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

Abstract

To provide a coloring composition capable of forming a film which has excellent storage stability and developability, and in which foreign matters are hardly generated in a high-temperature and high-humidity environment.SOLUTION: Provided is a coloring composition containing a color material (A), resin (B), and an organic solvent (C). The color material (A) contains a green color material (A1) and a blue color material (A2). The green color material (A1) contains a green color material (a1) represented by a specific general formula (1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a coloring composition used for forming a color filter used in a solid-state imaging device, an image display device, or the like. [Background technology]

[0002] In recent years, the demand for color filters used in liquid crystal displays, organic electroluminescence displays, digital cameras, smartphones, infrared sensors, etc. has been growing due to their widespread use. Color filters separate the light that passes through them, and these colors are then synthesized to form an image. For this reason, color filters are required to have high brightness, high contrast, and color reproducibility.

[0003] As colorants excellent in luminance, contrast and color reproducibility, the use of phthalocyanine compounds described in Patent Documents 1 to 4 has been investigated. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-113732 A [Patent Document 2] Patent Publication No. 2021-056382 [Patent Document 3] International Publication No. 2023 / 002875 [Patent Document 4] International Publication No. 2023 / 120268 Summary of the Invention [Problem to be solved by the invention]

[0005] As a result of extensive investigations into the phthalocyanine compounds described in Patent Documents 1 to 4, it was found that coloring compositions using these phthalocyanine compounds generate foreign matter during storage. It was also found that there are problems with development residues and foreign matter generation in films under high temperature and high humidity conditions.

[0006] An object of the present invention is to provide a coloring composition which is excellent in storage stability and developability and is capable of forming a film which is less likely to generate foreign matter in a high-temperature and high-humidity environment. [Means for solving the problem]

[0007] The present invention relates to a coloring composition comprising a colorant (A), a resin (B), and an organic solvent (C), the color material (A) includes a green color material (A1) and a blue color material (A2); The present invention relates to a coloring composition, wherein the green colorant (A1) contains a green colorant (a1) represented by the following general formula (1):

[0008] General formula (1) [ka] (In general formula (1), X1~X 16 each independently represents a hydrogen atom, a halogen atom, or -Y1-R1, where Y1 represents a divalent linking group and R1 represents a monovalent organic group. 16 At least one of them represents a halogen atom, and at least one of them represents -Y1-R1. M represents a metal atom, a metal oxide, or a metal halide. Effect of the Invention

[0009] According to the present invention, it is possible to provide a coloring composition capable of forming a film having excellent storage stability and developability and less generation of foreign matter under high temperature and high humidity conditions. The present invention also provides a film, a color filter, a solid-state imaging device, and an image display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the embodiment for carrying out the colored composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiment, and can be modified within the scope of the problem that can be solved.

[0011] In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). In this specification, a polymerizable unsaturated group is an ethylenically unsaturated double bond. As used herein, a monomer is a compound that will polymerize to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that has been polymerized to form a polymer. In this specification, for low molecular weight compounds whose molecular weight can be specified, the molecular weight is a calculated value or measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds having a molecular weight distribution, the molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit.

[0012] <Coloring composition> A coloring composition according to one embodiment of the present invention is a coloring composition comprising a colorant (A), a resin (B), and an organic solvent (C), the color material (A) includes a green color material (A1) and a blue color material (A2); The green color material (A1) is characterized in that it contains a green color material (a1) represented by the following general formula (1).

[0013] General formula (1) [ka] (In general formula (1), X1~X 16 each independently represents a hydrogen atom, a halogen atom, or -Y1-R1, where Y1 represents a divalent linking group and R1 represents a monovalent organic group. 16 At least one of them represents a halogen atom, and at least one of them represents -Y1-R1. M represents a metal atom, a metal oxide, or a metal halide.

[0014] The mechanism by which the colored composition having the above-mentioned configuration can solve the problems of the present invention is not clear, but is speculated as follows.

[0015] The green colorant (a1) represented by the general formula (1) (hereinafter, simply referred to as the green colorant (a1)) is not sufficiently dissolved in an organic solvent, and is prone to association and aggregation over time when the concentration is high or when stored at low temperature. However, when the blue colorant (A2) having a different structure from the green colorant (a1) is used in combination, the blue colorant (A2) acts on the green colorant (a1) and prevents the green colorant (a1) from associating and aggregating with itself, suppressing the generation of foreign matter during storage. It is presumed that the generation of residue due to aggregation during development and the generation of foreign matter in high temperature and high humidity environments can be suppressed by making the green colorant (a1) less likely to associate and aggregate. In addition, the blue colorant (A2) can reduce the impact on brightness and contrast.

[0016] Hereinafter, components that are or can be included in the colored composition of one embodiment will be described in detail.

[0017] Colorant The coloring composition of the present invention contains a colorant (A).

[0018] The color material (A) is not particularly limited, and examples thereof include chromatic color materials such as red color materials, yellow color materials, blue color materials, purple color materials, green color materials, and orange color materials, achromatic color materials such as white color materials and black color materials, near-infrared absorbing color materials, and fluorescent color materials. In this specification, the white colorant includes not only pure white but also light gray colorants close to white (for example, grayish white, light gray). The coloring material (A) may be either a pigment or a dye, or a pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment, or an inorganic pigment and an organic pigment may be used in combination. The pigment also includes an organic-inorganic composite.

[0019] The pigment is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle size is more preferably 10 to 70 nm.

[0020] The content of the coloring material (A) is preferably from 0.5 to 80 mass%, and more preferably from 1 to 70 mass%, in 100 mass% of the nonvolatile content of the colored composition.

[0021] (Green colorant (A1)) The colored composition of the present invention contains a green colorant (A1), and the green colorant (A1) contains a green colorant (a1) represented by the following general formula (1).

[0022] General formula (1) [ka]

[0023] In general formula (1), X1~X 16 each independently represents a hydrogen atom, a halogen atom, or -Y1-R1, where Y1 represents a divalent linking group and R1 represents a monovalent organic group. 16 At least one of them represents a halogen atom, and at least one of them represents -Y1-R1. M represents a metal atom, a metal oxide, or a metal halide.

[0024] X1~X 16Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among these, it is preferable to contain a fluorine atom from the viewpoint of color.

[0025] The number of halogen atoms is preferably 4 to 12, and more preferably 6 to 10.

[0026] When there are two or more halogen atoms, those halogen atoms may be the same or different.

[0027] The divalent linking group in Y1 is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, -NH-, etc. Among these, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0028] The monovalent organic group in R1 is not particularly limited as long as it is a group containing a carbon atom, and examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent.

[0029] The alkyl group which may have a substituent may be linear, branched, cyclic, or a combination thereof, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, etc. In addition, in the alkyl group which may have a substituent, a part of -CH2- in the alkyl group may be substituted with an oxygen atom.

[0030] The aryl group which may have a substituent may be either a single ring or a condensed ring, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group.

[0031] The heterocyclic group which may have a substituent may be either a saturated ring or an unsaturated ring, and examples thereof include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidinyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, and a thiomorpholinyl group.

[0032] When the alkyl group, aryl group, and heterocyclic group of R1 have a substituent, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, and an aryloxycarbonyl group.

[0033] When there are two or more -Y1-R1, those -Y1-R1 may be the same or different.

[0034] It is preferable that --Y1-R1 contains a group represented by the following general formula (2).

[0035] General formula (2) [ka]

[0036] In general formula (2), Z1 represents a single bond or an oxygen atom, R2 represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R3 represents a halogen atom, an alkyl group, or an alkoxy group. m is an integer of 1 to 3, and n is an integer of 0 to 2. When m is 2 or 3, multiple Z1s and R2s may be the same or different, and when n is 2, multiple R3s may be the same or different. Y1 represents a divalent linking group, and * represents a bond to the aromatic ring in general formula (1).

[0037] Z1 is preferably an oxygen atom.

[0038] The alkyl group in R2, which may have a substituent, may be linear, branched, cyclic, or a combination thereof, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group.

[0039] Examples of the aryl group in R2 which may have a substituent include a phenyl group, a naphthyl group, and a biphenyl group.

[0040] When the alkyl group and aryl group of R2 have a substituent, examples of the substituent include an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, and the like.

[0041] m is preferably 1 or 2, more preferably 1. When m=1, -CO-Z1-R2 is preferably bonded to the 3rd or 4th position relative to -Y1-, more preferably bonded to the 4th position. When m=2, the two -CO-Z1-R2 are preferably bonded to the 3rd and 5th positions or the 2nd and 4th positions relative to -Y1-, more preferably bonded to the 2nd and 4th positions.

[0042] n is preferably 0 or 1.

[0043] Formulae (2-1) to (2-12) which are specific examples of the group represented by general formula (2) are shown below. In the formulae, Y1 represents a divalent linking group, and * represents a bond. However, the present invention is not limited to these.

[0044] [ka]

[0045] X1~X 16 The number of -Y1-R1 in the formula (I) is preferably 4 to 12, and more preferably 6 to 10.

[0046] X1~X 16 X2, X3, X6, X7, X 10, X 11 , X 14 , and X 15 Of these, it is preferable that at least four of them are -Y1-R1, and all of them are -Y1-R1, and X1, X4, X5, X8, X9, and X 12 , X 13 , and X 16 It is more preferable that is a halogen atom.

[0047] Examples of the metal atom in M ​​include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.

[0048] The metal oxide for M includes oxytitanium, oxyvanadium, and the like.

[0049] Examples of the metal halide in M ​​include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride. Among these, from the viewpoints of light resistance and heat resistance, M is preferably zinc, copper, cobalt, or nickel, and more preferably zinc or copper.

[0050] The method for producing the green colorant (a1) is not particularly limited, and can be synthesized by a known method. For example, a method in which one selected from the group consisting of metals, metal oxides, and metal halides and a phthalonitrile compound are heated in an organic solvent to cause a cyclization reaction. The phthalonitrile compound can also be synthesized by a known method. Specifically, the methods described in JP-A-05-345861, JP-A-2010-077408, JP-A-2014-015542, JP-A-2023-003551, WO 2023 / 136027, etc. can be mentioned.

[0051] Specific examples of the green color material (a1) include (a1-1) to (a1-9), but the present invention is not limited to these.

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] The green color material (a1) can be used alone or in combination of two or more kinds.

[0058] The content of the green color material (a1) is preferably from 1 to 100% by mass, and more preferably from 10 to 100% by mass, in 100% by mass of the green color material (A1).

[0059] The green color material (A1) may contain a green color material other than the green color material (a1) as long as the effects of the present invention are not impaired.

[0060] The green colorant other than the green colorant (a1) is not particularly limited, and a known compound can be used. For example, 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, 63, 64, 65, 66, etc. can be mentioned. Further examples include dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, as well as lake compounds, salt-forming compounds, and polymers of these dyes. Among these, the green colorant other than the green colorant (a1) is preferably CI Pigment Green 7, 36, 58, 59, or 63 from the viewpoint of color reproducibility.

[0061] The content of the green color material (A1) is preferably from 1 to 99.9 mass %, and more preferably from 1 to 99.5 mass %, in 100 mass % of the color material (A).

[0062] (Blue color material (A2)) The coloring composition of the present invention contains a blue colorant (A2).

[0063] The blue colorant (A2) is not particularly limited, and known compounds can be used. For example, blue pigments such as 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, 79, 80, 87, and 88 can be mentioned. Further examples include blue dyes such as CI Acid Blue 1, 7, 9, 15, 18, 23, 80, 90, CI Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67, and lake compounds, salt-forming compounds, and polymers of these blue dyes. Among these, from the viewpoint of suppressing foreign matter, the blue colorant (A2) is preferably a compound having a phthalocyanine skeleton, and more preferably one or more selected from the group consisting of CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16.

[0064] From the viewpoint of luminance, the blue colorant (A2) is preferably at least one selected from the group consisting of CI Pigment Blue 15:3 and CI Pigment Blue 15:4.

[0065] The content of the blue color material (A2) is preferably from 0.1 to 100 parts by mass, and more preferably from 0.5 to 50 parts by mass, per 100 parts by mass of the green color material (a1).

[0066] The coloring composition of the present invention may contain, as the coloring material (A), a coloring material other than the green coloring material (A1) and the blue coloring material (A2).

[0067] Examples of color materials other than the green color material (A1) and the blue color material (A2) include chromatic color materials such as red color materials, yellow color materials, purple color materials, and orange color materials, and achromatic color materials such as white color materials and black color materials. Among these, it is preferable to contain a yellow colorant (A3).

[0068] (Yellow color material (A3)) The yellow colorant (A3) is not particularly limited, and known compounds can be used. 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, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139,147,150,151,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,174,175,176,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233,234,235,236, yellow pigments described in JP-A-2012-226110, and yellow pigments described in JP-A-2019-113676.

[0069] Further, examples of yellow pigments include metal azo pigments containing one or more anions selected from the group consisting of azo compounds represented by the following general formula (3) and mono-, di-, tri-, and tetraanions of azo compounds having a tautomeric structure thereof, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (4).

[0070] General formula (3) [ka]

[0071] In general formula (3), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and two R2s each independently represent -OH or -NH2.

[0072] General formula (4) [ka]

[0073] In general formula (4), three R3's each independently represent a hydrogen atom or an alkyl group.

[0074] Examples of the metal azo pigment include those described in JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, and JP-A-2022-61494.

[0075] Further examples include CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, yellow dyes having a methine structure described in JP-A-2019-073695, JP-A-2019-073696, JP-A-2019-073697, and JP-A-2019-073698, as well as lake compounds, salt-forming compounds, and polymers of these yellow dyes. Among these, the yellow colorant (A3) preferably contains one or more selected from the group consisting of CI Pigment Yellow 120, 138, 139, 150, 185, 231, and 233.

[0076] The content of the yellow color material (A3) is preferably 10 to 90 mass % in 100 mass % of the color material (A).

[0077] The mass ratio of the green color material (A1) to the yellow color material (A3) is preferably 10:90 to 90:10.

[0078] Examples of red colorants 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 , 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, 297, pigments described in JP 2014-134712 A, and pigments described in Japanese Patent No. 6368844. Further examples include dyes such as CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 150, 151, 158, 176, 183, 198, 211, 251, 216, 217, 249, 252, 257, 260, 266, and 274, as well as lake compounds, salt-forming compounds, and polymers of these dyes. Examples of purple colorants include pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61. In addition, examples of the purple colorant include dyes such as CI Basic Violet 1, 3, 7, 10, 11, 14, 16, and 25, CI Solvent Violet 8, 13, 14, 21, 27, 28, and 36, CI Acid Violet 9, 30, and 102, and CI Acid Red 51, 52, 87, 92, 94, 289, 388, and 463, as well as lake compounds, salt-forming compounds, and polymers of these dyes. Examples of orange colorants include pigments such as CI Pigment Orange 36, 38, 43, 64, 71, and 73. Examples of white colorants include CI Pigment White 1, 2, 3, 4, 5, 6, 6:1, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 18:1, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 32, and 33. Examples of black coloring materials include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0079] Further examples include near-infrared absorbing pigments, near-infrared absorbing dyes, metal pigments, hollow resin pigments, fluorescent pigments, pearl pigments, conductive pigments, and the like.

[0080] [Resin (B)] The coloring composition of the present invention contains a resin (B).

[0081] Resin (B) used mainly to disperse color material (A) is called dispersion resin, and resin (B) used mainly to impart film resistance is called binder resin. One type of resin (B) may have both the functions of dispersion resin and binder resin. Such uses of resin (B) are just examples, and resin (B) can also be used for other purposes.

[0082] The resin (B) is not particularly limited, and known compounds can be used, such as (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, urethane acrylic resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, polysiloxane resin, and cyclic olefin resin.

[0083] The weight average molecular weight of the resin (B) is preferably from 3,000 to 200,000, and more preferably from 4,000 to 150,000.

[0084] The resin (B) can be used alone or in combination of two or more kinds.

[0085] The content of the resin (B) is preferably from 1 to 70 mass %, and more preferably from 5 to 60 mass %, in 100 mass % of the nonvolatile content of the colored composition.

[0086] (Resin having an aromatic carboxyl group (B1)) From the viewpoint of storage stability and suppression of foreign matter under high temperature and high humidity environments, it is preferable that the resin (B1) contains a resin (B1) having an aromatic carboxyl group as a dispersing resin. It is presumed that the strong interaction between the aromatic ring in the green color material (a1) and the aromatic carboxyl group suppresses association and aggregation of the green color material (a1) itself. In this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring.

[0087] The aromatic carboxyl group may be contained in either the main chain or the side chain of the resin, but is preferably contained in the main chain.

[0088] The aromatic carboxyl group preferably has 1 to 4 carboxyl groups bonded to the aromatic ring.

[0089] The resin (B1) having an aromatic carboxyl group preferably contains a resin having a main chain based on an aromatic carboxylic acid ester moiety having an ester bond, which is a reaction product site between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety.

[0090] The aromatic carboxylate moiety in the main chain is obtained by a ring-opening reaction between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and an aromatic carboxyl group is generated simultaneously with the formation of an ester bond.

[0091] The vinyl polymer moiety in the side chain acts as a steric repulsion moiety and suppresses the association and aggregation of the green color material (a1). The vinyl polymer moiety in the side chain can be obtained, for example, by the following two methods. The first method is a method of copolymerizing a monomer in the presence of a compound having two or more hydroxyl groups. The compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule. The second method is a method in which a monomer is copolymerized in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and a hydroxyl group of a compound having two or more hydroxyl groups. The difference between the above two methods is whether the vinyl polymer moiety is introduced first or later by copolymerizing the monomer. Although the molecular weight may differ slightly depending on various conditions, the same compound can theoretically be synthesized if the raw materials and reaction conditions are the same.

[0092] The main chain and the side chain will be described in detail below.

[0093] [Main Chain] The aromatic carboxylate moiety can be obtained by a ring-opening reaction between an anhydride group of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups.

[0094] Examples of aromatic compounds having two or more acid anhydride groups include compounds represented by the following general formulas (5) and (6).

[0095] [ka]

[0096] In the general formula (5), n represents 1 or 2. In general formula (6), Q represents a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following general formula (7), or a group represented by the following general formula (8).

[0097] [ka]

[0098] Specific examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride. 3,3',4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-Furanetetracarboxylic dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether tert-butyl 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 dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, etc. Among these, aromatic tetracarboxylic acid dianhydrides are preferred, and pyromellitic dianhydride is more preferred.

[0099] As described above, the compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule.

[0100] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0101] The aromatic carboxylate moiety is preferably a reaction product site of 0.9 to 1.5 moles of an aromatic compound having two or more acid anhydride groups per mole of a compound having two or more hydroxyl groups. More preferably, it is a reaction product site of 1.0 to 1.3 moles of an aromatic compound having two or more acid anhydride groups per mole of a compound having two or more hydroxyl groups. Theoretically, when the aromatic compound having two or more acid anhydride groups exceeds 1 mole, the terminal becomes an acid anhydride group.

[0102] From the viewpoint of developability, it is preferable that the acid anhydride group present at the terminal of the aromatic carboxylate moiety is reacted with a monoalcohol, that is, the acid anhydride group is ring-opened by the monoalcohol to generate an alcohol ester and a carboxyl group.

[0103] Examples of the monoalcohol include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-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, and methylcyclohexanol; 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, and propylene glycol monomethyl ether; Examples of the lactate include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. Among these, from the viewpoint of developability, compounds having an ether group or a carbonyl group are preferred, and 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are more preferred. The monoalcohols may be used alone or in combination of two or more kinds.

[0104] The amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 equivalents, more preferably 1.5 to 20 equivalents, relative to 1 equivalent of the acid anhydride group in the main chain.

[0105] [Side Chain] As described above, the vinyl polymer segment can be synthesized by a method of copolymerizing a monomer in the presence of a compound having two or more hydroxyl groups, or a method of copolymerizing a monomer in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and hydroxyl groups of a compound having two or more hydroxyl groups.

[0106] Examples of the monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and the like. ) acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, or methoxypolyethylene glycol polypropylene glycol (meth)acrylate, or other linear or branched alkyl (meth)acrylates; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); (meth)acrylates having a heterocycle, such as tetrahydrofurfuryl (meth)acrylate or 3-methyl-3-oxetanyl (meth)acrylate; (meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (meth)acrylates having a carboxyl group, such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate; Vinyl such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; N-substituted (meth)acrylamide such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate; Nitriles such as (meth)acrylonitrile; styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; vinyl acetate, vinyl propionate and other vinyl fatty acids; Examples of the monomer include acidic group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0107] The vinyl polymer portion may have a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, and a blocked isocyanate group. A thermally crosslinkable group can be introduced by using a monomer having a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, a blocked isocyanate group, or the like. The polymerizable unsaturated group can be introduced, for example, by reacting a hydroxyl group present in the vinyl polymer moiety with an isocyanate group of a monomer having an isocyanate group.

[0108] A preferred method for synthesizing the resin (B1) having an aromatic carboxyl group is, for example, to radically polymerize a monomer in the presence of a compound (a) having two hydroxyl groups and one thiol group at one end, which is a compound having two or more hydroxyl groups, to generate a vinyl polymer having two hydroxyl groups at one end, and then react the resulting polymer with a tetracarboxylic dianhydride (b), which is an aromatic compound having two or more acid anhydride groups. Furthermore, when the end of the resin is an acid anhydride group, a blocking moiety derived from the monoalcohol can be introduced by reacting the resin with a monoalcohol.

[0109] [ka]

[0110] In (c), X is the reaction residue after the tetracarboxylic dianhydride (b) reacts with a hydroxyl group, Z is the reaction residue after a compound having two hydroxyl groups reacts with an acid anhydride group, and R is the residue of a monoalcohol.

[0111] The polymerization temperature of the vinyl polymer portion is preferably 40 to 150° C., more preferably 50 to 110° C. If it is 40° C. or higher, the polymerization proceeds easily, and if it is 150° C. or lower, it becomes easy to control the molecular weight.

[0112] When polymerizing the vinyl polymer portion, 0.001 to 5% by mass of a polymerization initiator can be used based on the total monomer mass of the monomers. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0113] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiators can be used alone or in combination of two or more.

[0114] The vinyl polymer portion is preferably synthesized by bulk polymerization or solution polymerization. Examples of polymerization solvents for solution polymerization include, but are not limited to, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. These polymerization solvents can be used alone or in combination of two or more.

[0115] A reaction catalyst can be used for the synthesis of the aromatic carboxylate moiety. The reaction catalyst is preferably a tertiary amine compound. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0116] For the synthesis of the aromatic carboxylate moiety, solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate can be used.

[0117] The synthesis temperature for the aromatic carboxylate moiety is preferably from 50 to 180°C, more preferably from 80 to 140°C.

[0118] The acid value of the resin (B1) having an aromatic carboxyl group is preferably from 20 to 250 mgKOH / g, more preferably from 30 to 200 mgKOH / g.

[0119] The weight average molecular weight of the resin (B1) having an aromatic carboxyl group is preferably from 3,000 to 40,000, and more preferably from 4,000 to 30,000.

[0120] The resin (B1) having an aromatic carboxyl group can be used alone or in combination of two or more kinds.

[0121] The amount of the resin (B1) having an aromatic carboxyl group is preferably from 5 to 75 mass %, and more preferably from 10 to 75 mass %, in 100 mass % of the resin (B).

[0122] (Resin not having an aromatic carboxyl group (B2)) From the viewpoint of durability, the resin (B) preferably contains, as a binder resin, a resin (B2) having no aromatic carboxyl group, in addition to the resin (B1) having an aromatic carboxyl group.

[0123] The resin (B2) having no aromatic carboxyl group is not particularly limited as long as it is a resin having no aromatic carboxyl group, and any known resin can be used.

[0124] From the viewpoint of suppressing foreign matter under high temperature and high humidity environments, the resin (B2) that does not have an aromatic carboxyl group preferably contains a resin having a polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and a polymerizable unsaturated group-containing monomer unit (b2). The polycyclic alicyclic hydrocarbon group has a high glass transition temperature and can form a highly resistant film. It is therefore presumed that the movement of the green color material (a1) is suppressed, suppressing the generation of foreign matter due to association and aggregation. Furthermore, it is presumed that the presence of a polymerizable unsaturated group causes crosslinking between resins upon exposure to suppress the movement of the green color material (a1), suppressing the generation of foreign matter due to association and aggregation.

[0125] Examples of the resin having the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and the polymerizable unsaturated group-containing monomer unit (b2) include a copolymer of a monomer forming the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and a monomer forming the polymerizable unsaturated group-containing monomer unit (b2); a copolymer obtained by reacting a compound having a polymerizable unsaturated group with a copolymer (precursor) of a monomer forming the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and another monomer copolymerizable therewith to introduce the polymerizable unsaturated group-containing monomer unit (b2); and a copolymer obtained by the method described in JP 2008-165059 A.

[0126] [Polycyclic alicyclic hydrocarbon group-containing monomer unit (b1)] Examples of monomers forming the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0127] The content of the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) is preferably from 1 to 60 mol %, and more preferably from 1 to 40 mol %, of all the structural units of the resin.

[0128] [Polymerizable unsaturated group-containing monomer unit (b2)] Methods for introducing the polymerizable unsaturated group-containing monomer unit (b2) into the resin include, for example, the following methods (i) to (iii).

[0129] <Method (i)> In the method (i), for example, a polymer (precursor) of an epoxy group-containing monomer and other monomers is first polymerized, and then a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0130] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0131] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0132] A moiety obtained by reacting an acid anhydride with a moiety obtained by adding a carboxyl group of a carboxyl group-containing monomer to an epoxy group of an epoxy group-containing monomer unit is also preferred as the polymerizable unsaturated group-containing monomer unit (b2).

[0133] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0134] <Method (ii)> In the method (ii), for example, a polymer (precursor) of a carboxyl group-containing monomer and other monomers is polymerized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0135] <Method (iii)> In the method (iii), for example, a polymer (precursor) of a hydroxyl group-containing monomer and other monomers is first polymerized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0136] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0137] The content of the polymerizable unsaturated group-containing monomer unit (b2) is preferably from 5 to 80 mol %, and more preferably from 10 to 80 mol %, of all the structural units of the resin.

[0138] The resin having the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and the polymerizable unsaturated group-containing monomer unit (b2) can contain a monomer unit other than the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and the polymerizable unsaturated group-containing monomer unit (b2). For example, a hydroxyl group-containing monomer unit (b3), an acidic group-containing monomer unit (b4), an epoxy group-containing monomer unit (b5), an aromatic ring-containing monomer unit (b6), a blocked isocyanate group-containing monomer unit (b7), and other monomer units (b8) can be mentioned. These monomer units can be contained alone or in combination of two or more kinds.

[0139] [Hydroxyl group-containing monomer unit (b3)] Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, etc. These monomers can be used alone or in combination of two or more.

[0140] [Acidic group-containing monomer unit (b4)] Examples of the acid group-containing monomer (excluding monomers having an aromatic carboxyl group) include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. These monomers can be used alone or in combination of two or more.

[0141] [Epoxy group-containing monomer unit (b5)] Examples of epoxy group-containing monomers include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, etc. These monomers can be used alone or in combination of two or more.

[0142] [Aromatic ring-containing monomer unit (b6)] Examples of aromatic ring-containing monomers include styrene, α-methylstyrene, vinylnaphthalene, phenyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate, phenol EO or PO modified (meth)acrylate, nonylphenol EO or PO modified (meth)acrylate, N-phenylmaleimide, N-benzylmaleimide, etc. These monomers can be used alone or in combination of two or more.

[0143] [Blocked isocyanate group-containing monomer unit (b7)] The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of the isocyanate group-containing monomer is protected with a compound that is eliminated by heat (hereinafter, also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C.

[0144] Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, etc. Also usable is an equimolar reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound.

[0145] Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0146] Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide. Examples of the urea compound include urea, thiourea, and ethyleneurea. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0147] The blocking agents can be used alone or in combination of two or more kinds.

[0148] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of the protection reaction and the deprotection reaction, is more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0149] Examples of the blocked isocyanate group-containing monomer include the following compounds, although the present invention is not limited thereto.

[0150] [ka]

[0151] Commercially available blocked isocyanate group-containing monomers include Karenz MOI-DEM (blocking agent desorption temperature: 85 to 95° C.), MOI-BP (blocking agent desorption temperature: 105 to 115° C.), and MOI-BM (blocking agent desorption temperature: 125 to 135° C.), all manufactured by Showa Denko Co., Ltd. These monomers can be used alone or in combination of two or more kinds.

[0152] [Other monomer units (b8)] Examples of other monomers include acrylic acid esters such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; (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; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl acetate or vinyl propionate or other vinyl fatty acids; N-substituted maleimides such as methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, and 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin; Examples of such monomers include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more kinds.

[0153] The acid value of the resin (B2) having no aromatic carboxyl group is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0154] The weight average molecular weight of the resin (B2) having no aromatic carboxyl group is preferably from 3,000 to 50,000, and more preferably from 4,000 to 40,000.

[0155] The resin (B2) having no aromatic carboxyl group can be used alone or in combination of two or more kinds.

[0156] The content of the resin (B2) having no aromatic carboxyl group is preferably from 25 to 95 mass % in 100 mass % of the resin (B).

[0157] [Organic solvent (C)] The coloring composition of the present invention contains an organic solvent (C).

[0158] The organic solvent (C) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.,

[0159] From the viewpoint of environmental aspects, the colored composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). Substantially not containing means that the content of such organic solvents in the colored composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0160] The organic solvent (C) can be used alone or in combination of two or more kinds.

[0161] The content of the organic solvent (C) is preferably an amount such that the non-volatile content of the colored composition is 5 to 95% by mass.

[0162] [Pigment derivatives having basic groups (D)] The coloring composition of the present invention further contains a pigment derivative (D) having a basic group. It is presumed that this aids the interaction between the coloring material (A) and the resin (B) and improves the storage stability and the effect of suppressing foreign matter. Note that such use of the pigment derivative (D) having a basic group is only one example, and it can also be used for other purposes.

[0163] The pigment derivative (D) having a basic group is not particularly limited, and a known compound can be used. For example, a compound having a structure in which a part of a compound having a pigment structure is substituted with a basic group can be mentioned.

[0164] Examples of compounds having a pigment structure include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazineindigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, naphthalocyanine compounds, azomethine compounds, pyrrolopyrrole compounds, azo compounds, thioindigo compounds, etc. Among these, one or more selected from the group consisting of benzimidazolone compounds, quinophthalone compounds, and phthalocyanine compounds are preferred, and phthalocyanine compounds are more preferred.

[0165] Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, etc. Examples of compounds that form salts include a hydroxide ion, a halogen ion, a carboxylate ion, a sulfonate ion, etc.

[0166] The timing of adding the pigment derivative (D) having a basic group is not particularly limited, and may be when the colorant (A) is micronized or when the colorant (A) is dispersed. The average primary particle size of the pigment derivative (D) having a basic group is preferably 1 to 200 nm.

[0167] The pigment derivative (D) having a basic group can be used alone or in combination of two or more kinds.

[0168] The content of the pigment derivative (D) having a basic group is preferably from 1 to 200 parts by mass, and more preferably from 5 to 100 parts by mass, per 100 parts by mass of the blue colorant (A2).

[0169] Specific examples of the pigment derivative (D) having a basic group are shown below, but the present invention is not limited to these.

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] [Polymerizable compound (E)] The colored composition of the present invention further contains a polymerizable compound (E).

[0174] The polymerizable compound (E) may be a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a styryl group.

[0175] The polymerizable compound (E) is not particularly limited, and a known compound can be used. For example, a polymerizable compound having an amine structure, a polymerizable compound having a hydroxyl group, a polymerizable compound having a dendrimer structure or a hyperbranch structure, a polymerizable compound having an acidic group, a polymerizable compound having a urethane bond, a lactone-modified polymerizable compound, and other polymerizable compounds can be mentioned. Among these, the polymerizable compound (E) preferably contains a polymerizable compound having an amine structure from the viewpoint of suppressing foreign matter in a high-temperature and high-humidity environment, and preferably contains one or more compounds selected from the group consisting of polymerizable compounds having a hydroxyl group and polymerizable compounds having an acidic group from the viewpoint of developability. It is more preferable to use, in combination, as the polymerizable compound (E) one or more compounds selected from the group consisting of a polymerizable compound having an amine structure, a polymerizable compound having a hydroxyl group, and a polymerizable compound having an acidic group.

[0176] The polymerizable compound (E) can be used alone or in combination of two or more kinds.

[0177] The content of the polymerizable compound (E) is preferably from 1 to 80 mass %, and more preferably from 5 to 70 mass %, in 100 mass % of the nonvolatile content of the colored composition.

[0178] (Polymerizable compound having an amine structure) The amine structure of the polymerizable compound having an amine structure includes primary amine, secondary amine, and tertiary amine. Among these, secondary amine and tertiary amine are preferable. However, the amine structure of the polymerizable compound having an amine structure does not include an amide structure, an imide structure, and a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0179] Examples of the polymerizable compound having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, and tris(2-hydroxy-3-methacryloyloxypropyl)amine, as well as a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0180] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta ...hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0181] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0182] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0183] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0184] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, the methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be mentioned.

[0185] The polymerizable compound having an amine structure may have an acidic group and / or a hydroxyl group. Examples of a method for introducing an acidic group and / or a hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after the Michael addition reaction.

[0186] The polymerizable compound having an amine structure may further have a urethane bond. The urethane bond may be introduced, for example, by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group and a polyisocyanate compound (Z).

[0187] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Polyisocyanate compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0188] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0189] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2018-517797 can be mentioned.

[0190] Examples of commercially available polymerizable compounds having an amine structure include Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383, 386, and 9906NS manufactured by Arkema.

[0191] (Polymerizable compound having a hydroxyl group) Examples of the polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid EO or PO. Examples of the acrylic acid ester include modified (meth)acrylate, isocyanuric acid EO or PO modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, and epoxy (meth)acrylate obtained by reacting an epoxy group of an epoxy compound with a carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0192] Examples of commercially available polymerizable compounds having a hydroxyl group include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., Aronix M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0193] (Polymerizable compound having a dendrimer structure or a hyperbranched structure) A compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and the compound has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

[0194] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) and SIRUS-501 (dendrimer structure, average number of acryloyl groups: 18) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18), and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), 6363 (hyperbranched structure, average number of acryloyl groups: 16), and DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials.

[0195] (Polymerizable compound having an acidic group) Examples of the polymerizable compound having an acidic group include an esterification product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; an esterification product of a polycarboxylic acid and a monohydroxyalkyl (meth)acrylate; and the like.

[0196] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0197] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0198] Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0199] Commercially available polymerizable compounds having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel Allnex Corporation.

[0200] (Polymerizable compound having urethane bond) Examples of the polymerizable compound having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.

[0201] Examples of the hydroxyl group-containing (meth)acrylate 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 (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0202] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate, as well as biuret forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0203] The polymerizable compound having a urethane bond may have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, the carboxyl group is preferred.

[0204] The method for introducing an acidic group into a polymerizable compound having a urethane bond can be, for example, by first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0205] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0206] Commercially available polymerizable compounds having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0207] (Lactone-modified polymerizable compound) The lactone-modified polymerizable compound is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethololmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0208] Commercially available lactone-modified polymerizable compounds include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0209] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (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 EO or PO modified tri(meth)acrylate, and EO isocyanuric acid. or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters such as methylolated melamine (meth)acrylic acid esters, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, acrylonitrile, and the like.

[0210] Other commercially available polymerizable compounds include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-21 manufactured by Toagosei Co., Ltd. 1B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples of such esters include EA-0200, EA-0300, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0211] Further examples include (meth)acrylates having a hydroxyl group and an acidic group, (meth)acrylates having a hydroxyl group and a urethane bond, and lactone-modified (meth)acrylates having a hydroxyl group.

[0212] [Polymerization initiator (F)] The colored composition of the present invention further contains a polymerization initiator (F).

[0213] The polymerization initiator (F) is not particularly limited, and any known compound can be used. For example, a compound that generates radicals by the action of light or heat to initiate or promote a radical polymerization reaction can be used. The polymerization initiator that generates radicals by light (hereinafter, also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals by light rays in the ultraviolet to visible light range. The polymerization initiator that generates radicals by heat (hereinafter, also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0214] Examples of the photopolymerization initiator include α-hydroxyketone compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; α-aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-[4-(morpholinophenyl)-butan-1-one; Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Examples of the quinone compounds include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

[0215] Commercially available products include Omnirad 127, 184, 1173, and 2959 manufactured by IGM Resins as α-hydroxyketone compounds, Omnirad 907, 369E, and 379EG manufactured by IGM Resins as α-aminoketone compounds, Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds, IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, Adeka Arcles N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistrys. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855 A, JP 2022-5115524 A, and the like are also included. Among these, the polymerization initiator (F) preferably contains an oxime compound from the viewpoint of suppressing foreign matter in a high-temperature and high-humidity environment, and preferably contains a compound other than an oxime compound from the viewpoint of developability. As the polymerization initiator (F), it is more preferable to use an oxime compound and a compound other than an oxime compound in combination.

[0216] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples of the organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide.

[0217] The polymerization initiator (F) can be used alone or in combination of two or more kinds.

[0218] The content of the polymerization initiator (F) is preferably from 0.1 to 20 mass %, and more preferably from 0.5 to 10 mass %, in 100 mass % of the nonvolatile content of the colored composition.

[0219] [Sensitizer (G)] The coloring composition of the present invention may contain a sensitizer (G).

[0220] The sensitizer (G) is not particularly limited, and known compounds can be used. For example, polymethine dyes such as chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, sucrose compounds, etc. Examples of suitable compounds include allylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds. Among these, thioxanthone compounds and benzophenone compounds are preferred.

[0221] Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

[0222] Examples of the benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0223] The sensitizer (G) can be used alone or in combination of two or more kinds.

[0224] The content of the sensitizer (G) is preferably from 10 to 400 parts by mass, and more preferably from 20 to 300 parts by mass, based on 100 parts by mass of the polymerization initiator (F).

[0225] [Thermosetting compound (H)] The colored composition of the present invention may contain a thermosetting compound (H).

[0226] Examples of the thermosetting compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, phenol compounds, and blocked isocyanate compounds. Among these, epoxy compounds, oxetane compounds, melamine compounds, and blocked isocyanate compounds are preferred.

[0227] (Epoxy compounds) The epoxy compound is not particularly limited, and known compounds can be used, such as polyglycidyl ether compounds of bisphenols, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone; Examples include an adduct of 2,2-bis(hydroxymethyl)-1-butanol with 1,2-epoxy-4-(2-oxiranyl)cyclohexane.

[0228] Commercially available epoxy compounds include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, and EPICLON manufactured by DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0229] The epoxy compound is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0230] The epoxy equivalent of the epoxy compound is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of an epoxy group.

[0231] The epoxy compounds can be used alone or in combination of two or more kinds.

[0232] The content of the epoxy compound is preferably from 0.5 to 20% by mass, and more preferably from 1 to 15% by mass, based on 100% by mass of the nonvolatile content of the coloring composition.

[0233] (Oxetane Compounds) The oxetane compound is not particularly limited, and known compounds can be used. For example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)] Methyl ether 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified bisphenol F(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether ethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, and the like.

[0234] Examples of commercially available oxetane compounds include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 121, 212, and 221 manufactured by Toagosei Co., Ltd., and OXBP and OXTP manufactured by Ube Industries, Ltd.

[0235] The oxetane compounds can be used alone or in combination of two or more kinds.

[0236] The content of the oxetane compound is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, in 100 mass % of the nonvolatile content of the colored composition.

[0237] (Melamine compounds) The melamine compound is a compound having a melamine ring structure, and is preferably a compound having a methylol group.

[0238] Examples of commercially available melamine compounds include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0239] The melamine compounds can be used alone or in combination of two or more kinds.

[0240] The content of the melamine compound is preferably from 0.01 to 10 mass %, and more preferably from 0.1 to 5 mass %, based on 100 mass % of the nonvolatile content of the colored composition.

[0241] (Blocked isocyanate compound) A blocked isocyanate compound is a compound obtained by reacting a compound having two or more isocyanate groups in the molecule with a blocking agent.

[0242] Examples of compounds having two or more isocyanate groups in the molecule include compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0243] Examples of the blocking agent include the above-mentioned compounds. Among these, at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds is preferred.

[0244] Examples of commercially available products include Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, and MF-K60B manufactured by Asahi Kasei Corporation; Takenate B-882, B-830, B-815N, and B-846 manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation; and BI7960, BI7961, BI7982, BI7991, BI7992, BI7950, BI7951, and BI7990 manufactured by Baxenden.

[0245] The blocked isocyanate compounds can be used alone or in combination of two or more kinds.

[0246] The content of the blocked isocyanate compound is preferably from 0.1 to 20 mass%, and more preferably from 0.5 to 15 mass%, in 100 mass% of the nonvolatile content of the colored composition.

[0247] The thermosetting compound (H) can be used alone or in combination of two or more kinds.

[0248] The content of the thermosetting compound (H) is preferably from 0.5 to 40 mass%, and more preferably from 1 to 30 mass%, in 100 mass% of the nonvolatile content of the colored composition.

[0249] [Hardening agent (curing accelerator)] The coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to assist the curing of the thermosetting compound (H). The curing agent is not particularly limited, and a known compound can be used. For example, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, etc. can be mentioned. The curing agent can be, for example, an amine compound (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), a quaternary ammonium salt compound (e.g., triethylbenzylammonium chloride, etc.), an imidazole derivative bicyclic amidine compound and its salt (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0250] The curing agents can be used alone or in combination of two or more kinds.

[0251] The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound (H).

[0252] [Thiol-based chain transfer agents (I)] The coloring composition of the present invention may contain a thiol chain transfer agent (I).

[0253] The thiol chain transfer agent (I) is not particularly limited, and known compounds can be used. For example, monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or an acidic group, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; Examples of polyfunctional thiol compounds 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 tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0254] The thiol chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0255] The content of the thiol chain transfer agent (I) is preferably from 0.5 to 10% by mass in 100% by mass of the nonvolatile content of the colored composition.

[0256] [Silane coupling agents (J)] The colored composition of the present invention may contain a silane coupling agent (J).

[0257] The silane coupling agent (J) is a compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of hydrolysis and condensation reactions. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group. Examples of the other functional groups include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, and a ureido group. In this specification, the silane coupling agent (J) is not included in the polymerizable compound (E), the thermosetting compound (H), and the thiol-based chain transfer agent (I).

[0258] The silane coupling agent (J) is not particularly limited, and known compounds can be used. For example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyl Examples of the silyl trimethoxysilane include vinyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, p-styryl trimethoxysilane, and 3-ureidopropyl trialkoxysilane.

[0259] Commercially available silane coupling agents (J) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, and KBE -1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-1048, X-12-50, etc.

[0260] The silane coupling agent (J) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0261] The polysiloxane type is a compound in which the hydrolyzable group and the other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Chemical Co., Ltd.

[0262] The organic polymer type is a silane coupling agent (J) in which the hydrolyzable group and the other functional groups are bonded to an organic polymer whose main chain is an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Chemical Co., Ltd.

[0263] The silane coupling agent (J) can be used alone or in combination of two or more kinds.

[0264] The content of the silane coupling agent (J) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the colored composition.

[0265] [Polymerization inhibitor (K)] The colored composition of the present invention may contain a polymerization inhibitor (K).

[0266] The polymerization inhibitor (K) is not particularly limited, and known compounds can be used. For example, alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl resorcinol; alkylresorcinol compounds such as resorcinol, 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 tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

[0267] The polymerization inhibitor (K) can be used alone or in combination of two or more kinds.

[0268] The content of the polymerization inhibitor (K) is preferably from 0.01 to 0.5% by mass in 100% by mass of the nonvolatile content of the colored composition.

[0269] [Ultraviolet absorber (L)] The colored composition of the present invention may contain an ultraviolet absorber (L).

[0270] The ultraviolet absorber (L) is not particularly limited, and known compounds can be used, such as benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0271] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl) -4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzo triazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0272] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA CORPORATION, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0273] 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 product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0274] Examples of commercially available products include KEMISORB102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adeka STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0275] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-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.

[0276] Examples of commercially available products include KEMISORB10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adeka STAB 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0277] Examples of the salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0278] The content of the ultraviolet absorber (L) is preferably from 0.1 to 5.0% by mass in 100% by mass of the nonvolatile content of the colored composition.

[0279] [Antioxidants (M)] The colouring composition of the present invention may contain an antioxidant (M).

[0280] The antioxidant (M) is not particularly limited, and known compounds can be used. For example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds can be mentioned. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0281] Examples of the hindered phenol antioxidant include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-butane, 4,4'-butylidene-bis-(2-tert-butyl-5-methylphenol), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t ert-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester , 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine , 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,6-di-tert-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and the like.

[0282] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0283] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi 1,2,2,6,6-pentamethyl-4-pyridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-Hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0284] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd., and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0285] Examples of phosphorus-based antioxidants include di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphonite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidenedipheno tris(diphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(biphenyl) phosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, hexatridecyl 1,1,3-tri Examples of such phosphite include bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-tert-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-tert-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite.

[0286] Examples of commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0287] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0288] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0289] The antioxidants (M) can be used alone or in combination of two or more kinds.

[0290] The content of the antioxidant (M) is preferably from 0.1 to 5.0% by mass in 100% by mass of the nonvolatile content of the colored composition.

[0291] [Leveling agent (N)] The coloring composition of the present invention can contain a leveling agent (N).

[0292] The leveling agent (N) is not particularly limited, and known compounds can be used. For example, silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, acetylene diol-based leveling agents, etc. can be mentioned.

[0293] Examples of commercially available silicone leveling agents include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd.; FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Toray Dow Corning Co., Ltd.; Examples of such products include 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, and KP-341 manufactured by Chemical Industry Co., Ltd.; TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik Corporation; and MEGAFACE EFS-131, EFS-321, EFS-521, and EFS-801 manufactured by DIC Corporation.

[0294] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, and RS-72-K manufactured by DIC Corporation, FC-4430 and 4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by Neos Corporation.

[0295] Commercially available acrylic leveling agents include, for example, BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie Co., Ltd., and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0296] Commercially available acetylene diol leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0297] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0298] The content of the leveling agent (N) is preferably from 0.001 to 2.0 mass %, and more preferably from 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the colored composition.

[0299] [Storage stabilizer (O)] The coloring composition of the present invention may contain a storage stabilizer (O).

[0300] The storage stabilizer (O) is not particularly limited, and known compounds can be used, such as quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine and tetraphenyl, and phosphites.

[0301] The content of the storage stabilizer (O) is preferably from 0.05 to 5.0% by mass in 100% by mass of the nonvolatile content of the colored composition. [Other components (P)] The coloring composition of the present invention may contain components other than those described above (hereinafter, also referred to as other components (P)). Examples of the other components (P) include pigment derivatives that do not have a basic group (for example, pigment derivatives that have a neutral group, pigment derivatives that have an acidic group, etc.), acid generators, salt generators, curing catalysts, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, insulating materials, etc. The content of the other components (P) may be appropriately set within a range that does not impair the effects of the present invention.

[0302] [Specific metal element content] The colored composition of the present invention preferably has a total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) of 500 mass ppm or less.

[0303] A coloring composition in which the total amount of the specific metal elements is within the above range has excellent dispersion stability and sensitivity even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0304] [Water content] The colored composition of the present invention preferably has a water content of 2.0% by mass or less.

[0305] A coloring composition having a water content within the above range has excellent storage stability. The water content can be measured by a known method such as the Karl Fischer method.

[0306] [Method of producing colored composition] The coloring composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the coloring composition, the components may be mixed at once, or each component may be dissolved or dispersed in an organic solvent (C) and then mixed successively. For example, a coloring material (A), a resin (B), an organic solvent (C), a pigment derivative having a basic group (D), etc. are added and dispersed. Then, if necessary, a polymerizable compound (E), a polymerization initiator (F), etc. are blended and mixed to produce the composition. The timing of blending each material is arbitrary. The dispersion process can also be performed multiple times.

[0307] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0308] The average dispersed particle size (secondary particle size) of the particles in the coloring composition is preferably from 30 to 200 nm, more preferably from 40 to 200 nm. If the particles have an appropriate particle size, a coloring composition having high dispersion stability is easily obtained.

[0309] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasonic waves immediately after sample preparation, as this tends to give results with less variation.

[0310] The coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0311] The colored composition of the present invention is preferably used for forming a pattern by a photolithography method, although the present invention is not limited thereto.

[0312] <Membrane> The film of the present invention is a film formed from the above-mentioned coloring composition. The film is preferably a patterned film, but may also be used as a flat film without forming a pattern.

[0313] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced through a step of applying the coloring composition of the present invention onto a substrate and a step of drying the applied composition.

[0314] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or a CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0315] The coating method is not particularly limited, and any known method can be used, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0316] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0317] [Drying process] The method for drying the film applied to the substrate is not particularly limited, and any known method can be used, such as reduced pressure drying using a vacuum drying device, heat drying using a hot plate, an IR oven, a convection oven, or a combination of these methods.

[0318] The drying temperature and time can be appropriately adjusted. The drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 5 seconds to 5 minutes.

[0319] Next, a pattern is formed. Examples of a method for forming a pattern include a photolithography method and a dry etching method. Among these, a photolithography method is preferable. Note that, when the film is used as a flat film, the step of forming a pattern is not necessary.

[0320] The method for forming the pattern will now be described in detail.

[0321] When a pattern is formed by a photolithography method, for example, the coloring composition of the present invention is applied onto a substrate, and a layer formed by drying is exposed to light in a pattern through a mask (exposure process), and the unexposed parts are removed with an alkaline developer (development process), and then the pattern is heat-treated (post-bake process).

[0322] [Exposure process] In the exposure process, the layer formed by coating and drying is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. 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). When using light with a specific wavelength, an optical filter can also be used. In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure). In addition, a plurality of active energy rays may be used in combination, or exposure may be performed in a plurality of steps.

[0323] [Development process] Next, an alkaline development process is carried out, whereby the unexposed portions of the layer are dissolved in an alkaline developer, and only the hardened portions remain, yielding a patterned film. Examples of the alkaline developer include aqueous solutions containing 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, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Two or more of these alkaline compounds can be used in combination. The alkaline developer may contain a surfactant and an organic solvent in addition to the alkaline compound and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0324] [Post-bake process] After development, a heat treatment (post-baking) is performed, which improves the resistance of the film. The temperature is preferably 100 to 300° C., more preferably 180 to 260° C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element as the light-emitting layer is used, or from the viewpoint of the environment, the temperature is preferably 180° C. or less.

[0325] <Color filters> The color filter of the present invention has the above-mentioned film. The color filter of the present invention can be produced in the same manner as the above-mentioned film.

[0326] <Solid-state imaging element> The solid-state imaging device of the present invention has the above-mentioned color filter. The solid-state imaging device is not particularly limited as long as it has the color filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0327] The color filter of the present invention is provided on the device protective film. The color filter may be ... An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0328] <Image display device> The image display device of the present invention has the above-mentioned color filter. The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, liquid crystal displays, organic EL displays, quantum dot displays, micro LED displays, etc. are included. For example, liquid crystal displays have the following configurations.

[0329] The liquid crystal display includes a color filter, a counter substrate having a TFT array substrate or the like, and a liquid crystal layer formed between the color filter and the counter substrate. Examples of driving methods for liquid crystal displays include the TN method, the IPS method, the OCB method, and the MVA method. The counter substrate can be appropriately selected according to the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropy and mixtures thereof according to the driving method.

[0330] Specifically, it is described in "Next Generation Liquid Crystal Display Technology" (by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994), "Electronic Display Devices" (by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0331] The color filter of the present invention can be used in devices other than solid-state imaging devices and image display devices, such as infrared sensors. EXAMPLES

[0332] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0333] Before going into the examples, the measurement methods and the raw materials used will be described.

[0334] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are measured as follows.

[0335] (Molecular weight) Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0336] (Acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of sample solution, and the solution was stirred to dissolve uniformly. The solution was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) was measured. The acid value per unit of nonvolatile content was calculated from the acid value of the solution and the concentration of nonvolatile content in the solution.

[0337] (amine value) The amine value is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074 and converted into non-volatile content.

[0338] <Production of Colorant (A)> (Green colorant (a1-1)) In a flask equipped with a stirrer, condenser, dropping funnel, and thermometer, 5.0 parts of tetrafluorophthalonitrile, 2.9 parts of potassium fluoride, and 10 parts of acetone were added and stirred at room temperature until dissolved. After cooling with ice, an acetone solution of 6.65 parts of ethyl p-hydroxybenzoate was added dropwise from the dropping funnel over 2 hours, and the mixture was stirred for another 2 hours. After that, the mixture was stirred for about 12 hours while the temperature was raised to room temperature. After the reaction was completed, the reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and dried in vacuum to obtain the following intermediate 1.

[0339] Intermediate 1 [ka]

[0340] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 6.2 parts of intermediate 1, 1.21 parts of zinc iodide, and 12 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned green color material (a1-1).

[0341] (Green colorant (a1-2)) In a flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, 10.8 parts of tetrafluorophthalonitrile, 6.9 parts of potassium fluoride, and 25 parts of acetone were added and stirred at room temperature until dissolved. After cooling with ice, 25.4 parts of 3-chloro-4-hydroxybenzoic acid methoxyethyl ester dissolved in acetone was added dropwise from the dropping funnel over 2 hours, and the mixture was stirred for another 2 hours. After that, the mixture was stirred for about 12 hours while raising the temperature to room temperature. The reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 2.

[0342] Intermediate 2 [ka]

[0343] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 15.0 parts of intermediate 2, 1.93 parts of zinc iodide, and 23 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned green color material (a1-2).

[0344] (Green colorant (a1-3)) In a flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, 5.0 parts of tetrafluorophthalonitrile, 3.4 parts of potassium carbonate, and 100 parts of acetone were added and stirred at room temperature until dissolved. After cooling with ice, an acetone solution of 7.5 parts of p-chlorophenol was added dropwise from the dropping funnel over 2 hours, and the mixture was stirred for another 2 hours. After that, the mixture was stirred for about 12 hours while the temperature was raised to room temperature. The reaction liquid was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 3.

[0345] Intermediate 3 [ka]

[0346] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 6.0 parts of intermediate 3, 1.38 parts of zinc iodide, and 15 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned green color material (a1-3).

[0347] (Green colorant (a1-4)) In a flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, 10.0 parts of tetrafluorophthalonitrile and 40 parts of acetone were added and stirred at room temperature until dissolved. After cooling with ice, a mixed solution of 13.3 parts of octanol, 100 parts of tetrahydrofuran, and 11.6 parts of potassium tert-butoxide was added dropwise from the dropping funnel over 2 hours, and the mixture was stirred for another 2 hours. After that, the mixture was stirred for about 12 hours while raising the temperature to room temperature. The reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 4.

[0348] Intermediate 4 [ka]

[0349] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 4.21 parts of intermediate 4, 0.96 parts of zinc iodide, and 10 parts of benzonitrile were added, and the mixture was stirred under a nitrogen stream at 160°C for 10 hours to react. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned green color material (a1-4).

[0350] (Green colorant (a1-5)) In a flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, 20.0 parts of tetrafluorophthalonitrile, 150 parts of ethanol, and 20 parts of tetrahydrofuran were added and stirred at room temperature until dissolved. After cooling with ice, an ethanol solution of 6.6 parts of potassium hydroxide was added dropwise from the dropping funnel over 1 hour, and the mixture was stirred for another 1 hour. The reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and dried in vacuum to obtain the following intermediate 5.

[0351] Intermediate 5 [ka]

[0352] In a flask equipped with a stirrer, condenser, dropping funnel, and thermometer, add 10.1 parts Intermediate 5, 2.88 parts of potassium fluoride, and 50 parts of acetone were added and stirred at room temperature until dissolved. After cooling on ice, an acetone solution of 7.46 parts of ethyl p-hydroxybenzoate was added dropwise from the dropping funnel over 2 hours, and the mixture was stirred for another 2 hours. The mixture was then stirred for about 12 hours while the temperature was raised to room temperature. The reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and dried in a vacuum to obtain the following intermediate 6.

[0353] Intermediate 6 [ka]

[0354] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 12.4 parts of intermediate 6, 3.2 parts of zinc iodide, and 23 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned green color material (a1-5).

[0355] <Production of Resin (B)> (Resin (B1-1) solution having aromatic carboxyl group) In a flask equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc), and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, calculated as non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-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, and the flask was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged, and IR showed that 2,270 cm3 based on the isocyanate group was obtained. -1The reaction was continued until the disappearance of the peak was confirmed (third step). After cooling, PGMAc was added so that the non-volatile content was 30 mass%, to prepare a resin (B1-1) solution having an aromatic carboxyl group. The molar ratio of pyromellitic dianhydride / 3-mercapto-1,2-propanediol was 0.8, the acid value was 68 mgKOH / g, and the weight average molecular weight was 13,000.

[0356] (Resin (B1-2) solution having aromatic carboxyl group) In a flask equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 20.0 parts of tert-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, 5.0 parts of methacrylic acid, and 25.0 parts of PGMAc were charged and replaced with nitrogen gas. The flask was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution in which 0.1 parts of 2,2'-azobisisobutyronitrile was dissolved in 45.7 parts of PGMAc was added and reacted for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride, 38.0 parts of PGMAc, 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. Then, 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 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a resin (B1-2) solution having an aromatic carboxyl group was prepared. The pyromellitic dianhydride / 3-mercapto-1,2-propanediol ratio was 1.2 (molar ratio), the acid value was 105 mg KOH / g, and the weight average molecular weight was 9,500.

[0357] (Resin (B1-3) solution having aromatic carboxyl group) A flask equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The flask was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a resin (B1-3) solution having aromatic carboxyl groups was prepared. The molar ratio of pyromellitic dianhydride / 3-mercapto-1,2-propanediol was 0.78, the acid value was 70 mgKOH / g, and the weight average molecular weight was 8,500.

[0358] (Resin (B2-1) solution not having aromatic carboxyl group) A flask equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 80.0 parts of PGMAc and substituted with nitrogen gas. The flask was heated to 90°C, and a mixture of 62.5 parts of methacrylic acid, 37.5 parts of n-butyl methacrylate, 4.0 parts of 2-mercaptoethanol, 30 parts of PGMAc, and 1.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1.5 hours. After the dropwise addition, the mixture was stirred at 90°C for 3 hours. Next, the flask was replaced with air, cooled to 80°C, and 8.74 parts of 2-methacryloyloxyethyl isocyanate, 0.13 parts of dibutyltin dilaurate, 0.13 parts of p-methoxyphenol, and 10 parts of PGMAc were added and stirred for 3 hours to obtain macromonomer a. A flask equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of PGMAc and substituted with nitrogen gas. The flask was heated to 90°C, and a mixture of 161.1 parts of macromonomer a (non-volatile content 80% by mass), 20.1 parts of methacrylic acid, 2.7 parts of n-dodecyl mercaptan, 40 parts of PGMAc, and 1.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1.5 hours. After the dropwise addition, the mixture was stirred at 90°C for 3 hours. Next, a mixture of 0.1 parts of 2,2'-azobisisobutyronitrile and PGMAc was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 90°C for 1 hour. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, to prepare a resin (B2-1) solution not having an aromatic carboxyl group. The acid value was 128 mgKOH / g and the weight average molecular weight was 13,500.

[0359] (Resin (B2-2) solution not having aromatic carboxyl group) According to WO 2016 / 103994, a solution of the following copolymer resin (B2-2) without aromatic carboxyl groups was prepared by adding PGMAc so that the non-volatile content was 30% by mass. The acid value was 51.7 mg KOH / g and the weight average molecular weight was 13,000. The value written next to the repeating unit of the main chain is the molar ratio, and the value written next to the repeating unit of the side chain is the number of repeating parts.

[0360] [ka]

[0361] (Resin (B2-3) solution not having aromatic carboxyl group) According to WO 2016 / 103994, a solution of the following copolymer resin (B2-3) without aromatic carboxyl groups was prepared by adding PGMAc so that the non-volatile content was 30% by mass. The acid value was 58.2 mg KOH / g and the weight average molecular weight was 10,000. The value written next to the repeating unit of the main chain is the molar ratio, and the value written next to the repeating unit of the side chain is the number of repeating parts.

[0362] [ka]

[0363] (Resin (B2-4) solution not having aromatic carboxyl group) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirrer was charged with 200 parts of propylene glycol monomethyl ether, and the flask was heated to 120°C while injecting nitrogen gas into the flask. At the same temperature, a mixture of 56.86 parts of glycidyl methacrylate, 66.09 parts of dicyclopentanyl methacrylate, and 31.25 parts of styrene, and a polymerization initiator dissolved in 5.0 parts of azobisisobutyronitrile PGMAc were dropped from the dropping tube over 2.5 hours to carry out a polymerization reaction. After the dropwise addition was completed, the mixture was stirred at 120°C for another 2 hours to carry out the reaction. Next, the atmosphere in the flask was replaced with air, and 28.82 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, followed by stirring at 120° C. for 5 hours to carry out the reaction. Further, 32.0 parts of succinic anhydride and 0.5 parts of triethylamine were added, and the mixture was reacted at 120° C. for 4 hours with stirring. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-4) having no aromatic carboxyl group. The acid value was 77 mgKOH / g, and the weight average molecular weight was 10,000.

[0364] (Resin (B2-5) solution not having aromatic carboxyl group) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirrer was charged with 196 parts of PGMAc, the temperature was raised to 80°C, and the flask was replaced with nitrogen. From the dropping tube, a mixture of 20.2 parts of methacrylic acid, 21.8 parts of 2-hydroxyethyl methacrylate, 38.9 parts of Aronix M-110 (manufactured by Toagosei Co., Ltd., paracumylphenol ethylene oxide modified acrylate), 35.8 parts of n-butyl methacrylate, 39.0 parts of benzyl methacrylate, and 1.0 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-5) having no aromatic carboxyl group. The acid value was 81 mgKOH / g, and the weight average molecular weight was 28,000.

[0365] <Production of Yellow Dispersion> (yellow dispersion 1) 15.00 parts of yellow colorant (A3-1), 30.00 parts of resin (B1-2) solution having aromatic carboxyl group, 1.00 parts of pigment derivative (D-1) having basic group, and 54.00 parts of organic solvent (C-1) were added and stirred until uniform. Then, the mixture was dispersed for 3 hours using zirconia beads having a diameter of 0.5 mm in an Eiger mill (Eiger Japan Co., Ltd. "Mini Model M-250 MKII") and filtered through a filter with a pore size of 1.0 μm. The non-volatile content was 25.0 mass%.

[0366] (yellow dispersion 2~7) Yellow Dispersions 2 to 7 were prepared in the same manner as Yellow Dispersion 1, except that the raw materials and amounts were changed as shown in Table 1.

[0367] [Table 1]

[0368] The raw materials listed in Table 1 are as follows.

[0369] Colorant (Yellow color material (A3)) A3-1: CI Pigment Yellow 138 A3-2: CI Pigment Yellow 139 A3-3: CI Pigment Yellow 150 A3-4: CI Pigment Yellow 185

[0370] [Pigment derivatives having basic groups (D)] D-1: The following compound D-2: The following compound

[0371] [ka]

[0372] [Organic solvent (C)] C-1: Propylene glycol monomethyl ether acetate

[0373] <Production of Colored Composition> [Example 1] (Coloring composition 1) 20.00 parts of green colorant (a1-1) represented by general formula (1), 1.75 parts of blue colorant (A2-2), 4.17 parts of resin (B1-2) solution having aromatic carboxyl group, 0.13 parts of pigment derivative (D-3) having basic group, and 69.50 parts of organic solvent (C-1) were added and stirred until homogeneous. Then, the mixture was dispersed for 3 hours using zirconia beads having a diameter of 0.5 mm with an Eiger mill (Eiger Japan "Mini Model M-250 MKII"). Next, 89.50 parts of yellow dispersion 1, 29.67 parts of resin (B2-4) solution not having aromatic carboxyl group, 8.33 parts of resin (B2-5) solution not having aromatic carboxyl group, 15.00 parts of polymerizable compound (E), 3.00 parts of polymerization initiator (F), 0.10 parts of leveling agent (N), and organic solvent (C) were added so that the non-volatile content of colored composition 1 was 15% by mass, and the mixture was stirred and mixed uniformly, and then filtered through a filter with a pore size of 1.0 μm. In Table 2, the raw materials are listed separately. In addition, organic solvent (C-1) was listed in addition to organic solvent (C).

[0374] [Examples 2 to 25 and Comparative Example 1] (Coloring composition 2-26) Colored compositions 2 to 26 were produced in the same manner as in Example 1 using the raw materials and amounts shown in Tables 2-1 to 2-3.

[0375] [Table 2-1]

[0376] [Table 2-2]

[0377] [Table 2-3]

[0378] The respective raw materials listed in Tables 2-1 to 2-3 are as follows.

[0379] Colorant (Blue color material (A2)) A2-1: CI Pigment Blue 15:2 A2-2: CI Pigment Blue 15:3 A2-3: CI Pigment Blue 15:4 A2-4: CI Pigment Blue 15:6 A2-5: CI Pigment Blue 16

[0380] [Resin (B)] (Resin not having an aromatic carboxyl group (B2)) B2-6: BYK-LPN6919 (BYK-Chemie, acrylic resin having a basic group with an amine value of 120 mg KOH / g, non-volatile content 60% by mass)

[0381] [Organic solvent (C)] C-1: Propylene glycol monomethyl ether acetate C-2: Cyclohexanone C-3: Ethyl 3-ethoxypropionate C-4: Propylene glycol monomethyl ether The above C-1, C-2, C-3, and C-4 were mixed in a mass ratio of 7:1:1:1 to obtain an organic solvent (C).

[0382] [Pigment derivatives having basic groups (D)] D-3: The following compound D-4: The following compound

[0383] [ka]

[0384] [Polymerizable compound (E)] E-1: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) E-2: Aronix M-520 (manufactured by Toagosei Co., Ltd., a multifunctional acrylate with acidic groups) E-3: CN9906NS (Arkema, multifunctional acrylate with amine structure) As described above, E-1, E-2, and E-3 were mixed in a mass ratio of 6:3:1 to obtain a polymerizable compound (E).

[0385] [Polymerization initiator (F)] F-1: The following compound F-2: The following compound F-3: The following compound The above F-1, F-2, and F-3 were mixed in a mass ratio of 4:4:2 to obtain a polymerization initiator (F).

[0386] [ka]

[0387] [Leveling agent (N)] N-1: BYK-330 (BYK-Chemie, silicone-based leveling agent) N-2: Megafac F-554 (DIC, fluorine-based leveling agent) The above N-1 and N-2 were mixed in a mass ratio of 5:5 to obtain a leveling agent (N).

[0388] [Other components (P)] The following compounds (pigment derivatives having an acidic group)

[0389] [ka]

[0390] <Evaluation of Coloring Composition> The following evaluations were carried out for the obtained colored compositions 1 to 26. The evaluation results are shown in Table 3.

[0391] [Storage stability evaluation (1): Viscosity] The obtained colored composition was placed in a sealed container and subjected to 12 cycles of temperature increase and decrease, 12 hours at 40°C and 12 hours at -10°C. The rate of change in viscosity before and after storage was calculated and evaluated using the following formula. The viscosity was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. The evaluation criteria are as follows, with 3 or more being considered practical. [Change rate of viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 5: The rate of change was less than 3%. 4: The rate of change was 3% or more but less than 6%. 3: The rate of change was 6% or more but less than 9%. 2: The rate of change was 9% or more but less than 12%. 1: The rate of change was 12% or more.

[0392] [Storage stability evaluation (2): Foreign matter] The obtained coloring composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm so that the film thickness after drying would be 2.0 μm, and dried on a hot plate at 70° C. for 2 minutes. Reflected light observation was performed using an optical microscope at a magnification of 200 times to confirm that the film made from the coloring composition before storage had no foreign matter. The colored composition was placed in a sealed container and subjected to 12 cycles of temperature rise and fall at 40°C for 12 hours and at -10°C for 12 hours. The colored composition after storage was then coated in the same manner as before storage, and the reflected light was observed using an optical microscope at a magnification of 200 times to count the number of foreign particles on the film. The evaluation criteria are as follows, with 3 or more being considered practical. 5: There were less than 5 foreign bodies smaller than 1 μm per 1 mm square. 4: There were 5 to less than 10 foreign bodies smaller than 1 μm per 1 mm square. 3: There were 10 to 15 foreign objects smaller than 1 μm per 1 mm square. 2: There were 15 to less than 20 foreign objects smaller than 1 μm per 1 mm square. 1: There were more than 20 aggregates smaller than 1 μm per 1 mm square.

[0393] [Development residue evaluation] The obtained colored composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70° C. for 2 minutes. Next, using an ultra-high pressure mercury lamp, the colored composition was irradiated with light at an illumination intensity of 30 mW / cm through a photomask with a stripe pattern of 100 μm width. 2 , 50mJ / cm 2The substrate was then spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development. The amount of residue remaining in the unexposed areas was measured using a scanning electron microscope at a magnification of 20,000 times. The evaluation criteria are as follows, with a rating of 3 or higher being considered practical. 5: No residue was found in the unexposed area. 4: 1 to 5 residues were found in a 1.0 μm square area in the unexposed area. 3: 6 to 10 residues were observed in an area of ​​1.0 μm square in the unexposed area. 2: 11 to 20 residues were observed in an area of ​​1.0 μm square in the unexposed area. 1: 21 or more residues were observed in an area of ​​1.0 μm square in the unexposed area.

[0394] [High temperature and humidity resistance evaluation] The obtained colored composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70° C. for 2 minutes. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm. 2 , exposure dose 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was heated in a clean oven at 230°C for 30 minutes. Reflected light observation was performed using an optical microscope at a magnification of 200 times to confirm that there were no foreign objects in the film before storage. The obtained substrate was stored for 336 hours under conditions of a temperature of 80°C and a humidity of 85%. After storage, the reflected light was observed using an optical microscope at a magnification of 200 times, and the number of foreign particles on the film was counted. The evaluation criteria are as follows, with 3 or more being practical. 5: There were less than 5 foreign bodies smaller than 1 μm per 1 mm square. 4: There were 5 to less than 10 foreign bodies smaller than 1 μm per 1 mm square. 3: There were 10 to 15 foreign objects smaller than 1 μm per 1 mm square. 2: There were 15 to less than 20 foreign objects smaller than 1 μm per 1 mm square. 1: There were more than 20 aggregates smaller than 1 μm per 1 mm square.

[0395] [Table 3]

Claims

1. A coloring composition comprising a colorant (A), a resin (B), and an organic solvent (C), The color material (A) includes a green color material (A1) and a blue color material (A2), The coloring composition, wherein the green colorant (A1) contains a green colorant (a1) represented by the following general formula (1): General formula (1) 【Chemistry 1】 (In general formula (1), X １ ~X １６ each independently represents a hydrogen atom, a halogen atom, or -Y １ -R １ represents Y １ represents a divalent linking group, R １ represents a monovalent organic group. １ ~X １６ At least one of the groups represents a halogen atom, and at least one of the groups represents -Y １ -R １ Represents. M represents a metal atom, a metal oxide, or a metal halide.

2. The coloring composition according to claim 1, wherein the content of the blue coloring material (A2) is 0.1 to 100 parts by mass relative to 100 parts by mass of the green coloring material (a1) represented by the general formula (1).

3. The coloring composition according to claim 1, wherein the blue colorant (A2) is one or more selected from the group consisting of C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and C.I. Pigment Blue 16.

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

5. The coloring composition according to claim 1 , further comprising a pigment derivative (D) having a basic group.

6. The colored composition according to claim 1 , further comprising a polymerizable compound (E) and a polymerization initiator (F).

7. A film formed from the colored composition according to any one of claims 1 to 6.

8. A color filter comprising the film according to claim 7.

9. A solid-state imaging device comprising the color filter according to claim 8.

10. An image display device comprising the color filter according to claim 8.

Images