption wavelength is 30% or more.

[0300] [Heat resistance] The substrate formed in the transmittance evaluation 1 described above was heated at 250°C for 1 hour to perform a heat resistance test. The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was determined according to the following criteria. ◎: The decrease in absorbance at the maximum absorption wavelength is less than 3%. ○: The rate of decrease in absorbance at the maximum absorption wavelength is 3% or more, but less than 5%. △: The decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30%. ×: The decrease in absorbance at the maximum absorption wavelength is 30% or more.

[0301] (Dispersion stability assessment) The dispersion stability of green colored compositions (GP-75) to (GP-107) was evaluated in the same manner as for green colored compositions (GP-1) to (GP-35). Thickness increase over time: 95% or more and less than 105%: ◎ Thickening rate over time: 90% or more and less than 110%: ○ Over time, the viscosity increases by 80% or more but less than 90%, or by 110% or more but less than 120%: △ Over time, viscosity increase rate is less than 80% or more than 120%: ×

[0302] [Table 5]

[0303] <Preparation of a photosensitive green colored composition> [Example 93] A mixture of the following compositions was stirred and mixed until homogeneous, then filtered through a 1 μm pore size filter to prepare a photosensitive colored composition (GR-1). Green coloring composition (GP-75) 73.0 parts Binder resin 1.4 parts Photopolymerizable monomer (Arronix M350, manufactured by Toagosei Co., Ltd.) 1.7 parts Photopolymerization initiator (BASF's "Irgacure OXE02") 0.13 parts Propylene glycol monomethyl ether acetate (PGMAC) 23.7 parts

[0304] [Examples 94-119, Comparative Examples 16-20] As shown in Table 6, photosensitive colored compositions (GR-2) to (GR-32) were prepared in the same manner as photosensitive colored composition (GR-1).

[0305] [Example 120] A mixture of the following compositions was stirred and mixed until homogeneous, then filtered through a 1 μm pore size filter to prepare a photosensitive colored composition (GR-1). Green coloring composition (GP-107) 90.0 parts Binder resin 1.4 parts Photopolymerizable monomer (Arronix M350, manufactured by Toagosei Co., Ltd.) 1.62 parts Photopolymerization initiator (BASF's "Irgacure OXE02") 0.10 parts Propylene glycol monomethyl ether acetate (PGMAC) 6.88 parts

[0306] [Table 6]

[0307] The photosensitive green coloring compositions (GR-1) to (GR-33) were applied to a 100mm x 100mm, 1.1mm thick glass substrate using a spin coater, adjusting the rotation speed to achieve a finished film thickness of 1μm. After drying at 70°C for 20 minutes, an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation) was used to expose the substrate through a photomask at a wavelength of 365nm to form 1.0μm square pixels at an exposure dose of 150mJ / cm². 2Pattern exposure was performed. After exposure, the coating film was paddle-developed with an organic alkaline developer for 1 minute. After paddle development, the wafer was rinsed with pure water using a spin shower for 20 seconds, and then rinsed again with pure water for 20 seconds. After that, any remaining water droplets on the wafer were blown off with high-pressure air, and the substrate was allowed to air dry to form a square pixel pattern. Then, the substrate was heated and dried at 230°C for 20 minutes to produce the substrate.

[0308] (Evaluation of coloring power) The absorbance of the obtained substrates was measured using a spectrophotometer (Hitachi "U-4100") to determine the absorption spectrum, and the coloring power was evaluated from the maximum absorbance value in the 630-680 nm range. The evaluation criteria are as follows. 1.4 or higher: ◎ 1.1 or higher and less than 1.4: ○ 0.8 or higher and less than 1.1: △ Less than 0.8: ×

[0309] (Evaluation of transmittance 1) The photosensitive green coloring compositions (GR-1) to (GR-33) were applied to a 100mm x 100mm, 1.1mm thick glass substrate using a spin coater, adjusting the rotation speed so that 10% of the finished coating film had a 650nm wavelength. After drying at 70°C for 20 minutes, an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation) was used to expose the substrate through a photomask to form 1.0μm square pixels at a wavelength of 365nm with an exposure dose of 150mJ / cm². 2 Pattern exposure was performed. After exposure, the coating film was paddle-developed with an organic alkaline developer for 1 minute. After paddle development, the wafer was rinsed with pure water using a spin shower for 20 seconds, and then rinsed again with pure water for 20 seconds. After that, any remaining water droplets on the wafer were blown off with high-pressure air, and the substrate was allowed to air dry to form a square pixel pattern. The substrate was then heated and dried at 230°C for 20 minutes to produce the final product. The transmission spectrum of the obtained substrate was measured using a spectrophotometer (Hitachi "U-4100"), and the transmittance at 600 nm was determined. The criteria for evaluation are as follows. 50% or more: ◎ 40% or more but less than 50%: ○ Less than 40%: ×

[0310] (Evaluation of transmittance 2) The transmittance at 650 nm was measured for the substrate formed in the transmittance evaluation 1 described above. Based on these measurements, the rotation speed was adjusted so that the transmittance at 650 nm was 10%, and a new substrate was fabricated using the same process. For this substrate, the maximum transmittance in the 520-540 nm range was determined. 90% or more: ◎ 80% or more but less than 90%: ○ Less than 80%: ×

[0311] [Lightfastness] The substrates formed in the above-mentioned transmittance evaluation 1 were subjected to a lightfastness test by exposing them to a xenon weather meter at an illuminance of 60 W / m2 at 300-400 nm for 20 hours. The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was determined according to the following criteria. ◎: The decrease in absorbance at the maximum absorption wavelength is less than 3%. ○: The rate of decrease in absorbance at the maximum absorption wavelength is 3% or more, but less than 5%. △: The decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30%. ×: The decrease in absorbance at the maximum absorption wavelength is 30% or more.

[0312] [Heat resistance] The substrate formed in the transmittance evaluation 1 described above was heated at 250°C for 1 hour to perform a heat resistance test. The change in absorbance at the maximum absorption wavelength between 400 and 700 nm was determined according to the following criteria. ◎: The decrease in absorbance at the maximum absorption wavelength is less than 3%. ○: The rate of decrease in absorbance at the maximum absorption wavelength is 3% or more, but less than 5%. △: The decrease in absorbance at the maximum absorption wavelength is 5% or more, but less than 30%. ×: The decrease in absorbance at the maximum absorption wavelength is 30% or more.

[0313] (Dispersion stability assessment) The dispersion stability of the photosensitive green colored compositions (GR-1) to (GR-33) was evaluated in the same manner as the green colored compositions (GP-1) to (GP-35). Thickness increase over time: 95% or more and less than 105%: ◎ Thickening rate over time: 90% or more and less than 110%: ○ Over time, the viscosity increases by 80% or more but less than 90%, or by 110% or more but less than 120%: △ Over time, viscosity increase rate is less than 80% or more than 120%: ×

[0314] [Table 7]

[0315] As described above, the phthalocyanine compound of the present invention can be used to obtain a colored composition exhibiting excellent dispersion stability, coloring power, and transmittance.

[0316] Furthermore, by using these coloring compositions, it is possible to provide color filters and sensors for image sensors that offer thinner films, improved color separation, and enhanced color reproduction.

Claims

1. A coloring composition for color filters comprising a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains a phthalocyanine compound represented by the following general formula (1). General formula (1) 【Chemistry 1】 [In the formula, R １ ~R ８ Each of these independently comprises a hydrogen atom and an alkoxyl group which may have substituents. R represents an aryloxy group which may have substituents, １ ~R ８ At least one of them is an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. M represents Al, and Z represents a monovalent ligand.

2. The above R １ ~R ８ In, the total number of an alkoxyl group which may have a substituent and an aryloxy group which may have a substituent is 1 to 4, and the above R １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ In, at least one of each is a hydrogen atom, The coloring composition for a color filter according to Claim 1.

3. The aforementioned R １ ~R ８ The coloring composition for color filters according to claim 2, wherein the total number of optionally substituted alkoxy groups and optionally substituted aryloxy groups is 1 to 2.

4. The phthalocyanine compound is The colored composition for a color filter according to claim 1, wherein when a colored composition comprising 20% ​​by mass of the phthalocyanine compound in the total solid content and a resin having a spectral transmittance of 95% or more in the entire wavelength range of 400 to 700 nm is heated at 230°C for 20 minutes and adjusted to a film thickness of 1 μm to produce a coating film, the maximum absorbance at 630 to 680 nm is 1.1 or more.

5. The coloring composition for color filters according to claim 1, further comprising a resin-type dispersant.

6. The coloring composition for color filters according to claim 1, further comprising a yellow pigment.

7. The coloring composition for color filters according to claim 1, further comprising a photopolymerization initiator.

8. The coloring composition for color filters according to claim 1, further comprising a polymerizable compound.

9. A color filter having a film formed on a substrate using a colored composition for color filters according to any one of claims 1 to 8.

10. A solid-state image sensor comprising the color filter described in claim 9.

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