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

Abstract

To provide a photosensitive composition that enables formation of a film having excellent resistance even after low-temperature heat treatment.SOLUTION: A photosensitive composition comprises a colorant and an alkali-soluble resin, the colorant containing a compound represented by the following formula, the alkali-soluble resin containing a thermally crosslinkable group-containing monomer unit and a hydroxyl group-containing monomer unit.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive composition used for forming a color filter for use 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. 2020 / 171060 [Patent Document 4] International Publication No. 2023 / 002875 Summary of the Invention [Problem to be solved by the invention]

[0005] As a result of thorough investigation of the phthalocyanine compounds described in Patent Documents 1 to 4, it was found that color filters using these phthalocyanine compounds generate aggregates when heat-treated at high temperatures. Therefore, it is required to heat-treat at low temperatures. However, when heat-treated at low temperatures, there is a problem that the resistance of the film is deteriorated.

[0006] An object of the present invention is to provide a photosensitive composition which is capable of forming a film which is suppressed in occurrence of aggregates and has excellent resistance even in a heat treatment at a low temperature. [Means for solving the problem]

[0007] The present invention relates to a photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The colorant (A) contains a compound (A1) represented by the following general formula (1), The present invention relates to a photosensitive composition, wherein the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2). 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

[0008] According to the present invention, it is possible to provide a photosensitive composition capable of forming a film having excellent resistance even in a heat treatment at a low temperature while suppressing the generation of aggregates. 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

[0009] Hereinafter, the embodiment for carrying out the photosensitive 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.

[0010] 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. In this specification, "low temperature" means 180° C. or below.

[0011] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The colorant (A) contains a compound (A1) represented by the following general formula (1), The alkali-soluble resin (B) is characterized in that it contains an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2). 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.

[0012] The mechanism by which the photosensitive composition having the above-mentioned configuration can solve the problems of the present invention is not clear, but is speculated as follows.

[0013] When the alkali-soluble resin (B) contains an alkali-soluble resin (B1) (hereinafter simply referred to as alkali-soluble resin (B1)) having a thermal crosslinking group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2), the alkali-soluble resins (B1) tend to be close to each other or to compounds having other functional groups due to the interaction of the hydroxyl groups, and the reaction of the thermal crosslinking groups proceeds, improving the resistance of the film even in low-temperature heat treatment. In addition, the low-temperature heat treatment can also suppress the generation of aggregates.

[0014] Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[0015] [Colorant (A)] The photosensitive composition of the present invention contains a colorant (A).

[0016] The colorant (A) is not particularly limited and may be either a pigment or a dye, which may be used in combination. The pigment may be either an organic pigment or an inorganic pigment, which may be used in combination.

[0017] (Pigments) The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

[0018] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 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, Nos. 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, and JP-A-2014-134712. Also included are the pigments described in Japanese Patent No. 6368844.

[0019] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0020] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129,138,139,147,150,151,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233, pigments described in JP-A-2012-226110, and pigments described in JP-A-2019-113676.

[0021] Further, examples of yellow pigments include pigments containing at least one anion selected from the group consisting of an azo compound represented by the following general formula (7) 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 (8):

[0022] General formula (7) [ka]

[0023] In general formula (7), R1's each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and R2's each independently represent -OH or -NH2.

[0024] General formula (8) [ka]

[0025] In formula (8), each R3 independently represents a hydrogen atom or an alkyl group.

[0026] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63.

[0027] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0028] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0029] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0030] Other examples include inorganic pigments such as silica, talc, titanium oxide, zinc oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0031] 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 solution 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 viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

[0032] In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0033] (dye) Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Furthermore, the dye may be a derivative of these dyes or a lake compound of the dye.

[0034] The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid. The direct dye preferably forms an inorganic salt of the acid dye, or a salt-forming compound of the acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Also preferred are salt-forming compounds that are salts of a resin component having these functional groups and an acid dye. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive coloring composition with excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0035] Although the basic dye can be used as it is, a salt-forming compound formed with an organic acid, perchloric acid, or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it has excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion component acting as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0036] The chemical structure of the dye may be, for example, an azo dye, a disazo dye, an azomethine dye (such as indoaniline dye, indophenol dye), a dipyrromethene dye, a quinone dye (such as benzoquinone dye, naphthoquinone dye, anthraquinone dye, anthrapyridone dye), a carbonium dye (such as diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye), a quinoneimine dye (such as oxazine dye, thiazine dye), an azine dye, a poly Examples of dye structures derived from dyes selected from methine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof, but are not particularly limited to these.

[0037] Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0038] The colorant (A) can be used alone or in combination of two or more kinds.

[0039] The content of the colorant (A) is preferably from 1 to 80 mass %, and more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0040] (Compound (A1) represented by general formula (1)) The photosensitive composition of the present invention contains a compound (A1) represented by the following general formula (1) as a colorant (A).

[0041] General formula (1) [ka]

[0042] 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. In the general formula (1), M represents a metal atom, a metal oxide, or a metal halide.

[0043] X1~X 16Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among these, the halogen atom preferably contains a fluorine atom from the viewpoint of color.

[0044] The number of halogen atoms is preferably 4 to 12, and more preferably 6 to 10.

[0045] When there are two or more halogen atoms, those halogen atoms may be the same or different.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] When there are two or more -Y1-R1, those -Y1-R1 may be the same or different.

[0053] It is preferable that --Y1-R1 contains a group represented by the following general formula (9).

[0054] General formula (9) [ka]

[0055] In general formula (9), 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).

[0056] Z1 is preferably an oxygen atom.

[0057] 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.

[0058] Examples of the aryl group in R2 which may have a substituent include a phenyl group, a naphthyl group, and a biphenyl group.

[0059] 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.

[0060] 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.

[0061] n is preferably 0 or 1.

[0062] Specific examples of the group represented by general formula (9) include groups represented by formulae (9-1) to (9-12). In the formulae, Y1 represents a divalent linking group, and * represents a bond. However, the present invention is not limited to these.

[0063] [ka]

[0064] X1~X 16 The number of -Y1-R1 in the formula (I) is preferably 4 to 12, and more preferably 6 to 10.

[0065] X1~X 16 X2, X3, X6, X7, X10 , 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.

[0066] Examples of the metal atom in M ​​include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.

[0067] The metal oxide for M includes oxytitanium, oxyvanadium, and the like.

[0068] 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.

[0069] The method for producing the compound (A1) represented by the general formula (1) 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, and WO 2023 / 136027 can be mentioned.

[0070] Specific examples of the compound (A1) represented by general formula (1) are shown below, which are represented by formulas (A1-1) to (A1-9), although the present invention is not limited thereto.

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] The compound (A1) represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0077] The content of the compound (A1) represented by general formula (1) is preferably from 1 to 100 mass %, and more preferably from 10 to 90 mass %, in 100 mass % of the colorant (A).

[0078] (Colorant (A2) other than the compound (A1) represented by general formula (1)) The photosensitive composition of the present invention may contain, as the colorant (A), a colorant (A2) (hereinafter also simply referred to as colorant (A2)) other than the compound (A1) represented by general formula (1).

[0079] The colorant (A2) is not particularly limited, and any known compound can be used. Specific examples include the pigments and dyes described above. Among these, the colorant (A2) is preferably a compound represented by the following general formula (10) from the viewpoint of color reproducibility.

[0080] General formula (10) [ka]

[0081] In general formula (10), R1~R 13 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. Adjacent groups of R1 to R4 and / or R5 to R8 may join together to form an aromatic ring which may have a substituent.

[0082] R1~R 13 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0083] R1~R 13 The alkyl group which may have a substituent in the formula (I) 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, an n-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group.

[0084] R1~R 13 The alkoxy group which may have a substituent in the formula (I) may be linear, branched, or a combination thereof, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentoxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group.

[0085] R1~R 13 The aryl group which may have a substituent in the above formula (I) may be either a single ring or a condensed ring, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, and an anthranyl group.

[0086] R1~R 13 When the alkyl group, alkoxy group or aryl group has a substituent, examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, and an aryloxycarbonyl group.

[0087] When adjacent groups of R1 to R4 and / or R5 to R8 are joined together to form an aromatic ring which may have a substituent, the aromatic ring may be either a hydrocarbon aromatic ring or a heteroaromatic ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

[0088] When the aromatic ring has a substituent, examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, and an aryloxycarbonyl group.

[0089] From the viewpoint of suppressing aggregates, the compound represented by general formula (10) is preferably a compound represented by the following general formulas (11) to (13).

[0090] [ka]

[0091] In general formulas (11) to (13), R 14 ~R 28 , R 29 ~R 43 , R 44 ~R 60each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent.

[0092] R 14 ~R 28 , R 29 ~R 43 , R 44 ~R 60 The alkyl group which may have a substituent, the alkoxy group which may have a substituent, and the aryl group which may have a substituent in the formula (13) have the same meanings as those explained in relation to the general formula (10).

[0093] Specific examples of the compound represented by general formula (10) include compounds represented by formulas (10-1) to (10-16), although the present invention is not limited thereto.

[0094] [ka]

[0095] [ka]

[0096] The colorant (A2) can be used alone or in combination of two or more kinds.

[0097] The content of the colorant (A2) is preferably 10 to 90 mass % in 100 mass % of the colorant (A).

[0098] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0099] The alkali-soluble resin (B) is not particularly limited as long as it dissolves in the alkali developer described below, and any known resin can be used. Examples of the resin include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, cyclic olefin resin, polysiloxane resin, etc.

[0100] The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably from 3,000 to 50,000, and more preferably from 4,000 to 40,000.

[0101] The acid value of the alkali-soluble resin (B) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0102] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0103] The content of the alkali-soluble resin (B) is preferably from 1 to 90 mass %, and more preferably from 5 to 80 mass %, in 100 mass % of the nonvolatile content of the photosensitive composition.

[0104] (Alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2)) The photosensitive composition of the present invention contains, as the alkali-soluble resin (B), an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2).

[0105] The alkali-soluble resin (B1) is not particularly limited, and known resins can be used. The thermal crosslinking group is a group that undergoes a crosslinking reaction by heating to crosslink. Examples of the thermal crosslinking group include a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group. Examples of the alkali-soluble resin (B1) include a monomer that forms a thermally crosslinkable group-containing monomer unit (b1), a monomer that forms a hydroxyl group-containing monomer unit (b2), and a copolymer with any other copolymerizable monomer.

[0106] [Thermal crosslinkable group-containing monomer unit (b1)] From the viewpoint of resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit (b1) is preferably a monomer unit formed from at least one monomer selected from the group consisting of monomers represented by the following general formulas (2) to (6).

[0107] General formula (2) [ka]

[0108] In general formula (2), R 1 represents a hydrogen atom or a methyl group.

[0109] In general formula (2), R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0110] In general formula (2), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0111] In general formula (2), L 2 represents a single bond or an oxygen atom.

[0112] In general formula (2), L 3 and L 4 each independently represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0113] The method for producing the monomer represented by the general formula (2) is not particularly limited, and a known method can be used. For example, the methods described in JP-A-10-316643 and WO 2022 / 145298 can be mentioned.

[0114] Specific examples of the monomer represented by formula (2) include compounds of formulas (2-1) to (2-11), although the present invention is not limited thereto.

[0115] [ka]

[0116] From the viewpoint of resistance after low-temperature heating, the monomer represented by general formula (2) is preferably at least one selected from the compounds represented by the above formulae (2-1), (2-2), (2-3), (2-4), (2-9), and (2-10).

[0117] The monomer represented by formula (2) can be used alone or in combination of two or more kinds.

[0118] General formula (3) [ka]

[0119] In general formula (3), R 1 represents a hydrogen atom or a methyl group.

[0120] In general formula (3), R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or a combination thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, R 4 and R 5 is preferably a hydrogen atom, R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0121] In general formula (3), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0122] The method for producing the monomer represented by the general formula (3) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2022 / 145298 can be mentioned.

[0123] Specific examples of the monomer represented by formula (3) include compounds of formulas (3-1) to (3-6), although the present invention is not limited thereto.

[0124] [ka]

[0125] The monomer represented by formula (3) can be used alone or in combination of two or more kinds.

[0126] General formula (4) [ka]

[0127] In general formula (4), R 1 represents a hydrogen atom or a methyl group.

[0128] In general formula (4), R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0129] In general formula (4), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0130] The method for producing the monomer represented by the general formula (4) is not particularly limited, and any known method can be used, for example, the method described in Coatings Technology, Vol. 62, by Witzeman, JS, and Dell Rector, FJ.

[0131] Specific examples of the monomer represented by formula (4) include compounds of formulas (4-1) to (4-4), although the present invention is not limited thereto.

[0132] [ka]

[0133] The monomer represented by formula (4) can be used alone or in combination of two or more kinds.

[0134] General formula (5) [ka]

[0135] In general formula (5), R 1 represents a hydrogen atom or a methyl group.

[0136] In general formula (5), R 8 ~R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 8 ~R 10 At least one of them is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, from the viewpoint of resistance after low-temperature heating, a methoxy group and an ethoxy group are preferred. From the viewpoint of resistance after low-temperature heating, R 8 ~R 10 At least two of them are preferably alkoxy groups having 1 to 6 carbon atoms.

[0137] In general formula (5), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0138] Specific examples of the monomer represented by formula (5) include compounds of formulas (5-1) to (5-6), although the present invention is not limited thereto.

[0139] [ka]

[0140] Commercially available products of the monomer represented by the general formula (5) include, for example, KBM-502, 503, 5103, 5803, KBE-502, 503, and the like manufactured by Shin-Etsu Chemical Co., Ltd.

[0141] The monomer represented by formula (5) can be used alone or in combination of two or more kinds.

[0142] General formula (6) [ka]

[0143] In general formula (6), R 1 represents a hydrogen atom or a methyl group.

[0144] In general formula (6), R 11 ~R 13 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, the methyl group is preferred.

[0145] In general formula (6), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, a group having --NH--, or a combination thereof. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0146] Specific examples of the monomer represented by formula (6) include compounds of formulas (6-1) to (6-6), although the present invention is not limited thereto.

[0147] [ka]

[0148] The monomer represented by formula (6) can be used alone or in combination of two or more kinds.

[0149] From the viewpoint of resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit (b1) is more preferably a monomer unit formed from one or more of the monomers represented by general formula (2) and the monomers represented by general formula (3).

[0150] The thermally crosslinkable group-containing monomer unit (b1) can be formed by using the monomers represented by the general formulae (2) to (6) alone or in combination of two or more kinds.

[0151] The thermally crosslinkable group-containing monomer unit (b1) can be a combination of a monomer unit formed of a monomer represented by any one of the general formulae (2) to (6) and a monomer unit formed of a monomer other than the monomer represented by any one of the general formulae (2) to (6).

[0152] Examples of the monomer other than the monomers represented by the general formulas (2) to (6) include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, and the like.

[0153] The content of the thermally crosslinkable group-containing monomer unit (b1) is preferably 1 to 80 mol %, more preferably 5 to 75 mol %, of all monomer units in the alkali-soluble resin (B1) from the viewpoint of resistance after low-temperature heating.

[0154] [Hydroxyl group-containing monomer unit (b2)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

[0155] The hydroxyl group-containing monomers can be used alone or in combination of two or more kinds.

[0156] The content of the hydroxyl group-containing monomer units (b2) is preferably from 1 to 60 mol %, more preferably from 5 to 50 mol %, of all monomer units in the alkali-soluble resin (B1), from the viewpoint of resistance after low-temperature heating.

[0157] From the viewpoint of resistance after low-temperature heating, the total content of the thermally crosslinkable group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2) is preferably 5 to 85 mol %, and more preferably 15 to 80 mol %, of all the structural units of the alkali-soluble resin (B1).

[0158] The molar ratio of the thermally crosslinkable group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2) is preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20, from the viewpoint of resistance after low-temperature heating.

[0159] The method for introducing the hydroxyl group-containing monomer unit (b2) into the alkali-soluble resin (B1) may include, in addition to copolymerizing a thermally crosslinkable group-containing monomer with a hydroxyl group-containing monomer, a method for adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in the resin (precursor) or a method for adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in the resin (precursor).

[0160] The alkali-soluble resin (B1) may contain monomer units other than the thermally crosslinkable group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2), such as an acidic group-containing monomer unit (b3), an aliphatic condensed ring structure-containing monomer unit (b4), a polymerizable unsaturated group-containing monomer unit (b5), and other monomer units (b6).

[0161] [Acidic group-containing monomer unit (b3)] Examples of the acidic group-containing monomer 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 phthalic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0162] The acidic group-containing monomers can be used alone or in combination of two or more kinds.

[0163] The content of the acidic group-containing monomer unit (b3) is preferably from 1 to 40 mol %, and more preferably from 5 to 35 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0164] The method for introducing the acidic group-containing monomer unit (b3) into the alkali-soluble resin (B1) may be a method of copolymerizing a thermally crosslinkable group-containing monomer, a hydroxyl group-containing monomer, and an acidic group-containing monomer, or a method of adding an acid anhydride (modifying compound) to the hydroxyl group contained in the resin (precursor). Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0165] [Aliphatic condensed ring structure-containing monomer unit (b4)] Examples of the aliphatic condensed ring structure-containing monomer include isobornyl (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.

[0166] The aliphatic fused ring structure-containing monomers can be used alone or in combination of two or more kinds.

[0167] [Polymerizable unsaturated group-containing monomer unit (b5)] Methods for incorporating the polymerizable unsaturated group-containing monomer unit (b5) into the alkali-soluble resin (B1) include, for example, the following methods (i) to (iii).

[0168] <Method (i)> In the method (i), for example, a precursor having an epoxy group is first synthesized, and then a monomer having a carboxyl group, among the above-mentioned acid group-containing monomers, is added to the epoxy group of the precursor.

[0169] It is also possible to further react an acid anhydride with the above precursor obtained by adding a monomer having a carboxyl group to the epoxy group of the precursor.

[0170] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0171] <Method (ii)> In the method (ii), for example, a precursor having a carboxyl group is first synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0172] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.

[0173] <Method (iii)> In the method (iii), for example, a precursor having a hydroxyl group is first synthesized, and then the hydroxyl group of the precursor is reacted with an isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0174] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0175] [Other monomer units (b6)] Examples of other monomers include acrylic acid esters such as methyl (meth)acrylate, 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, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene; (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; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N- N-substituted maleimides such as (4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples of such dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate include 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, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.

[0176] The other monomers can be used alone or in combination of two or more.

[0177] The weight average molecular weight of the alkali-soluble resin (B1) is preferably from 3,000 to 50,000, and more preferably from 3,000 to 20,000.

[0178] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the alkali-soluble resin (B1) is preferably from 1.2 to 3.0, more preferably from 1.3 to 2.8.

[0179] The acid value of the alkali-soluble resin (B1) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0180] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0181] The content of the alkali-soluble resin (B1) is preferably from 10 to 100 mass %, and more preferably from 20 to 100 mass %, in 100 mass % of the alkali-soluble resin (B), from the viewpoint of resistance after low-temperature heating.

[0182] (Alkali-soluble resin (B2) other than alkali-soluble resin (B1)) The photosensitive composition of the present invention can contain, as the alkali-soluble resin (B), an alkali-soluble resin (B2) other than the alkali-soluble resin (B1) (hereinafter, also simply referred to as the alkali-soluble resin (B2)).

[0183] From the viewpoint of resistance after low-temperature heating, the alkali-soluble resin (B2) preferably contains the above-mentioned hydroxyl group-containing monomer unit (b2).

[0184] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0185] The polymerizable compound (C) 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.

[0186] The polymerizable compound (C) is not particularly limited, and a known compound can be used. For example, a polymerizable compound (C1) having a hydroxyl group, a polymerizable compound (C2) having an acidic group, a lactone-modified polymerizable compound (C3), a polymerizable compound (C4) having a urethane bond, a polymerizable compound (C5) having an amine structure, a polymerizable compound (C6) having a dendrimer structure or a hyperbranch structure, and other polymerizable compounds (C7) can be mentioned. Among these, the polymerizable compound (C) preferably contains a polymerizable compound (C1) having a hydroxyl group from the viewpoint of resistance after low-temperature heating. It is presumed that the resistance is further improved by reacting the hydroxyl group of the polymerizable compound (C1) having a hydroxyl group with the thermal crosslinking group of the alkali-soluble resin (B1) by heating.

[0187] The polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0188] The content of the polymerizable compound (C) is preferably from 1 to 80 mass %, and more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0189] (Polymerizable compound having a hydroxyl group (C1)) Examples of the polymerizable compound (C1) 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, EO isocyanuric acid, or the like. Examples of the acrylic acid ester include PO-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.

[0190] Examples of commercially available polymerizable compounds (C1) 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.

[0191] The polymerizable compound (C1) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0192] The content of the polymerizable compound (C1) having a hydroxyl group is preferably from 10 to 100 mass %, and more preferably from 30 to 100 mass %, in 100 mass % of the polymerizable compound (C).

[0193] (Polymerizable compound having an acidic group (C2)) Examples of the polymerizable compound (C2) 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.

[0194] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0195] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0196] 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.

[0197] Commercially available polymerizable compounds (C2) 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.

[0198] The polymerizable compound (C2) having an acidic group can be used alone or in combination of two or more kinds.

[0199] (Lactone-modified polymerizable compound (C3)) The lactone-modified polymerizable compound (C3) is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound (C4) is obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compound.

[0200] Commercially available lactone-modified polymerizable compounds (C3) include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0201] The lactone-modified polymerizable compounds (C3) can be used alone or in combination of two or more kinds.

[0202] (Polymerizable compound having a urethane bond (C4)) Examples of the polymerizable compound (C4) 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.

[0203] 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.

[0204] 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.

[0205] The polymerizable compound (C4) 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.

[0206] The method for introducing an acidic group into the polymerizable compound (C4) 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.

[0207] 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.

[0208] Commercially available polymerizable compounds (C4) 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.

[0209] The polymerizable compound (C4) having a urethane bond can be used alone or in combination of two or more kinds.

[0210] (Polymerizable compound having an amine structure (C5)) The amine structure of the polymerizable compound (C5) having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structures, but is preferably a secondary or tertiary amine structure, provided that the amine structure of the polymerizable compound (C5) having an amine structure does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0211] Examples of the polymerizable compound (C5) having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0212] 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.

[0213] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0214] 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.

[0215] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0216] 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.

[0217] The polymerizable compound (C5) 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 a Michael addition reaction.

[0218] The polymerizable compound (C5) 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).

[0219] 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.

[0220] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0221] 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.

[0222] Commercially available polymerizable compounds (C5) having an amine structure include, for example, ARONIX MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383, 386, and 9906NS manufactured by Arkema.

[0223] The polymerizable compound (C5) having an amine structure can be used alone or in combination of two or more kinds.

[0224] (Polymerizable compound (C6) 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.

[0225] Commercially available polymerizable compounds (C6) 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.

[0226] The polymerizable compound (C6) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0227] (Other polymerizable compounds (C7)) Examples of other polymerizable compounds (C7) include 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, isocyanuric acid. Examples of the methacrylic acid ester include EO- 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, and (meth)acrylic acid ester of methylolated melamine; styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0228] Other commercially available polymerizable compounds (C7) 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.

[0229] The other polymerizable compounds (C7) can be used alone or in combination of two or more kinds.

[0230] [Polymerization initiator (D)] The photosensitive composition of the present invention contains a polymerization initiator (D).

[0231] The polymerization initiator (D) 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.

[0232] 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.

[0233] 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, a compound having one oxime ester group is preferred, and a compound having two oxime ester groups is more preferred. By having two oxime ester groups, the radical generating ability is high and the compound is less susceptible to oxygen inhibition. Therefore, the photocuring proceeds and the resistance is further improved.

[0234] Specific examples of compounds having two oxime ester groups are shown below, which are represented by the formulae (D-1) to (D-5), although the present invention is not limited thereto.

[0235] [ka]

[0236] The content of the compound having two oxime ester groups is preferably from 10 to 100% by mass in 100% by mass of the polymerization initiator (D).

[0237] 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.

[0238] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0239] The content of the polymerization initiator (D) is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0240] [Silane coupling agent (E)] From the viewpoint of resistance after low-temperature heating, the photosensitive composition of the present invention preferably contains a silane coupling agent (E). It is presumed that the silane coupling agent (E) reacts with functional groups on the substrate surface or functional groups of other components contained in the photosensitive composition, improving resistance after low-temperature heating.

[0241] The silane coupling agent (E) 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 (E) is not included in the alkali-soluble resin (B) and the polymerizable compound (C).

[0242] Examples of the silane coupling agent (E) include 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, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0243] Commercially available silane coupling agents (E) 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.

[0244] The silane coupling agent (E) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0245] 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.

[0246] The organic polymer type is a silane coupling agent (E) 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.

[0247] The silane coupling agent (E) preferably contains a compound represented by the following general formula (14). The compound represented by general formula (14) has a urethane bond, and therefore forms hydrogen bonds between the urethane bonds and with functional groups of other components contained in the photosensitive composition, forming a strong film. In addition, it is presumed that the urethane bond has flexibility, resulting in a strong yet flexible film.

[0248] General formula (14) [ka]

[0249] In general formula (14), R1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, Q represents a group represented by any one of the following general formulae (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0250] [ka]

[0251] In the general formula (Q-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulae (Q-1) to (Q-4), R4 each independently represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0252] In the general formula (14), R1 is preferably a methyl group.

[0253] In the general formula (14), Q is preferably any of the general formulae (Q-1) to (Q-3).

[0254] The molecular weight (formula weight) or weight average molecular weight of the silane coupling agent (E) is preferably from 100 to 3,000, and more preferably from 150 to 1,500.

[0255] The acid value of the silane coupling agent (E) is preferably 10 mgKOH / g or less.

[0256] The silane coupling agent (E) can be used alone or in combination of two or more kinds.

[0257] The content of the silane coupling agent (E) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0258] [Thermal crosslinkable compound (F)] From the viewpoint of resistance after low-temperature heating, the photosensitive composition of the present invention preferably contains a thermally crosslinkable compound (F), which crosslinks the thermally crosslinkable compound (F) with other components upon heating, improving resistance. In this specification, the thermally crosslinkable compound (F) is different from the alkali-soluble resin (B), the polymerizable compound (C), and the silane coupling agent (E).

[0259] The thermally crosslinkable compound (F) is not particularly limited as long as it is a compound having a thermally crosslinkable group, and a known compound can be used. For example, a compound having an epoxy group, a compound having a blocked isocyanate group, a compound having an oxetanyl group, a compound having a methylol group, a compound having a phenol group, a compound having an alkoxyalkyl group, etc. can be mentioned. Among these, it is preferable to contain one or more compounds selected from the group consisting of a compound having a blocked isocyanate group and a compound having an epoxy group, and it is more preferable to contain a compound having a blocked isocyanate group.

[0260] The thermally crosslinkable compound (F) can be used alone or in combination of two or more kinds.

[0261] The content of the thermally crosslinkable compound (F) is preferably from 0.5 to 40 mass %, and more preferably from 1 to 30 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0262] (Compound (F1) Having a Blocked Isocyanate Group) The compound (F1) having a blocked isocyanate group is a compound in which the isocyanate group of a compound having an isocyanate group is protected with a blocking agent. The desorption temperature of the blocking agent of the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 110°C.

[0263] The compound (F1) having a blocked isocyanate group is synthesized by reacting a compound having an isocyanate group with a blocking agent by a known method, for example, the methods described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, JP-A-2012-012567, etc.

[0264] 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, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and from the viewpoint of resistance after low-temperature heating, active methylene compounds are particularly preferred. The elimination temperature of the active methylene compound or the temperature of the ester exchange reaction is low at 80 to 110°C, and the reaction is sufficient even at low temperatures, improving resistance.

[0265] Examples of the compound having an isocyanate group 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 examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms, and reaction products of these compounds with polyols.

[0266] The compound having an isocyanate group is preferably a biuret, isocyanurate, adduct or allophanate of a compound having an aliphatic structure or a compound having an alicyclic structure.

[0267] Examples of the compound (F1) having a blocked isocyanate group include the following compounds: In the following structural formula, X represents a blocked isocyanate group, but the present invention is not limited thereto.

[0268] [ka]

[0269] Examples of X (blocked isocyanate group) in the above compound include the structures shown in (X-1) to (X-7) below. In the following structures, * represents a bond. However, the present invention is not limited to these.

[0270] [ka]

[0271] Examples of commercially available compounds (F1) having a blocked isocyanate group and an aliphatic structure include Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882 manufactured by Mitsui Chemicals, Inc., and BI7960, BI7961, BI7982, BI7991, and BI7992 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an alicyclic structure include Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation, and BI7950, BI7951, and BI7990 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an aromatic structure include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0272] The compound (F1) having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0273] The weight average molecular weight of the compound (F1) having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0274] The acid value of the compound (F1) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0275] The compound (F1) having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0276] The content of the compound (F1) having a blocked isocyanate group 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 photosensitive composition.

[0277] (Compound (F2) having an epoxy group) The epoxy group is a group having a three-membered cyclic ether structure, and includes an alicyclic epoxy group.

[0278] Examples of the compound (F2) having an epoxy group include 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.

[0279] Commercially available products of the compound (F2) having an epoxy group 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.

[0280] The compound (F2) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0281] The epoxy equivalent of the compound (F2) having an epoxy group 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.

[0282] From the viewpoint of resistance after low-temperature heating, the compound (F2) having an epoxy group more preferably contains a compound represented by the following general formula (15).

[0283] General formula (15) [ka]

[0284] In formula (15), R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0285] R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol. The group obtained by removing m hydroxyl groups from the m-hydric alcohol is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, or cyclic, or a group in which they are combined. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2,2-dimethylpropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 3,3-dimethylbutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable. m represents an integer of 1 to 6, and n represents an integer of 1 to 30. When m is 2 or more, n in each group in parentheses in general formula (15) may be the same or different.

[0286] The compound represented by the general formula (15) is, for example, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0287] The acid value of the compound (F2) having an epoxy group is preferably 10 mgKOH / g or less.

[0288] The compound (F2) having an epoxy group can be used alone or in combination of two or more kinds.

[0289] The content of the compound (F2) having an epoxy group is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0290] From the viewpoint of resistance after low-temperature heating, it is particularly preferable to use the thermally crosslinkable compound (F) in combination with a compound (F1) having a blocked isocyanate group and a compound (F2) having an epoxy group. The mass ratio of the compound (F1) having a blocked isocyanate group to the compound (F2) having an epoxy group is preferably from 5:95 to 95:5, and more preferably from 10:90 to 90:10.

[0291] [Pigment derivatives (G)] The photosensitive composition of the present invention can contain a pigment derivative (G).

[0292] The pigment derivative (G) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be mentioned. Specifically, compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphoric acid groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminals, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups can be mentioned. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

[0293] Specifically, pyrrolopyrrole pigment derivatives are described in JP 2001-220520 A, WO 2009 / 081930 A, WO 2011 / 052617 A, WO 2012 / 102399 A, JP 2017-156397 A, and WO 2018 / 101189 A, phthalocyanine pigment derivatives are described in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone pigment derivatives are described in JP 63-2 64674, JP09-272812A, JP10-245501A, JP10-265697A, JP2007-079094A, WO 2009 / 025325A, quinacridone pigment derivatives are shown in JP48-54128A, JP03-9961A, and JP2000-273383A, dioxazine pigment derivatives are shown in JP2011-162662A, thiazine indigo pigment derivatives are shown in JP2007-314785A, triazine pigment derivatives are shown in Examples of benzoisoindole pigment derivatives include JP-A-2009-57478, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226110. Examples of naphthol pigment derivatives include Examples of squarylium pigment derivatives include those described in JP 2012-208329 A and JP 2014-5439 A; examples of azo pigment derivatives include those described in JP 2001-172520 A and JP 2012-172092 A; examples of acidic substituents include those described in JP 2004-307854 A; and examples of basic substituents include those described in JP 2002-201377 A, JP 2003-171594 A, JP 2005-181383 A, JP 2005-213404 A, and the like.In these documents, the term "derivative," "dye derivative," "dispersant," "dispersing aid," "pigment dispersant," or simply "compound" is sometimes used, but these terms are synonymous with the pigment derivative (G).

[0294] The pigment derivative (G) is preferably added during the micronization of the colorant (A) described above, or during the dispersion treatment of the colorant (A) described below. The average primary particle size of the pigment derivative (G) is preferably 5 to 200 nm.

[0295] The pigment derivative (G) can be used alone or in combination of two or more kinds.

[0296] The content of the pigment derivative (G) is preferably from 1 to 50 parts by mass, and more preferably from 2 to 40 parts by mass, based on 100 parts by mass of the colorant (A).

[0297] [Dispersion resin (H)] The photosensitive composition of the present invention can contain a dispersing resin (H). In this specification, the dispersing resin (H) is not included in the alkali-soluble resin (B).

[0298] The dispersing resin (H) is preferably a resin having an adsorptive group having a high affinity for the colorant (A). The adsorptive group preferably has at least one type of basic group and acidic group.

[0299] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0300] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0301] Examples of the resin type of the dispersion resin (H) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0302] Examples of the structure of the dispersing resin (H) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, the block structure, the graft structure, and the comb structure are preferred.

[0303] Commercially available dispersion resins (H) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, and 2095 manufactured by BYK Japan Co., Ltd. ,2150,2155,2163,2164, or Anti-Terra-U203,204, or BYK-P104,P104S,220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000,9000,13000,13240,13650,13940,16000,17000,18000,20000,21000,24000,26 000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Aji Super PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, the resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, and paragraphs 0122 to 0155 of WO 2013175978 A, the resins described in paragraphs 0317 to 0321 of JP 2019-78878 A, and paragraph 00 of WO 2018 / 139534 A are also usable. 83, the resins described in paragraphs 0167 to 0191 of WO 2019 / 163505, the resins described in paragraphs 0299 ​​to 0310 of WO 2021 / 131927, the resins described in paragraphs 0080 to 0085 of WO 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of WO 2022 / 172607.

[0304] The dispersing resin (H) can be used alone or in combination of two or more kinds.

[0305] The content of the dispersing resin (H) is preferably from 3 to 200 parts by mass, and more preferably from 5 to 100 parts by mass, based on 100 parts by mass of the colorant (A).

[0306] [Sensitizer (I)] The photosensitive composition of the present invention can contain a sensitizer (I).

[0307] The sensitizer (I) 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 the compound include allylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, tetrabenzoporphyrin-based compounds, tetrapyrazinoporphyrazine-based compounds, phthalocyanine-based compounds, tetraazaporphyrazine-based compounds, tetraquinoxalylporphyrazine-based compounds, naphthalocyanine-based compounds, subphthalocyanine-based compounds, pyrylium-based compounds, thiopyrylium-based compounds, tetraphylline-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, organic ruthenium complexes, and benzophenone-based compounds. Among these, thioxanthone-based compounds and benzophenone-based compounds are preferred from the viewpoint of pattern formability.

[0308] (Thioxanthone compounds) 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.

[0309] (Benzophenone compounds) 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.

[0310] The sensitizers (I) can be used alone or in combination of two or more kinds.

[0311] The content of the sensitizer (I) is preferably from 5 to 200 parts by mass, and more preferably from 10 to 150 parts by mass, based on 100 parts by mass of the polymerization initiator (D).

[0312] [Hardening agent (curing accelerator)] The photosensitive composition of the present invention may be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermally crosslinkable compound (F). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (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.).

[0313] The curing agents can be used alone or in combination of two or more kinds.

[0314] The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermally crosslinkable compound (F).

[0315] [Thiol-based chain transfer agents (J)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (J). When used in combination with a polymerization initiator (D), the thiol chain transfer agent (J) generates thiyl radicals that are not easily inhibited by oxygen during radical polymerization after irradiation with light, thereby improving the photosensitivity of the photosensitive composition. In this specification, the thiol chain transfer agent (J) is not included in the silane coupling agent (E).

[0316] The thiol-based chain transfer agent (J) 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.

[0317] The thiol chain transfer agent (J) can be used alone or in combination of two or more kinds.

[0318] The content of the thiol chain transfer agent (J) is preferably from 0.1 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0319] [Polymerization inhibitor (K)] The photosensitive composition of the present invention may contain a polymerization inhibitor (K).

[0320] 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.

[0321] The polymerization inhibitor (K) can be used alone or in combination of two or more kinds.

[0322] 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 photosensitive composition.

[0323] [Ultraviolet absorber (L)] The photosensitive composition of the present invention may contain an ultraviolet absorber (L).

[0324] 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.

[0325] 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, and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole. , 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 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)benzotriazole, 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.

[0326] 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.

[0327] 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.

[0328] 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.

[0329] Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid trihydrate, 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.

[0330] 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.

[0331] Examples of the salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0332] The content of the ultraviolet absorber (L) is preferably from 0.1 to 5% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0333] [Antioxidants (M)] The photosensitive composition of the present invention can contain an antioxidant (M).

[0334] 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.

[0335] 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- tert-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 ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester salt, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid]ethylene bisoxybisethylene, 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-trimethylanilino Azine, 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-t-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, etc.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0343] The antioxidants (M) can be used alone or in combination of two or more kinds.

[0344] The content of the antioxidant (M) is preferably from 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0345] [Leveling agent (N)] The photosensitive composition of the present invention can contain a leveling agent (N).

[0346] 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.

[0347] 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., and FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Dow Corning Toray Co., Ltd. Examples of such silicone rubbers 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 Shin-Etsu Silicones Co., Ltd., and TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik Corporation.

[0348] 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, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 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.

[0349] 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.

[0350] 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.

[0351] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0352] 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 photosensitive composition.

[0353] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0354] 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.

[0355] The content of the storage stabilizer (O) is preferably from 0.05 to 5% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0356] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0357] The organic solvent (P) 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-methoxy-1-butanol, 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.,

[0358] From the viewpoint of the environment, the photosensitive 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 photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0359] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0360] The content of the organic solvent (P) is preferably such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0361] The photosensitive composition of the present invention may contain components other than those described above. Examples of the other components include an acid generator, a salt generator, a curing catalyst, a semiconductor nanocrystal, a semiconductor material, an organic electroluminescent material, an insulating material, etc. The content of the other components may be appropriately set within a range that does not impair the effects of the present invention.

[0362] [Specific metal element content] The photosensitive 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.

[0363] A photosensitive 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).

[0364] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

[0365] A photosensitive composition having a water content within the above range has excellent dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0366] [Method of producing photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, the components may be mixed at once, or each component may be dissolved or dispersed in the polymerizable compound (C) or the organic solvent (P) and then mixed successively. When a pigment is used as the colorant (A), it is preferable to disperse the pigment. For example, a dispersion is produced by adding a colorant (A), a dispersion resin (H), an organic solvent (P), etc., and carrying out a dispersion treatment. Then, an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), etc. are blended and mixed with the dispersion to produce the dispersion. The timing of blending each material is arbitrary. The dispersion process can also be carried out multiple times.

[0367] 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.

[0368] The average dispersed particle size (secondary particle size) of the particles in the dispersion is preferably from 30 to 200 nm, more preferably from 40 to 200 nm. If the particles have an appropriate particle size, a photosensitive composition having high dispersion stability is easily obtained.

[0369] 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.

[0370] The photosensitive 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 photosensitive 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.

[0371] The photosensitive composition of the present invention is preferably used for forming a pattern by a photolithography method, although the present invention is not limited thereto.

[0372] <Membrane> The film of the present invention is a film formed from the above-mentioned photosensitive composition. The film is preferably a patterned film, but may also be used as a flat film without forming a pattern.

[0373] [Membrane manufacturing method] The method for producing the membrane is not particularly limited, and known methods can be used. In the production of the membrane of the present invention, from the viewpoint of suppressing agglomeration, the heating temperature is preferably 180° C. or less throughout the entire process, more preferably 150° C. or less. The lower limit of the heating temperature is not particularly limited, but is preferably 50° C. or more, more preferably 70° C. or more.

[0374] [Coating process] In the production of the film, first, the photosensitive composition is applied onto a substrate. The substrate may be, for example, a substrate made of a material such as glass, resin, or silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. The resin may be a polyester resin such as polyester terephthalate, a polyolefin resin such as polypropylene or polyethylene, a polycarbonate resin, or an epoxy resin. 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.

[0375] 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.

[0376] 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.

[0377] [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.

[0378] 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.

[0379] 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. When the film is used as a flat film, the step of forming a pattern is not necessary, and the entire surface can be exposed to light.

[0380] The method for forming the pattern will now be described in detail.

[0381] When a pattern is formed by a photolithography method, for example, the photosensitive composition of the present invention is applied onto a substrate, and the layer formed by drying is exposed to light in a pattern through a mask (exposure step), and the unexposed parts are removed with an alkaline developer (development step), and the pattern is then heat-treated (post-bake step).

[0382] [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.

[0383] [Development process] Next, an alkaline development process is carried out, whereby the unexposed portions of the layer are dissolved in an alkaline developer, leaving only the hardened portions to obtain 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.

[0384] [Post-bake process] After development, a heat treatment (post-baking) is performed, which improves the resistance of the film. The heating temperature is preferably equal to or lower than 180° C., more preferably equal to or lower than 150° C. The heating time is preferably about 2 minutes to 2 hours.

[0385] <Color filters> The color filter of the present invention has the above-mentioned film. The color filter of the present invention can be produced by the same method as that for the above-mentioned film.

[0386] <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.

[0387] 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.

[0388] <Image display device> The image display device of the present invention includes the above-mentioned color filter. Examples of the image display device include a liquid crystal display, an organic EL display, a quantum dot display, and a micro LED display. The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the following liquid crystal display configuration can be given.

[0389] 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.

[0390] 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).

[0391] 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

[0392] 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.

[0393] Before describing the examples, each measurement method will be described.

[0394] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and extinction coefficient (L / mol cm) of the resin are measured as follows.

[0395] (molecular weight) The 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.

[0396] (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.

[0397] (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.

[0398] <Production of Colorant (A)> (Compound (A1-1) represented by general formula (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 liquid was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 1.

[0399] Intermediate 1 [ka]

[0400] 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 compound (A1-1) represented by the above general formula (1).

[0401] (Compound (A1-2) represented by general formula (1)) 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.

[0402] Intermediate 2 [ka]

[0403] 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 compound (A1-2) represented by the above general formula (1).

[0404] (Compound (A1-3) represented by general formula (1)) 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 solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 3.

[0405] Intermediate 3 [ka]

[0406] 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 compound (A1-3) represented by the above general formula (1).

[0407] (Compound (A1-4) represented by general formula (1)) 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.

[0408] Intermediate 4 [ka]

[0409] 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 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 compound (A1-4) represented by the above general formula (1).

[0410] (Compound (A1-5) represented by general formula (1)) 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.

[0411] Intermediate 5 [ka]

[0412] 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 temperature was then raised to room temperature and the mixture was stirred for about 12 hours. 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.

[0413] Intermediate 6 [ka]

[0414] 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 compound (A1-5) represented by the above general formula (1).

[0415] (Colorant (A2-1) other than the compound (A1) represented by general formula (1)) According to the description of JP2012-226110A, a compound represented by the following chemical formula (16) was obtained.

[0416] Chemical formula (16) [ka]

[0417] (Colorant (A2-2) other than the compound (A1) represented by general formula (1)) A compound represented by the following formula (17) was obtained according to the description of JP 2019-113676 A.

[0418] Chemical formula (17) [ka]

[0419] <Production of alkali-soluble resin (B)> (Alkali-soluble resin (B1-1) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc), which was stirred while replacing with nitrogen and heated to 78° C. Next, a mixture of 25.2 parts of KarenzMOI-DEM (malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester manufactured by Showa Denko Co., Ltd.), which is a monomer represented by general formula (2), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid and 27.0 parts of methyl methacrylate, and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were each dropped into the flask from the dropping funnel. After the dropwise addition was completed, the mixture was stirred at 78° C. for 3 hours to cause a reaction. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B1-1) solution. The acid value was 74 mgKOH / g, and the weight average molecular weight was 8,000.

[0420] (Alkali-soluble resin (B1-2) solution) In a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate were added and stirred, and cooled to 15 to 20°C. Then, while maintaining the temperature at 15 to 20°C and stirring, 141.1 parts of 2-acryloyloxyethyl isocyanate were dropped from the dropping funnel. After the dropwise addition, the mixture was stirred and reacted at 25°C for 13 hours to obtain compound a. Next, 150 parts of propylene glycol monomethyl ether was put into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and then the mixture was stirred while replacing with nitrogen and heated to 78 ° C. 48.8 parts of compound a, Karenz MOI-BP (2- [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate manufactured by Showa Denko K.K.) 10.0 parts, dicyclopentanyl methacrylate 14.7 parts, 2-hydroxyethyl methacrylate 25.5 parts, 2-ethylhexyl acrylate 8.6 parts, and 17.4 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 78 ° C for 3 hours to react, and then 0.2 parts of 1,8-diazabicyclo [5.4.0] -undecene-7 was added and further stirred at 78 ° C for 30 minutes. As a result, a thermally crosslinkable group-containing monomer unit (b1) formed from the following chemical formula (18), which is a monomer represented by general formula (3), was introduced.

[0421] Chemical formula (18) [ka]

[0422] Next, 9.9 parts of succinic anhydride and 0.5 parts of lithium naphthenate (catalyst) were added and stirred for 1 hour at 78° C. This caused a part of the hydroxyl groups of 2-hydroxyethyl methacrylate to react with succinic anhydride. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B1-2) solution. The acid value was 44 mgKOH / g, and the weight average molecular weight was 12,500.

[0423] (Alkali-soluble resin (B1-3) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of propylene glycol monomethyl ether, which was then stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 30.0 parts of 2-(acetoacetoxy)ethyl methacrylate, which is a monomer represented by general formula (4), 26.4 parts of methacrylic acid, 21.7 parts of 2-hydroxyethyl methacrylate, 54.4 parts of dicyclopentanyl methacrylate and 19.1 parts of n-butyl methacrylate, and 5.0 parts of 2,2'-azobis(isobutyric acid)dimethyl dissolved in 30 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 90°C for 6 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B1-3) solution. The acid value was 98 mgKOH / g, and the weight average molecular weight was 14,300.

[0424] (Alkali-soluble resin (B1-4) solution) 200 parts of 3-methoxy-1-butanol was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 105°C. Next, a mixture of 130.2 parts of 3-methacryloyloxypropylmethyldiethoxysilane, which is a monomer represented by general formula (5), 17.2 parts of methacrylic acid, 26.0 parts of 2-hydroxyethyl methacrylate and 22.0 parts of dicyclopentanyl methacrylate, and 30.3 parts of 2,2'-azobis(isobutyrate)dimethyl was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was reacted for 2 hours while stirring at 105°C. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, and an alkali-soluble resin (B1-4) solution was prepared. The acid value was 50 mgKOH / g and the weight average molecular weight was 5,100.

[0425] (Alkali-soluble resin (B1-5) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of propylene glycol monomethyl ether, which was then stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 35.0 parts of tert-butyl methacrylate, which is a monomer represented by general formula (6), 5.0 parts of 2-(acetoacetoxy)ethyl methacrylate, which is a monomer represented by general formula (4), 10.0 parts of N-benzylmaleimide, 20.0 parts of 2-hydroxyethyl methacrylate, 17.1 parts of methacrylic acid, and 2.0 parts of tert-butylperoxy-2-ethylhexanoate (polymerization initiator), and a mixture of 0.6 parts of n-dodecyl mercaptan and 20 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was kept at 90°C for 30 minutes, then heated to 115°C and reacted with stirring for 90 minutes. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B1-5) solution. The acid value was 98 mgKOH / g, and the weight average molecular weight was 19,500.

[0426] (Alkali-soluble resin (B1-6) solution) The Karenz MOI-DEM of alkali-soluble resin (B1-1) was treated with 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 An alkali-soluble resin (B1-6) was synthesized in the same manner as for the alkali-soluble resin (B1-1), except that a mixture of 1-methyl-2-phenylpropanediol and 1-decane-9-yl acrylate (molar ratio 1:1) was used instead. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B1-6) solution. The acid value was 73 mgKOH / g, and the weight average molecular weight was 8,200.

[0427] (Alkali-soluble resin (B1-7) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while replacing with nitrogen and heated to 78° C. Next, a mixture of 15.8 parts of KarenzMOI-DEM (malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester manufactured by Showa Denko Co., Ltd.), which is a monomer represented by general formula (2), 6.5 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, 31.3 parts of n-butyl methacrylate and 27.0 parts of methyl methacrylate, and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were each dropped into the flask from the dropping funnel. After the dropwise addition was completed, the mixture was stirred at 78° C. for 3 hours to cause a reaction. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, and an alkali-soluble resin (B1-7) solution was prepared. The alkali-soluble resin (B1-7) had an acid value of 75 mgKOH / g and a weight average molecular weight of 7,900.

[0428] (Alkali-soluble resin (B2-1) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while being replaced with nitrogen, and the temperature was raised to 80°C. Next, a mixture of 43.2 parts of benzyl methacrylate, 45.3 parts of 2-hydroxyethyl methacrylate, 24.4 parts of methacrylic acid, 38.5 parts of ARONIX M-110 (manufactured by Toagosei Co., Ltd., paracumylphenol ethylene oxide modified acrylate), and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for another 3 hours to allow the reaction to proceed. Next, the atmosphere in the flask was replaced with air, and 31.1 parts of 2-isocyanatoethyl methacrylate and 0.1 parts of hydroquinone were added, and the IR analysis revealed that the 2,270 cm3 reaction was based on the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B2-1) solution. The acid value was 91 mgKOH / g, and the weight average molecular weight was 21,000.

[0429] (Alkali-soluble resin (B2-2) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was stirred while being replaced with nitrogen, and heated to 120°C. Next, a mixture of 76.8 parts of glycidyl methacrylate, 66.1 parts of dicyclopentanyl methacrylate, and 16.7 parts of styrene, and a mixture of 5.5 parts of azobisisobutyronitrile as a polymerization initiator dissolved in PGMAc, was dropped into the flask from the dropping funnel over 2.5 hours. After the dropwise addition was completed, the mixture was stirred at 120°C for another 2 hours. Next, the flask was replaced with air, and 38.9 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added as modified compounds, and reacted at 120°C for 5 hours. This caused all of the epoxy groups of glycidyl methacrylate to react with the carboxyl groups of acrylic acid. Next, 40.0 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted for 4 hours at 120° C. As a result, some of the hydroxyl groups generated by cleavage of the epoxy groups of glycidyl methacrylate reacted with succinic anhydride. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B2-2) solution. The acid value was 95 mgKOH / g, and the weight average molecular weight was 9,000.

[0430] (Alkali-soluble resin (B2-3) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was stirred while replacing with nitrogen, and heated to 120°C. Next, a mixture of 109.25 parts of benzyl methacrylate, 24.1 parts of methacrylic acid, 22.03 parts of dicyclopentanyl methacrylate, 1.0 part of azobisisobutyronitrile as a polymerization initiator, and PGMAc was dropped into the flask from the dropping funnel over 2.5 hours. After the dropwise addition, the mixture was stirred at 120°C for another 2 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare an alkali-soluble resin (B2-3) solution. The acid value was 98 mgKOH / g, and the weight average molecular weight was 17,500.

[0431] <Production of silane coupling agent (E)> (Silane coupling agent (E-1)) 116 parts of 2-hydroxyethyl acrylate was charged into a 1L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and heated to 80°C. 205 parts of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto, and stirred at 80°C for 4 hours. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared, and instead, an absorption peak derived from a urethane bond had been generated, and a silane coupling agent (E-1) whose main component is represented by the following chemical formula (19) was obtained. In addition, as a secondary component, a dimer to decamer (a compound in which n is 2 to 10 in the general formula (14)) which is a condensate of the chemical formula (19) was included.

[0432] Chemical formula (19) [ka]

[0433] <Production of Dispersion Resin (H)> (Dispersion resin (H-1) solution) In a reactor equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the non-volatile content. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a dispersion resin (H-1) solution was prepared. The amine value was 169.8 mg KOH / g.

[0434] (Dispersed resin (H-2)) In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the non-volatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added so that the non-volatile content was 30% by mass, and a dispersion resin (H-2) solution was prepared. The amine value was 57 mgKOH / g.

[0435] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The non-volatile content was 25.0 mass%. Colorant (A2-1) other than the compound (A1) represented by formula (1): 15.0 parts Pigment derivative (G-1): 1.0 part Dispersion resin (H-1) solution: 15.0 parts Dispersion resin (H-2) solution: 15.0 parts Organic solvent (P-1): 54.0 parts

[0436] Dispersions 2 to 8 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 1 were changed.

[0437] [Table 1]

[0438] The respective raw materials listed in Table 1 are as follows.

[0439] [Colorant (A)] (Colorant (A2) other than the compound (A1) represented by general formula (1)) A2-3: CI Pigment Yellow 138 A2-4: CI Pigment Yellow 139 A2-5: CI Pigment Yellow 150 A2-6: CI Pigment Yellow 185 A2-7: CI Pigment Green 58 A2-8: CI Pigment Green 63

[0440] [Pigment derivatives (G)] G-1: The following compound

[0441] [ka]

[0442] [Organic solvent (P)] P-1: Propylene glycol monomethyl ether acetate

[0443] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain Photosensitive Composition 1. The nonvolatile content was 15.0% by mass. Compound (A1-1) represented by formula (1): 2.70 parts Dispersion 1: 16.50 parts Alkali-soluble resin (B1-1) solution: 9.00 parts Polymerizable compound having a hydroxyl group (C1-3): 2.60 parts Other polymerizable compounds (C7-2): 1.10 parts Polymerization initiator (D-1): 0.50 parts Silane coupling agent (E-1): 0.15 parts Compound having a blocked isocyanate group (F1-1): 1.00 part Compound having an epoxy group (F2-1): 0.40 parts Thiol chain transfer agent (J): 0.10 parts Leveling agent (N): 0.02 parts Organic solvent (P): 65.93 parts

[0444] [Examples 2 to 39 and Comparative Example 1] (Photosensitive composition 2-40) Photosensitive compositions 2 to 40 were produced in the same manner as in Example 1 using the raw materials and amounts shown in Tables 2-1 to 2-4.

[0445] [Table 2-1]

[0446] [Table 2-2]

[0447] [Table 2-3]

[0448] [Table 2-4]

[0449] The respective raw materials listed in Tables 2-1 to 2-4 are as follows.

[0450] [Polymerizable compound (C)] (Polymerizable compound having a hydroxyl group (C1)) C1-1: Isocyanuric acid EO modified diacrylate C1-2: Glycerol diacrylate C1-3: Pentaerythritol triacrylate C1-4: Dipentaerythritol pentaacrylate

[0451] (Other polymerizable compounds (C7)) C7-1: Isocyanuric acid EO modified triacrylate C7-2: Pentaerythritol tetraacrylate C7-3: Dipentaerythritol hexaacrylate C7-4: Trimethylolpropane triacrylate

[0452] [Polymerization initiator (D)] D-1: Compound (D-1) described above D-2: Compound (D-2) described above D-6: The following compound D-7: The following compound D-8: The following compound

[0453] [ka]

[0454] [Silane coupling agent (E)] E-2: KBE-403 (Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane)

[0455] [Thermal crosslinkable compound (F)] (Compound (F1) Having a Blocked Isocyanate Group) F1-1: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, a compound blocked with an active methylene compound, non-volatile content 60% by mass) F1-2: BI7982 (manufactured by Baxenden Chemical, compound blocked with a pyrazole compound, non-volatile content 70% by mass) F1-3: BI7984 (manufactured by Baxenden Chemical, a compound blocked with an oxime compound, non-volatile content 75% by mass)

[0456] (Compound (F2) having an epoxy group) F2-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (15), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq)

[0457] [Thiol-based chain transfer agents (J)] Pentaerythritol tetrakis(3-mercaptopropionate)

[0458] [Leveling agent (N)] DOWSIL FZ-2122 (Dow Toray, silicone-based leveling agent)

[0459] [Organic solvent (P)] P-1: Propylene glycol monomethyl ether acetate P-2: Propylene glycol monomethyl ether P-3: 3-Methoxy-1-butanol P-4: Ethyl 3-ethoxypropionate P-5: Dipropylene glycol monomethyl ether acetate The above P-1, P-2, P-3, P-4, and P-5 were mixed in a mass ratio of 80:2:2:15:1 to prepare an organic solvent (P).

[0460] <Evaluation of Photosensitive Composition 1> The following evaluations were carried out on the obtained Photosensitive Compositions 1 to 40. The evaluation results are shown in Table 3.

[0461] [Agglomerate evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater 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, 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 Then, the film was heat-treated in a clean oven at 180° C. for 30 minutes. The number of aggregates on the film was counted by observing reflected light using an optical microscope at a magnification of 200. The evaluation criteria are as follows, with 3 or more being considered practical. 5: There were less than 5 aggregates smaller than 1 μm per 1 mm square. 4: There were 5 to less than 10 aggregates smaller than 1 μm per 1 mm square. 3: There were 10 to less than 15 aggregates smaller than 1 μm per 1 mm square. 2: There were 15 or more but less than 20 aggregates smaller than 1 μm per 1 mm square. 1: There were 20 or more aggregates smaller than 1 μm per 1 mm square.

[0462] [High temperature and humidity resistance evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater 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, 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 , 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23° C., washed with ion-exchanged water, air-dried, and heat-treated in a clean oven at 180° C. for 30 minutes. The spray development was carried out for each photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained substrate was stored for 3 hours under conditions of a temperature of 120°C and humidity of 100%. After storage, the film was cut with a cutter knife to create a lattice pattern of 1 mm squares (total of 100 squares), and a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was firmly pressed against the film and peeled off in a direction of about 180 degrees. The state of the lattice patterns was observed, and the number of peeled lattice patterns was counted. The evaluation criteria are as follows, with 3 or more being considered practical. 5: Less than 2. 4: 2 or more but less than 5. 3: 5 or more but less than 10. 2: 10 or more but less than 15. 1:15 or more.

[0463] [Solvent resistance evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater 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, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a 100 μm-wide stripe pattern at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heat-treated in a clean oven at 180°C for 30 minutes. The spray development was carried out for each photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained substrate was immersed in N-methylpyrrolidone at room temperature for 30 minutes, washed with ion-exchanged water, air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being considered practical. 5: There was no change in appearance or color. 4: Slight wrinkles etc. occurred, but there was no change in color. 3: Some wrinkles or other imperfections occurred, but there was no change in color. 2: Wrinkles and other imperfections have appeared all over the surface, and the color has faded slightly. 1: Peeling or fading has occurred.

[0464] <Evaluation of Photosensitive Composition 2> For the obtained photosensitive compositions 1 to 40, evaluation of aggregates, evaluation of high temperature and high humidity resistance, and evaluation of solvent resistance were performed in the same manner as in evaluation 1 of photosensitive composition, except that the conditions of the heat treatment in the clean oven were changed from 180°C 30 minutes to 150°C 30 minutes. The evaluation results are shown in Table 3.

[0465] [Table 3]

Claims

1. A photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The colorant (A) contains a compound (A1) represented by the following general formula (1), The photosensitive composition, wherein the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2). 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 photosensitive composition according to claim 1, wherein the thermally crosslinkable group-containing monomer unit (b1) is a monomer unit formed from at least one monomer unit selected from the group consisting of monomers represented by the following general formulas (2) to (6): 【Chemistry 2】 (In general formulas (2) to (6), R １ each independently represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. In general formula (2), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms. ２ represents a single bond or an oxygen atom. ３ and L ４ each independently represents a single bond or a divalent organic group. In general formula (3), R ４ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In general formula (4), R ７ represents an alkyl group having 1 to 10 carbon atoms. In general formula (5), R ８ ~R １０ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. ８ ~R １０ At least one of these is an alkoxy group having 1 to 6 carbon atoms. In general formula (6), R １１ ~R １３ each independently represents an alkyl group having 1 to 10 carbon atoms.

3. 2. The photosensitive composition according to claim 1, wherein the thermally crosslinkable group-containing monomer unit (b1) accounts for 1 to 80 mol % of all monomer units in the alkali-soluble resin (B1).

4. The photosensitive composition according to claim 1 , wherein the polymerizable compound (C) comprises a polymerizable compound (C1) having a hydroxyl group.

5. The photosensitive composition according to claim 1 , further comprising a silane coupling agent (E).

6. A film formed from the photosensitive composition according to any one of claims 1 to 5.

7. A color filter comprising the film according to claim 6.

8. A solid-state imaging device comprising the color filter according to claim 7.

9. An image display device comprising the color filter according to claim 7.

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