Photosensitive composition, film, optical filter, solid-state imaging device, image display device, and infrared sensor

Abstract

To provide a photosensitive composition capable of forming a film having superior line width stability and having superior bending resistance and heat cycle resistance.SOLUTION: The problem can be solved by a photosensitive composition comprising: a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) comprises a phthalocyanine compound (A1) of a specific structure, and the polymerizable compound (C) comprises a polymerizable compound (C1) of an amine structure, and a polymerizable compound other than the polymerizable compound (C1) of an amine structure.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] 2. Description of the Related Art Color filters, which are a type of optical filter, are used in image display devices, solid-state imaging devices, and the like. Color filters are produced, for example, through the following steps: a step of applying a photosensitive composition to a substrate such as glass (hereinafter referred to as a coating step), a step of removing the solvent from the coating film by drying (hereinafter referred to as a drying step), a step of irradiating and curing this coating film with ultraviolet light through a photomask having a desired pattern shape (hereinafter referred to as an exposure step), a step of washing and removing the unexposed parts of this coating film with a developer (hereinafter referred to as a development step), and a step of heat treating the film to sufficiently cure it (hereinafter referred to as a post-baking step) to obtain a pattern of the first color. Then, the same operation is performed using photosensitive compositions of different colors to sequentially form patterns of the second and subsequent colors to produce a color filter.

[0003] In recent years, with the miniaturization and increased pixel count of image display devices and solid-state imaging devices, there has been a demand for color filters with higher brightness and contrast, and the use of phthalocyanine compounds as described in Patent Documents 1 to 6 as colorants has been considered. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-113732 A [Patent Document 2] Patent Publication No. 2021-056382 [Patent Document 3] Patent Publication No. 2021-105175 [Patent Document 4] International Publication No. 2020 / 171060 [Patent Document 5] International Publication No. 2023 / 002875 [Patent Document 6] JP 2023-003551 A 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 6, it was found that compositions using these phthalocyanine compounds are insufficient in terms of bending resistance and heat cycle resistance, and are particularly susceptible to the effects of post-bake temperature.

[0006] An object of the present invention is to provide a photosensitive composition capable of forming a film having excellent line width stability, bending resistance, and heat cycle resistance. [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 phthalocyanine compound (A1) represented by the following general formula (1), The present invention relates to a photosensitive composition in which the polymerizable compound (C) contains a polymerizable compound (C1) having an amine structure and a polymerizable compound other than the polymerizable compound (C1) having an amine structure.

[0008] General formula (1) [ka] (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. Effect of the Invention

[0009] According to the present invention, there is provided a photosensitive composition capable of forming a film having excellent line width stability, bending resistance, and heat cycle resistance. The present invention also provides a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of an infrared sensor having an optical filter of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 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.

[0012] 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 and upper limits.

[0013] <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 phthalocyanine compound (A1) represented by the following general formula (1), The polymerizable compound (C) contains a polymerizable compound (C1) having an amine structure and a polymerizable compound other than the polymerizable compound (C1) having an amine structure.

[0014] General formula (1) [ka] (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.

[0015] 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.

[0016] In the photosensitive composition, the polymerization initiator is decomposed by light or heat to generate active species. These active species are added to the polymerizable compound to generate new active species, which proceed in a chain reaction to polymerize. However, if these active species are inactivated by an external factor, the polymerization reaction stops. When the active species is a radical, oxygen inhibits the polymerization (also called oxygen inhibition). Oxygen is in a triplet state in the ground state, so it is highly reactive with radicals and easily reacts with radical active species to form a peroxy radical. This peroxy radical is less reactive with the polymerizable compound, so the polymerization reaction is inhibited. Normally, optical filters such as color filters are manufactured in an air atmosphere, and therefore polymerization is inhibited by oxygen during the exposure process, making it difficult for polymerization to proceed sufficiently, so polymerization is promoted by heat treatment in the post-bake process, and therefore performance is easily affected by the post-bake temperature. Since the polymerizable compound (C1) having an amine structure has a nitrogen atom in the molecule, hydrogen is easily extracted to generate a carbon radical, and the generated peroxy radical extracts hydrogen from the polymerizable compound (C1) having an amine structure, and the newly generated carbon radical starts polymerization. In addition, the generated carbon radical can also capture oxygen, which has the effect of reducing the oxygen concentration. These mechanisms suppress the inhibition of polymerization by oxygen, and polymerization proceeds sufficiently, making it possible to form a film that is less susceptible to the post-bake temperature, and it is presumed that the bending resistance and heat cycle resistance are improved. In addition, since the amine structure has polarity, it is presumed that the bending resistance and heat cycle resistance are easily interacted with the substrate and other components. In addition, it is not necessary to increase the exposure dose or exposure time for curing, and a pattern with a desired line width can be obtained.

[0017] Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[0018] [Colorant (A)] The photosensitive composition of the present invention contains a colorant (A).

[0019] 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.

[0020] (Pigments) The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

[0021] 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.

[0022] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0023] 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.

[0024] 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 (2) 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 (3):

[0025] General formula (2) [ka]

[0026] In general formula (2), R 1 are each independently -OH, -NH 2 , -NH-CN, an acylamino group, an alkylamino group, or an arylamino group; R 2 are each independently -OH or -NH 2 Represents.

[0027] General formula (3) [ka]

[0028] In general formula (3), R 3 each independently represents a hydrogen atom or an alkyl group.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] (dye) Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Furthermore, the dye may be a derivative of these dyes or a lake pigment obtained by converting the dye into a lake.

[0037] 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.

[0038] Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it has excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion component that acts as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0039] 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.

[0040] 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.

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

[0042] 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.

[0043] (Phthalocyanine compound (A1) represented by general formula (1)) The photosensitive composition of the present invention contains, as a colorant (A), a phthalocyanine compound (A1) represented by the following general formula (1) (hereinafter, also simply referred to as phthalocyanine compound (A1)).

[0044] General formula (1) [ka]

[0045] 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. In the general formula (1), M represents a metal atom, a metal oxide, or a metal halide.

[0046] X 1 ~X 16 Examples 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.

[0047] The number of halogen atoms is preferably 4 to 12, and more preferably 6 to 10.

[0048] When there are two or more halogen atoms, those halogen atoms may be the same or different.

[0049] Y 1 The divalent linking group in 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.

[0050] R 1 The monovalent organic group in is not particularly limited as long as it is a group containing carbon atoms, 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.

[0051] 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. The alkyl group which may have a substituent may be a -CH 2 A portion of - may be substituted with an oxygen atom.

[0052] 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.

[0053] 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.

[0054] R 1 When the alkyl group, aryl group, and heterocyclic group 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.

[0055] -Y 1 -R 1 If there are two or more -Y 1 -R 1 may be the same or different from each other.

[0056] -Y 1 -R 1 preferably contains a group represented by the following general formula (4).

[0057] General formula (4) [ka]

[0058] In general formula (4), Z 1 represents a single bond or an oxygen atom, R 2 represents an alkyl group which may have a substituent or an aryl group which may have a substituent; R 3 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. However, when m is 2 or 3, multiple Z 1 , R 2 may be the same or different, and when n is 2, multiple R 3 may be the same or different. Y 1represents a divalent linking group, and * represents a bond to the aromatic ring in general formula (1).

[0059] Z 1 is preferably an oxygen atom.

[0060] R 2 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, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a cyclopentyl group, and a cyclohexyl group.

[0061] R 2 Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and a biphenyl group.

[0062] R 2 When the alkyl group and aryl group have a substituent, examples of the substituent include an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, and the like.

[0063] m is preferably 1 or 2, more preferably 1. When m=1, -CO-Z 1 -R 2 -Y 1 - is preferably bonded to the 3- or 4-position, more preferably bonded to the 4-position. 1 -R 2 -Y 1 - is preferably bonded to the 3,5-position or the 2,4-position, and more preferably bonded to the 2,4-position.

[0064] n is preferably 0 or 1.

[0065] Specific examples of the group represented by general formula (4) are shown below, which are represented by formulas (4-1) to (4-12). In the formulas, Y 1 represents a divalent linking group, and * represents a bond, although the present invention is not limited thereto.

[0066] [ka]

[0067] X 1 ~X 16 -Y in 1 -R 1 The number of is preferably 4 to 12, and more preferably 6 to 10.

[0068] X 1 ~X 16 X 2 , X 3 , X 6 , X 7 , X 10 , X 11 , X 14 , and X 15 At least four of them are -Y 1 -R 1 and preferably all -Y 1 -R 1 And X 1 , X 4 , X 5 , X 8 , X 9 , X 12 , X 13 , and X 16 It is more preferable that is a halogen atom.

[0069] Examples of the metal atom in M ​​include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.

[0070] The metal oxide for M includes oxytitanium, oxyvanadium, and the like.

[0071] 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.

[0072] The method for producing the phthalocyanine 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.

[0073] Specific examples of the phthalocyanine compound (A1) represented by general formula (1) are shown below as compounds of formulae (A1-1) to (A1-9), although the present invention is not limited thereto.

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] The phthalocyanine compounds (A1) represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0080] The content of the phthalocyanine compound (A1) represented by the 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).

[0081] (Colorant (A2) other than the phthalocyanine compound (A1) represented by the 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 phthalocyanine compound (A1) represented by general formula (1).

[0082] The colorant (A2) is not particularly limited, and any known compound can be used. Specific examples include the pigments and dyes described above.

[0083] The colorant (A2) preferably contains one or more selected from the group consisting of CI Pigment Yellow 120, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 231, CI Pigment Yellow 233, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 63, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 15:6.

[0084] The colorant (A2) can be used alone or in combination of two or more kinds.

[0085] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0086] 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 alkali-soluble resin (B) include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, polysiloxane resin, and cyclic olefin resin.

[0087] The weight average molecular weight of the alkali-soluble resin (B) is preferably from 3,000 to 50,000, and more preferably from 4,000 to 40,000.

[0088] The acid value of the alkali-soluble resin (B) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0089] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0090] 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.

[0091] (Alkali-soluble resin (B1) having polycyclic alicyclic hydrocarbon group-containing monomer unit (b1)) From the viewpoint of durability, the photosensitive composition of the present invention preferably contains an alkali-soluble resin (B1) having a polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) (hereinafter, also simply referred to as alkali-soluble resin (B1)) as the alkali-soluble resin (B). The polycyclic alicyclic hydrocarbon group-containing monomer has a high glass transition temperature of the homopolymer, and therefore can form a highly durable film.

[0092] The alkali-soluble resin (B1) may be, for example, a copolymer of a monomer forming a polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) and another monomer copolymerizable therewith.

[0093] [Polycyclic alicyclic hydrocarbon group-containing monomer unit (b1)] Examples of the monomer forming the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred. These monomers can be used alone or in combination of two or more.

[0094] The content of the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) is preferably from 1 to 60 mol %, and more preferably from 1 to 40 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0095] The alkali-soluble resin (B1) can contain a monomer unit other than the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1). The monomer unit other than the polycyclic alicyclic hydrocarbon group-containing monomer unit (b1) is not particularly limited, and examples thereof include monomer units formed from monomers copolymerizable with the polycyclic alicyclic hydrocarbon group-containing monomer. For example, examples thereof include hydroxyl group-containing monomer units (b2), acidic group-containing monomer units (b3), epoxy group-containing monomer units (b4), polymerizable unsaturated group-containing monomer units (b5), aromatic ring-containing monomer units (b6), blocked isocyanate group-containing monomer units (b7), and other monomer units (b8). Among these, it is more preferable that the alkali-soluble resin (B1) has a blocked isocyanate group-containing monomer unit (b7). This can suppress the effect of the post-bake temperature on the resistance.

[0096] [Hydroxyl group-containing monomer unit (b2)] Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, etc. These monomers can be used alone or in combination of two or more.

[0097] 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 the monomer units in the alkali-soluble resin (B1).

[0098] The method for introducing the hydroxyl group-containing monomer unit (b2) into the alkali-soluble resin (B1) may include, in addition to the method of copolymerizing a polycyclic alicyclic hydrocarbon group-containing monomer with a hydroxyl group-containing monomer, a method of adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in the resin (precursor), or a method of adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in the resin (precursor).

[0099] [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-acryloyloxyethyl hexyl hydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. These monomers can be used alone or in combination of two or more.

[0100] From the viewpoint of alkali solubility, the content of the acidic group-containing monomer unit (b3) is preferably from 1 to 40 mol %, and more preferably from 5 to 30 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0101] The method of introducing the acidic group-containing monomer unit (b3) into the alkali-soluble resin (B1) may be a method of copolymerizing a polycyclic alicyclic hydrocarbon group-containing monomer with 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.

[0102] [Epoxy group-containing monomer unit (b4)] Examples of epoxy group-containing monomers include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, etc. These monomers can be used alone or in combination of two or more.

[0103] [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).

[0104] <Method (i)> In the method (i), for example, a precursor having an epoxy group-containing monomer unit (b4) 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.

[0105] 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.

[0106] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0107] <Method (ii)> In the method (ii), for example, a precursor having an acidic group-containing monomer unit (b3) in which the acidic group is a carboxyl group is first synthesized, and then the above-mentioned epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0108] <Method (iii)> In the method (iii), for example, first, a precursor having a hydroxyl group-containing monomer (b2) is synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0109] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, etc. These monomers can be used alone or in combination of two or more kinds.

[0110] [Aromatic ring-containing monomer unit (b6)] Examples of aromatic ring-containing monomers include styrene, α-methylstyrene, vinylnaphthalene, phenyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate, phenol EO or PO modified (meth)acrylate, nonylphenol EO or PO modified (meth)acrylate, N-phenylmaleimide, N-benzylmaleimide, etc. These monomers can be used alone or in combination of two or more. [Blocked isocyanate group-containing monomer unit (b7)] The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of the isocyanate group-containing monomer is protected with a compound that is eliminated by heat (hereinafter, also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C.

[0111] Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, etc. Also usable is an equimolar reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound.

[0112] Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0113] Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide. Examples of the urea compound include urea, thiourea, and ethyleneurea. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0114] The blocking agents can be used alone or in combination of two or more kinds.

[0115] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of the protection reaction and the deprotection reaction, is more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0116] Examples of the blocked isocyanate group-containing monomer include the following compounds, although the present invention is not limited thereto.

[0117] [ka]

[0118] Commercially available blocked isocyanate group-containing monomers include Karenz MOI-DEM (blocking agent desorption temperature: 85 to 95° C.), MOI-BP (blocking agent desorption temperature: 105 to 115° C.), and MOI-BM (blocking agent desorption temperature: 125 to 135° C.), all manufactured by Showa Denko Co., Ltd. These monomers can be used alone or in combination of two or more kinds.

[0119] From the viewpoint of resistance, the content of the blocked isocyanate group-containing monomer unit (b7) is preferably from 1 to 50 mol %, and more preferably from 3 to 40 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0120] [Other monomer units (b8)] Examples of other monomers include acrylic acid esters such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl acetate or vinyl propionate or other vinyl fatty acids; N-substituted maleimides such as methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, and 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin; Examples of such monomers include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more kinds.

[0121] The weight average molecular weight of the alkali-soluble resin (B1) is preferably from 3,000 to 50,000, and more preferably from 4,000 to 40,000.

[0122] 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.

[0123] 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.

[0124] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0125] 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).

[0126] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0127] The polymerizable compound (C) is not particularly limited as long as it is polymerizable, and any known compound can be used. For example, a monomer or oligomer having a polymerizable unsaturated group may be used. 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.

[0128] The polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0129] 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.

[0130] (Polymerizable compound (C1) having an amine structure) The photosensitive composition of the present invention contains, as the polymerizable compound (C), a polymerizable compound (C1) having an amine structure.

[0131] The amine structure of the polymerizable compound (C1) having an amine structure may be any of primary amine, secondary amine, and tertiary amine structures, but is preferably a secondary or tertiary amine structure, but 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.

[0132] Examples of the polymerizable compound (C1) 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).

[0133] 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.

[0134] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0135] 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.

[0136] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0137] 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.

[0138] The polymerizable compound (C1) 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.

[0139] Commercially available polymerizable compounds (C1) 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 and 386 manufactured by Arkema.

[0140] The polymerizable compound (C1) having an amine structure preferably further has a urethane bond. This forms a chemical crosslinked structure by polymerization as well as a physical crosslinked structure by intermolecular hydrogen bonds between the urethane bonds or between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds of the urethane bonds is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interaction between the urethane bonds, improving its resistance.

[0141] The urethane bond can 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).

[0142] 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.

[0143] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0144] 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.

[0145] An example of a commercially available polymerizable compound (C1) having an amine structure and a urethane bond is CN9906NS manufactured by Arkema.

[0146] The polymerizable compound (C1) having an amine structure can be used alone or in combination of two or more kinds.

[0147] The content of the polymerizable compound (C1) having an amine structure is preferably from 1 to 80 mass %, and more preferably from 5 to 60 mass %, in 100 mass % of the polymerizable compound (C).

[0148] (Polymerizable compounds other than the polymerizable compound (C1) having an amine structure) The photosensitive composition of the present invention contains, as the polymerizable compound (C), a polymerizable compound other than the polymerizable compound (C1) having an amine structure.

[0149] Examples of the polymerizable compound other than the polymerizable compound (C1) having an amine structure include a polymerizable compound (C2) having a hydroxyl group, a polymerizable compound (C3) having an acidic group, a lactone-modified polymerizable compound (C4), a polymerizable compound (C5) having a urethane bond, a polymerizable compound (C6) having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds (C7). Among these, from the viewpoints of flex resistance and heat cycle resistance, it is preferable to contain at least one selected from the group consisting of a polymerizable compound (C2) having a hydroxyl group and a polymerizable compound (C3) having an acidic group.

[0150] The polymerizable compound (C2) having a hydroxyl group and the polymerizable compound (C3) having an acidic group preferably have three or less polymerizable unsaturated groups from the viewpoint of flexibility.

[0151] The content of the polymerizable compound other than the polymerizable compound (C1) having an amine structure is preferably from 20 to 99 mass%, more preferably from 40 to 95 mass%, in 100 mass% of the polymerizable compound (C).

[0152] [Polymerizable compound (C2) having a hydroxyl group] Examples of the polymerizable compound (C2) 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, isocyanuric acid EO or PO-modified di(meth)acrylate, and pentaerythritol tri(meth)acrylate are preferred.

[0153] Examples of commercially available polymerizable compounds (C2) 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.

[0154] The polymerizable compound (C2) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0155] The content of the polymerizable compound (C2) having a hydroxyl group is preferably from 10 to 99 mass %, and more preferably from 20 to 90 mass %, in 100 mass % of the polymerizable compound (C).

[0156] [Polymerizable compound having an acidic group (C3)] Examples of the polymerizable compound (C3) 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.

[0157] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0158] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0159] 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.

[0160] Commercially available polymerizable compounds (C3) 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.

[0161] The polymerizable compound (C3) having an acidic group can be used alone or in combination of two or more kinds.

[0162] The content of the polymerizable compound (C3) having an acidic group is preferably from 0 to 40 mass %, more preferably from 1 to 30 mass %, in 100 mass % of the polymerizable compound (C).

[0163] The mass ratio of the content of the polymerizable compound (C1) having an amine structure to the total content of the polymerizable compound (C2) having a hydroxyl group and the polymerizable compound (C3) having an acidic group is preferably 10:90 to 90:10, and more preferably 15:85 to 85:15.

[0164] [Lactone-modified polymerizable compound (C4)] The lactone-modified polymerizable compound (C4) 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 trimethololmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0165] Commercially available lactone-modified polymerizable compounds (C4) include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0166] [Polymerizable compound having a urethane bond (C5)] Examples of the polymerizable compound (C5) 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. The polymerizable compound (C5) having a urethane bond does not contain an amine structure.

[0167] 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.

[0168] 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.

[0169] The polymerizable compound (C5) 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.

[0170] The method for introducing an acidic group into the polymerizable compound (C5) having a urethane bond can be, for example, synthesized 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.

[0171] 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.

[0172] Commercially available polymerizable compounds (C5) 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.

[0173] [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.

[0174] 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.

[0175] The polymerizable compound (C6) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0176] [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.

[0177] 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.

[0178] The other polymerizable compounds (C7) can be used alone or in combination of two or more kinds.

[0179] [Polymerization initiator (D)] The photosensitive composition of the present invention contains a polymerization initiator (D).

[0180] 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 (D1) that generates radicals by light (hereinafter, also simply referred to as photopolymerization initiator (D1)) is preferably a compound that generates radicals in response to light in the ultraviolet to visible light range. The polymerization initiator (D2) that generates radicals by heat (hereinafter, also simply referred to as the thermal polymerization initiator (D2)) may be a compound that generates radicals by the action of heat and light.

[0181] Examples of the photopolymerization initiator (D1) 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.

[0182] 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-1919T, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistrys. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855 A, JP 2022-5115524 A, and the like are also included. Among these, the photopolymerization initiator (D1) preferably contains an oxime compound.

[0183] Examples of the thermal polymerization initiator (D2) 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-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenyl Pinacol compounds such as ethane, 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. Further examples include oxime sulfonate compounds described in WO 2012 / 101245, WO 2016 / 030790, and the like.

[0184] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0185] 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.

[0186] It is preferable to use a photopolymerization initiator (D1) and a thermal polymerization initiator (D2) in combination as the polymerization initiator (D). It is presumed that resistance is further improved by carrying out a radical polymerization reaction in both the exposure step and the post-bake step.

[0187] The mass ratio of the photopolymerization initiator (D1) to the thermal polymerization initiator (D2) is preferably from 90:10 to 10:90, and more preferably from 80:20 to 20:80.

[0188] [Thermal crosslinkable compound (E)] The photosensitive composition of the present invention preferably contains a thermally crosslinkable compound (E), whereby the thermally crosslinkable compound (E) crosslinks with other components upon heating, thereby further improving resistance. In this specification, the thermally crosslinkable compound (E) is different from the alkali-soluble resin (B) and the polymerizable compound (C).

[0189] The thermally crosslinkable compound (E) 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.

[0190] The thermally crosslinkable compound (E) can be used alone or in combination of two or more kinds.

[0191] The content of the thermally crosslinkable compound (E) 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.

[0192] (Compound (E1) Having a Blocked Isocyanate Group) The compound (E1) 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.

[0193] The compound (E1) 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.

[0194] 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 particularly preferably active methylene compounds from the viewpoint of resistance after low-temperature heating. 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.

[0195] 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.

[0196] 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.

[0197] Examples of the compound (E1) 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.

[0198] [ka]

[0199] Examples of X (blocked isocyanate group) in the above compound include the structures shown in (X-1) to (X-6) below. In the following structures, * represents a bond. However, the present invention is not limited to these.

[0200] [ka]

[0201] Examples of commercially available compounds (E1) 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.

[0202] The compound (E1) having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0203] The weight average molecular weight of the compound (E1) having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0204] The acid value of the compound (E1) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0205] The compound (E1) having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0206] The content of the compound (E1) 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.

[0207] (Compound (E2) having an epoxy group) The epoxy group is a group having a three-membered cyclic ether structure, and includes an alicyclic epoxy group.

[0208] Examples of the compound (E2) 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.

[0209] Commercially available products of the compound (E2) 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.

[0210] The compound (E2) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0211] The epoxy equivalent of the compound (E2) 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.

[0212] From the viewpoint of resistance, the compound (E2) having an epoxy group more preferably contains a compound represented by the following general formula (5).

[0213] General formula (5) [ka]

[0214] In formula (5), 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.

[0215] 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 (5) may be the same or different.

[0216] The compound represented by the general formula (5) 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.

[0217] The acid value of the compound (E2) having an epoxy group is preferably 10 mgKOH / g or less.

[0218] The compound (E2) having an epoxy group can be used alone or in combination of two or more kinds.

[0219] The content of the compound (E2) 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.

[0220] As the thermally crosslinkable compound (E), it is particularly preferable to use a compound (E1) having a blocked isocyanate group and a compound (E2) having an epoxy group in combination. The mass ratio of the compound (E1) having a blocked isocyanate group to the compound (E2) having an epoxy group is preferably from 5:95 to 95:5, and more preferably from 10:90 to 90:10.

[0221] [Ultraviolet absorber (F)] The photosensitive composition of the present invention preferably contains an ultraviolet absorber (F), which suppresses the influence of changes in the amount of exposure and the type and amount of the polymerization initiator, thereby obtaining a more stable line width.

[0222] From the viewpoint of line width stability, the ultraviolet absorber (F) is preferably a compound having a maximum absorption wavelength in the wavelength range of 300 to 400 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 320 to 380 nm.

[0223] Examples of the ultraviolet absorber (F) include benzotriazole compounds, benzophenone compounds, triazine compounds, conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, and salicylate compounds.

[0224] (Benzotriazole compound (F1)) Benzotriazole compounds (F1) include, for example, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and linear alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, and the like. Examples of commercially available products include Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT manufactured by BASF Japan Ltd., and Adeka STAB LA-31RG and LA-31G manufactured by ADEKA Corporation.

[0225] (Benzophenone compounds (F2)) Examples of the benzophenone compound (F2) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylaminohydroxybenzoylhexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Examples of commercially available products include Ubinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan Ltd., and Adeka STAB 1413 manufactured by ADEKA Corporation.

[0226] (Triazine compounds (F3)) Examples of the triazine compound (F3) include a reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl with [(C10-C16 (mainly C12-C13) alkyloxy)methyl]oxirane, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2, Examples of such phenols include 4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol. Examples of commercially available products include Tinuvin 400, 405, 406, 477, and 479 manufactured by BASF Japan, and Adeka STAB LA-46 and LA-F70 manufactured by ADEKA Corporation.

[0227] (Conjugated diene compounds (F4)) An example of the conjugated diene compound (F4) is UV503 manufactured by Daito Chemical Industry Co., Ltd.

[0228] (Methyldibenzoyl compounds (F5)) Examples of the methyldibenzoyl compound (F5) include 1,3-diphenyl-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione.

[0229] (Coumarin compounds (F6)) Examples of the coumarin compound (F6) include 4-hydroxycoumarin and 7-hydroxycoumarin.

[0230] From the viewpoint of line width stability, the ultraviolet absorber (F) preferably contains at least one selected from the group consisting of a benzotriazole compound (F1), a benzophenone compound (F2), and a triazine compound (F3), and more preferably contains at least one selected from the group consisting of a benzotriazole compound (F1) and a benzophenone compound (F2).

[0231] The ultraviolet absorbents (F) can be used alone or in combination of two or more kinds.

[0232] The content of the ultraviolet absorber (F) is preferably from 30 to 300 parts by mass, and more preferably from 60 to 200 parts by mass, based on 100 parts by mass of the polymerization initiator (D).

[0233] [Pigment derivatives (G)] The photosensitive composition of the present invention can contain a pigment derivative (G).

[0234] 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.

[0235] 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).

[0236] 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.

[0237] The pigment derivative (G) can be used alone or in combination of two or more kinds.

[0238] 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).

[0239] [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).

[0240] 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.

[0241] 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.

[0242] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0243] 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-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.

[0244] 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.

[0245] 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.

[0246] The dispersing resin (H) can be used alone or in combination of two or more kinds.

[0247] 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).

[0248] [Sensitizer (I)] The photosensitive composition of the present invention can contain a sensitizer (I).

[0249] 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.

[0250] The sensitizers (I) can be used alone or in combination of two or more kinds.

[0251] 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).

[0252] [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.).

[0253] The curing agents can be used alone or in combination of two or more kinds.

[0254] 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 (E).

[0255] [Thiol-based chain transfer agents (J)] The photosensitive composition of the present invention may contain a thiol-based chain transfer agent (J).

[0256] 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.

[0257] The thiol chain transfer agent (J) can be used alone or in combination of two or more kinds.

[0258] The content of the thiol chain transfer agent (J) is preferably from 1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0259] [Silane coupling agent (K)] The photosensitive composition of the present invention may contain a silane coupling agent (K).

[0260] The silane coupling agent (K) is a compound having a hydrolyzable group. 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. 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. In addition, the silane coupling agent (K) may have a functional group other than the hydrolyzable group, such as 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, or a ureido group. In this specification, the silane coupling agent (K) is not included in the polymerizable compound (C), the thermally crosslinkable compound (E), and the thiol-based chain transfer agent (J).

[0261] The silane coupling agent (K) is not particularly limited, and known compounds can be used. For example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3-triethoxysilyl)propyl)tetrasulfide, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, tris(-trimethoxysilylpropyl)isocyanate, and the like.

[0262] Commercially available silane coupling agents (K) 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, KBE-1003, and KBM-5 manufactured by Shin-Etsu Chemical Co., Ltd. 02, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBM-3086, KBE-585A, X-12-1048, X-12-50, X-12-5263HP, etc.

[0263] The silane coupling agent (K) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0264] The polysiloxane type is a compound in which the hydrolyzable group is 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.

[0265] The organic polymer type is a silane coupling agent (K) in which the hydrolyzable group is 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.

[0266] The silane coupling agent (K) can be used alone or in combination of two or more kinds.

[0267] The content of the silane coupling agent (K) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0268] [Polymerization inhibitor (L)] The photosensitive composition of the present invention may contain a polymerization inhibitor (L).

[0269] The polymerization inhibitor (L) 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.

[0270] The polymerization inhibitor (L) can be used alone or in combination of two or more kinds.

[0271] The content of the polymerization inhibitor (L) is preferably from 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0272] [Antioxidants (M)] The photosensitive composition of the present invention can contain an antioxidant (M).

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0282] The antioxidants (M) can be used alone or in combination of two or more kinds.

[0283] 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.

[0284] [Leveling agent (N)] The photosensitive composition of the present invention can contain a leveling agent (N).

[0285] 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.

[0286] 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.

[0287] 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.

[0288] 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.

[0289] 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.

[0290] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0291] 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.

[0292] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0293] 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.

[0294] 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.

[0295] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0296] 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.,

[0297] 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.

[0298] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0299] The content of the organic solvent (P) is preferably such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0300] The photosensitive composition of the present invention may contain components other than those described above. Examples of the other components include surfactants, acid generators, salt generators, curing catalysts, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, insulating materials, etc. The content of the other components may be appropriately set within a range that does not impair the effects of the present invention.

[0301] [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.

[0302] 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).

[0303] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

[0304] 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.

[0305] [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.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] 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.

[0310] 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.

[0311] <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.

[0312] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced through a step of applying the coloring composition of the present invention onto a substrate and a step of drying the applied composition.

[0313] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or a CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0314] The coating method may be a known method, 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, or offset printing.

[0315] 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.

[0316] [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.

[0317] 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.

[0318] 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 after coating, the film is dried or the entire surface is exposed to light as necessary.

[0319] A method for forming a pattern by photolithography will be described in detail below. In the photolithography method, the photosensitive composition of the present invention is applied onto a substrate, the layer formed by drying is exposed to light in a pattern through a mask (exposure process), the unexposed parts are removed by alkaline development (development process), and the pattern is then heat-treated (post-bake process).

[0320] [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.

[0321] [Development process] Next, an alkaline development process is carried out, whereby the unexposed portions of the layer are dissolved in an alkaline developer, and only the hardened portions remain, yielding a patterned film. Examples of the alkaline developer include aqueous solutions containing alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Two or more of these alkaline compounds can be used in combination. The alkaline developer may contain a surfactant and an organic solvent in addition to the alkaline compound and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0322] [Post-bake process] After development, a heat treatment (post-baking) is performed, which improves the resistance of the film. The temperature is preferably 80 to 260° C., and from the environmental viewpoint, 150° C. or less is more preferable. The time is preferably about 2 minutes to 2 hours.

[0323] <Optical filters> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, as a color filter, a black matrix, a light-shielding filter, an anti-reflection filter, an infrared cut filter, an infrared transmission filter, etc. The optical filter of the present invention can be produced by the same method as the above-mentioned film.

[0324] <Solid-state imaging element> The solid-state imaging device of the present invention has the above optical filter. The solid-state imaging device is not particularly limited as long as it includes the optical filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0325] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film with only the light receiving portion of the photodiode open on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and the optical filter (color filter) of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the optical filter (the side closer to the substrate), or a light collecting means on the optical filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each color pixel. 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.

[0326] <Image display device> The image display device of the present invention includes the above optical filter. Examples of the image display device include a liquid crystal display and an organic EL 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.

[0327] 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.

[0328] 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).

[0329] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor used is not particularly limited as long as it is provided with the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0330] A substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like. A light shielding film with only the light receiving portion of the photodiodes open is provided on the photodiodes and the transfer electrodes. A device protection film is provided on this light shielding film, and the optical filter of the present invention is provided on this device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same applies below) below the optical filter (the side closer to the substrate) on the device protection film, or the light collecting means may be provided on the optical filter.

[0331] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with an optical filter of the present invention.

[0332] The imaging area provided on the solid-state imaging element 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0333] The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0334] The color filter 112 is a color filter having pixels formed therein that transmit and absorb light of specific wavelengths in the visible light region, and for example, a color filter having red (R), green (G), and blue (B) pixels formed therein is used.

[0335] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 113 is disposed.

[0336] The infrared transmission filter 113 is a filter that has a visible light blocking property and transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0337] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A flat film 116 is formed so as to cover the microlens 115.

[0338] In the embodiment shown in FIG. 1, the resin film 114 is disposed, but instead of the resin film 114, an infrared transmission filter 113 may be formed.

[0339] This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor. EXAMPLES

[0340] 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.

[0341] Before describing the examples, each measurement method will be described.

[0342] 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.

[0343] (Molecular weight) Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0344] (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.

[0345] (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.

[0346] <Production of Colorant (A)> (Phthalocyanine compound (A1-1) 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, 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 raising the temperature to room temperature. After the reaction was completed, the reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 1.

[0347] Intermediate 1 [ka]

[0348] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 6.2 parts of intermediate 1, 1.21 parts of zinc iodide, and 12 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned phthalocyanine compound (A1-1).

[0349] (Phthalocyanine 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.

[0350] Intermediate 2 [ka]

[0351] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 15.0 parts of intermediate 2, 1.93 parts of zinc iodide, and 23 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned phthalocyanine compound (A1-2).

[0352] (Phthalocyanine 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 liquid was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and vacuum dried to obtain the following intermediate 3.

[0353] Intermediate 3 [ka]

[0354] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 6.0 parts of intermediate 3, 1.38 parts of zinc iodide, and 15 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned phthalocyanine compound (A1-3).

[0355] (Phthalocyanine 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.

[0356] Intermediate 4 [ka]

[0357] 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 above-mentioned phthalocyanine compound (A1-4).

[0358] (Phthalocyanine 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.

[0359] Intermediate 5 [ka]

[0360] In a flask equipped with a stirrer, condenser, dropping funnel, and thermometer, add 10.1 parts Intermediate 5, 2.88 parts of potassium fluoride, and 50 parts of acetone were added and stirred at room temperature until dissolved. After cooling on ice, an acetone solution of 7.46 parts of ethyl p-hydroxybenzoate was added dropwise from the dropping funnel over 2 hours, and the mixture was stirred for another 2 hours. The mixture was then stirred for about 12 hours while the temperature was raised to room temperature. The reaction solution was filtered and concentrated, and recrystallized by adding methanol. The obtained crystals were filtered and dried in a vacuum to obtain the following intermediate 6.

[0361] Intermediate 6 [ka]

[0362] In a flask equipped with a stirrer, a condenser, a gas inlet tube, and a thermometer, 12.4 parts of intermediate 6, 3.2 parts of zinc iodide, and 23 parts of benzonitrile were added, and the mixture was reacted under nitrogen gas flow at 160°C for 10 hours while stirring. After cooling to room temperature, methyl cellosolve was added to the reaction solution, and the reaction solution was then dropped into a mixture of methanol and water, stirred for 30 minutes, and filtered. The resulting product was washed several times with methanol and vacuum dried to obtain the above-mentioned phthalocyanine compound (A1-5).

[0363] <Production of alkali-soluble resin (B)> (Solution of alkali-soluble resin (B1-1) having polycyclic alicyclic hydrocarbon group-containing monomer unit (b1)) 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 then stirred while replacing with nitrogen and heated to 78° C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-methyl-1-oxo-2-propenyl oxy] ethyl] amino] carbonyl malonic acid ester manufactured by Showa Denko K.K.), 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.

[0364] (Solution of alkali-soluble resin (B2-1) not having polycyclic alicyclic hydrocarbon group-containing monomer unit (b1)) A separable 4-neck flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 100 parts of PGMAc was charged in the reaction vessel, which was then heated to 80°C and replaced with nitrogen in the reaction vessel. From the dropping tube, a mixture of 25.1 parts of benzyl methacrylate, 23.0 parts of n-butyl methacrylate, 14.3 parts of 2-hydroxyethyl methacrylate, 13.4 parts of methacrylic acid, 24.1 parts of Aronix M-110 (manufactured by Toagosei Co., Ltd., paracumylphenol ethylene oxide modified acrylate), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was stirred for another 3 hours to react. 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 87 mgKOH / g, and the weight average molecular weight was 25,000.

[0365] <Production of polymerizable compound (C)> (Polymerizable compound having an amine structure (C1-1)) In a four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, 250 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-402, manufactured by Toagosei Co., Ltd.) was added, and 17.3 parts of di-n-butylamine was added at room temperature, followed by reaction at 50° C. for 4 hours to obtain a polymerizable compound (C1-1) having an amine structure. The reaction was carried out under a mixed atmosphere of air / nitrogen.

[0366] (Polymerizable compound having an amine structure (C1-2)) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were placed, and the mixture was heated to 50°C while stirring. Next, 160.8 parts of N-methylethanolamine was gradually dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was reacted at 50°C for 2 hours while stirring. Next, the temperature was raised to 100° C., and 149.7 parts of hexamethylene diisocyanate was gradually dropped into the flask from the dropping funnel. After the dropping was completed, the reaction was carried out with stirring at 100° C. for 4 hours, to obtain a polymerizable compound (C1-2) having a urethane bond and an amine structure.

[0367] <Production of Dispersion Resin (H)> (Dispersion resin (H-1) solution) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% or more of the monomer had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged, and IR showed a 2,270 cm 3 reaction based on the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After cooling, PGMAc was added so that the non-volatile content was 30 mass %, to obtain a dispersion resin (H-1) solution having a polymerizable unsaturated group. The acid value was 68 mgKOH / g, and the weight average molecular weight was 13,000.

[0368] (Dispersed resin (H-2) solution) In a reactor equipped with a gas inlet tube, condenser, stirring blade, and 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-2) solution was prepared. The amine value was 169.8 mg KOH / g.

[0369] <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): 15.0 parts Pigment derivative (G-1): 1.0 part Dispersion resin (H-1) solution: 30.0 parts Organic solvent (P-1): 54.0 parts

[0370] 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.

[0371] [Table 1]

[0372] The respective raw materials listed in Table 1 are as follows.

[0373] [Colorant (A)] (Colorant (A2)) A2-1: CI Pigment Yellow 120 A2-2: CI Pigment Yellow 138 A2-3: CI Pigment Yellow 139 A2-4: CI Pigment Yellow 150 A2-5: CI Pigment Yellow 185 A2-6: CI Pigment Yellow 233 A2-7: CI Pigment Green 58 A2-8: CI Pigment Green 63

[0374] [Pigment derivatives (G)] G-1: The following compound

[0375] [ka]

[0376] [Organic solvent (P)] P-1: Propylene glycol monomethyl ether acetate

[0377] <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. Phthalocyanine compound (A1-1) represented by general formula (1): 3.50 parts Dispersion 4: 15.00 parts Alkali-soluble resin (B1-1) solution: 6.67 parts Alkali-soluble resin (B2-1) solution: 1.33 parts Polymerizable compound having an amine structure (C1-4): 0.50 parts Polymerizable compound having a hydroxyl group (C2-1): 0.80 parts Polymerizable compound having an acidic group (C3-1): 0.50 parts Other polymerizable compounds (C7-3): 1.20 parts Photopolymerization initiator (D1-1): 0.30 parts Thermal polymerization initiator (D2-1): 0.20 parts Compound having a blocked isocyanate group (E1-1): 1.67 parts Compound having an epoxy group (E2-1): 0.40 parts Benzotriazole compound (F1-1): 0.15 parts Thiol chain transfer agent (J): 0.18 parts Silane coupling agent (K): 0.10 parts Leveling agent (N): 0.02 parts Organic solvent (P): 67.48 parts

[0378] [Examples 2 to 38 and Comparative Example 1] (Photosensitive compositions 2-39) Photosensitive compositions 2 to 39 were produced in the same manner as in Example 1 using the raw materials and amounts shown in Tables 2-1 to 2-4.

[0379] [Table 2-1]

[0380] [Table 2-2]

[0381] [Table 2-3]

[0382] [Table 2-4]

[0383] The respective raw materials listed in Tables 2-1 to 2-4 are as follows.

[0384] [Polymerizable compound (C)] (Polymerizable compound (C1) having an amine structure) C1-3: Aronix MT-3041 (manufactured by Toagosei Co., Ltd., a multifunctional acrylate having a tertiary amine structure) C1-4: CN9906NS (Arkema, acrylate having a urethane bond and a tertiary amine structure)

[0385] (Polymerizable compound having a hydroxyl group (C2)) C2-1: Isocyanuric acid EO modified diacrylate C2-2: Pentaerythritol triacrylate

[0386] (Polymerizable compound having an acidic group (C3)) C3-1: Aronix M-5300 (manufactured by Toagosei Co., Ltd., a monofunctional acrylate having an acidic group) C3-2: Aronix M-520 (manufactured by Toagosei Co., Ltd., a trifunctional acrylate with an acidic group)

[0387] (Lactone-modified polymerizable compound (C4)) C4-1: KAYARAD DPCA-20 (lactone-modified multifunctional acrylate manufactured by Nippon Kayaku Co., Ltd.)

[0388] (Other polymerizable compounds (C7)) C7-1: Tricyclodecane dimethanol diacrylate C7-2: Trimethylolpropane triacrylate C7-3: Isocyanuric acid EO modified triacrylate C7-4: Pentaerythritol tetraacrylate

[0389] [Polymerization initiator (D)] (Photopolymerization initiator (D1)) D1-1: Compound having the following structure D1-2: Compound of the following structure D1-3: Omnirad379 (IGM Resins)

[0390] [ka]

[0391] (Thermal polymerization initiator (D2)) D2-1: Benzopiconal D2-2: 1,1-bis(tert-hexylperoxy)cyclohexane D2-3: Di-tert-hexyl peroxide D2-4: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane

[0392] [Thermal crosslinkable compound (E)] (Compound (E1) Having a Blocked Isocyanate Group) E1-1: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, a compound blocked with an active methylene compound, non-volatile content 60% by mass) E1-2: BI7982 (manufactured by Baxenden Chemical, compound blocked with a pyrazole compound, non-volatile content 70% by mass) E1-3: BI7984 (manufactured by Baxenden Chemical, a compound blocked with an oxime compound, non-volatile content 75% by mass)

[0393] (Compound (E2) having an epoxy group) E2-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (5), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq)

[0394] [Ultraviolet absorber (F)] (Benzotriazole compound (F1)) F1-1: Tinuvin 326 (BASF, maximum absorption wavelength 355 nm)

[0395] (Benzophenone compounds (F2)) F2-1: 4,4'-bis(diethylamino)benzophenone (maximum absorption wavelength 352 nm) F2-2: 2,2',4,4'-tetrahydroxybenzophenone (maximum absorption wavelength 350 nm)

[0396] (Triazine compounds (F3)) F3-1: Tinuvin 460 (BASF, maximum absorption wavelength 349 nm)

[0397] [Thiol chain transfer (J)] J-1: Mercaptosuccinic acid J-2: Pentaerythritol tetrakis(3-mercaptopropionate) The above J-1 and J-2 were mixed in a mass ratio of 50:50 to obtain thiol-based chain transfer (J).

[0398] [Silane coupling agent (K)] K-1: KBM-803 (Shin-Etsu Chemical Co., Ltd., 3-mercaptopropyltrimethoxysilane) K-2: KBE-403 (Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane) The above K-1 and K-2 were mixed in a mass ratio of 50:50 to prepare a silane coupling agent (K).

[0399] [Leveling agent (N)] N-1: Megafac F-554 (DIC, fluorine-based leveling agent) N-2: DOWSIL FZ-2122 (Dow Toray, silicone-based leveling agent) The above N-1 and N-2 were mixed in a mass ratio of 50:50 to prepare a leveling agent (N).

[0400] [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).

[0401] <Evaluation of Photosensitive Composition 1> The following evaluations were carried out on the obtained photosensitive compositions 1 to 39. The evaluation results are shown in Table 3.

[0402] [Line width stability 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 2.5 μm, and then dried on a hot plate at 90° 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 and 100 mJ / cm 2 The substrate was exposed to light through a photomask with a stripe pattern of 100 μm width at two levels. After cooling to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23° C., washed with ion-exchanged water, and air-dried. The 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 evaluation substrate was subjected to an exposure of 50 mJ / cm using a Nikon ECLIPSE LV100POL Model optical microscope. 2 Line width (CD 50 ) and 100 mJ / cm 2 Line width (CD 100 The difference in line width (ΔCD) due to the difference in exposure dose was calculated using the following formula (1). The evaluation criteria are as follows, with a score of 3 or higher being considered practical. Equation (1): ΔCD = CD 100 -CD 50 5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6μm or more

[0403] [Flexibility evaluation] The obtained photosensitive composition was applied to a PET film by spin coating so that the film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Then, the substrate was cooled to room temperature, and then irradiated with an ultra-high pressure mercury lamp with an illumination intensity of 30 mW / cm. 2 , 100mJ / cm 2 Thereafter, the substrate was 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 post-baked in a clean oven at 130° C. for 30 minutes. The obtained evaluation film was cut to a width of 2 cm and a length of 10 cm, and a bending test (bending width 2 mm, frequency 117 Hz, number of times 100,000) was performed using a bending tester (YUASA SYSTEM's "DMLHB"). After the test, the coating film was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being considered usable. 5: No cracks 4: 1 to less than 5 cracks 3: 5 to less than 10 cracks 2: 10 to less than 20 cracks 1: 20 or more cracks

[0404] [Heat cycle resistance evaluation] The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dry film thickness was 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, the substrate was irradiated with light at an illumination intensity of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask with a 100 μm-wide stripe pattern. 2 , 100mJ / cm 2The substrate was then spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 130°C for 30 minutes to obtain an evaluation substrate. The obtained substrate was subjected to 500 cycles of temperature increase and decrease, i.e., 10 minutes at -20°C and 10 minutes at 100°C, and the pattern was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being practical. 5: No visible abnormalities after 500 cycles 4: Slight cracking and / or peeling occurs at 500 cycles 3: After 500 cycles, some cracks and / or peeling occurred. 2: Cracks and / or peeling occurs after 200 cycles 1:100 cycles before cracking and / or peeling

[0405] [Table 3]

[0406] <Evaluation of Photosensitive Composition 2> For the obtained photosensitive compositions 1 to 39, evaluation of bending resistance and evaluation of heat cycle resistance were performed in the same manner as in evaluation 1 of photosensitive composition, except that the post-baking conditions in the clean oven were changed from 130° C. 30 minutes to 110° C. 30 minutes. The evaluation results are shown in Table 4.

[0407] [Table 4] [Explanation of symbols]

[0408] 100 Infrared Sensor 110 Solid-state image sensor 111 Infrared cut filter 112 Color Filter 113 Infrared transmission filter 114 Resin Film 115 Micro Lens 116 Flat membrane

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 phthalocyanine compound (A1) represented by the following general formula (1), The photosensitive composition, wherein the polymerizable compound (C) comprises a polymerizable compound (C1) having an amine structure and a polymerizable compound other than the polymerizable compound (C1) having an amine structure. 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 polymerizable compound (C1) having an amine structure has a urethane bond.

3. 2. The photosensitive composition according to claim 1, wherein the polymerizable compound other than the polymerizable compound (C1) having an amine structure includes at least one selected from the group consisting of a polymerizable compound (C2) having a hydroxyl group and a polymerizable compound (C3) having an acidic group.

4. 4. The photosensitive composition according to claim 3, wherein a mass ratio of a content of the polymerizable compound (C1) having an amine structure to a total content of the polymerizable compound (C2) having a hydroxyl group and the polymerizable compound (C3) having an acidic group is from 10:90 to 90:

10.

5. The photosensitive composition according to claim 1 , wherein the polymerization initiator (D) comprises a photopolymerization initiator (D1) and a thermal polymerization initiator (D2).

6. The photosensitive composition according to claim 1 , further comprising an ultraviolet absorber (F).

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

8. An optical filter comprising the film according to claim 7.

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

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

11. An infrared sensor comprising the optical filter according to claim 8.

Images