Photosensitive composition, and film, color filter, solid-state imaging element, image display device, and infrared sensor using same

Abstract

An object of the present invention is to provide a photosensitive composition capable of forming a pattern excellent in suppression of water stains after development and smoothness and having a small amount of change in line width.SOLUTION: Specifically disclosed is a photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the polymerization initiator (D) comprises a polymerization initiator (D1) represented by general formula (1) and a glyoxylate-based polymerization initiator (D2). (In General Formula (1), R1 and R2 each independently represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. R3 represents hydrogen or a monovalent group. ) SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition used for forming a color filter or the like. [Background technology]

[0002] Color filters used in image display devices, solid-state imaging devices, etc. are generally patterned by photolithography. The exposure process in photolithography is carried out in an atmospheric environment, and therefore polymerization does not proceed sufficiently due to oxygen inhibition, resulting in problems such as discoloration of the film during the development process (hereinafter referred to as water stains) and a rough film surface that reduces smoothness. Furthermore, when a highly sensitive polymerization initiator is used to promote polymerization, the amount of change in the pattern width tends to increase, resulting in a problem of the pattern width being larger than the desired width.

[0003] To address these issues, Patent Document 1 discloses a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, and a solvent, with the aim of preventing development stains (water stains), where the alkali-soluble resin contains a monomer of a specific structure, has a molecular weight of 12,000 to 17,000, and an acid value of 60 to 120 KOH mg / g, and the photopolymerization initiator contains an oxime ester fluorene derivative compound. Patent Document 2 also discloses a resist composition containing a fluorine-based surfactant of a specific structure with the aim of suppressing water stains. Patent Document 3 also discloses a curable composition with the aim of producing a cured film with excellent line width stability, which contains a black colorant, a polymerizable compound, resin A, a photopolymerization initiator, and a polymerization inhibitor, where resin A satisfies either one of the requirements of having an acid value of 120 to 350 KOH / g and a weight-average molecular weight of 3,000 to 7,500. Furthermore, Patent Document 4 discloses a photosensitive colored resin composition for the purpose of suppressing changes in line width, which contains a colorant, a photopolymerizable compound, an initiator, a latent antioxidant of a specific structure, and a solvent, wherein the colorant includes one or more selected from dyes and lake colorants, and the initiator includes a photopolymerization initiator having a tertiary amine structure and an oxime ester photoinitiator having a diphenyl sulfide skeleton. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2017-173787 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-102212 [Patent Document 3] International Publication No. 2019 / 171902 [Patent Document 4] Japanese Patent Publication No. 2022-62022 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the compositions described in Patent Documents 1 to 4 were unable to satisfy all of the requirements for water stain prevention, smoothness, and line width stability at a certain level or higher.

[0006] An object of the present invention is to provide a photosensitive composition that can suppress water stains after development, has excellent smoothness, and can form a pattern with little change in line width. [Means for solving the problem]

[0007] <1> The present invention provides a photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), The photosensitive composition, wherein the polymerization initiator (D) comprises a polymerization initiator (D1) represented by the following general formula (1) and a glyoxylate-based polymerization initiator (D2):

[0008] [ka] (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent. <2> the mass ratio of the polymerization initiator (D1) represented by the general formula (1) to the glyoxylate-based polymerization initiator (D2) is 95:5 to 5:95; <1> A photosensitive composition according to claim 1. <3> The glyoxylate-based polymerization initiator (D2) contains a polymerization initiator represented by the following general formula (2): <1> or <2> A photosensitive composition according to claim 1. [ka] (In general formula (2), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. X1 represents a structure represented by the following general formula (3). n represents 0 or 1. [ka] (In the general formula (3), Y2 represents an oxygen atom or a sulfur atom. R3 represents a monovalent substituent. m represents an integer of 0 to 3; *1 and *2 represent bonds to the carbon atom in general formula (2). However, when n in general formula (2) is 0, the bond is either *1 or *2. <4> the polymerization initiator (D) further comprises a polymerization initiator (D1) represented by the general formula (1) and a polymerization initiator (D3) other than the glyoxylate-based polymerization initiator (D2); <1> ~ <3> Any photosensitive composition. <5> The alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a repeating unit represented by the following general formula (4): the content of the repeating unit represented by the general formula (4) is 1 to 50 mol % of all repeating units of the alkali-soluble resin (B1); <1> ~ <4> Any photosensitive composition. [ka] (In the general formula (4), R1 represents a hydrogen atom or a methyl group. R2 represents an alkyl group having 4 to 22 carbon atoms. <6> The colorant (A) contains a salt-forming compound of a dye and a resin that forms a salt with the dye. <1> ~ <5> Any photosensitive composition. <7> <1> ~ <6> A film formed from any one of the photosensitive compositions. <8> <7> A color filter having a film of <9> <8> A solid-state imaging device having a color filter. <10> <8> An image display device having a color filter. <11> <8> an infrared sensor having a color filter; [Effects of the Invention]

[0009] According to the present invention, there is provided a photosensitive composition capable of suppressing water stains after development, having excellent smoothness, and capable of forming a pattern with little line width change. The present invention also provides a film, a color filter, a solid-state imaging device, an image display device, and an infrared sensor using the photosensitive composition. [Brief explanation of the drawings]

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

[0011] Hereinafter, embodiments 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 embodiments, and can be modified and carried out within a range that can solve the problems.

[0012] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Additionally, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). In this specification, the molecular weight of a low-molecular-weight compound that can be determined is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight of a compound having a molecular weight distribution is a weight-average molecular weight in terms of polystyrene 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 polymerization initiator (D) contains a polymerization initiator (D1) represented by the following general formula (1) and a glyoxylate-based polymerization initiator (D2).

[0014] [ka]

[0015] In the general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.

[0016] The mechanism by which the photosensitive composition having the above-described structure can solve the problems of the present invention is not clear, but is speculated as follows.

[0017] The polymerization initiator (D1) represented by general formula (1) (hereinafter simply referred to as polymerization initiator (D1)) has lower sensitivity than oxime ester-based polymerization initiators. However, its rigid, hydrophobic, and heat-resistant fluorene skeleton contributes to the formation of highly resistant films and the suppression of water staining. Furthermore, its low sensitivity contributes to the reduction of pattern width variation. On the other hand, the glyoxylate-based polymerization initiator (D2) (hereinafter simply referred to as polymerization initiator (D2)) is a hydrogen-abstraction polymerization initiator that abstracts hydrogen from other components to generate active radicals. Because hydrogen-abstraction polymerization initiators can create polymerization initiation sites in addition to polymerizable compounds, polymerization on the film surface proceeds without being affected by oxygen. Therefore, it is believed that the film surface roughness during development is reduced, resulting in improved smoothness. The use of these two types of polymerization initiators contributes to the suppression of water staining after development, resulting in the formation of patterns with excellent smoothness and minimal linewidth variation.

[0018] Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[0019] [Colorant (A)] The photosensitive composition of the present invention contains a colorant (A).

[0020] The colorant (A) is not limited, and examples thereof include pigments and dyes. Pigments and dyes can be used in combination. Examples of pigments include inorganic pigments and organic pigments. Inorganic pigments and organic pigments can be used in combination. Examples of pigments include organic-inorganic composites.

[0021] The colorant (A) can be used alone or in combination of two or more kinds.

[0022] The content of the colorant (A) is preferably from 1 to 70 mass %, more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0023] (pigment) The pigment is not limited, and examples thereof include compounds classified as pigments in the Color Index.

[0024] 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, 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, JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844.

[0025] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0026] 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, and 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, and the pigments described in JP-A-2012-226110.

[0027] Further, examples of the yellow pigment include pigments containing at least one anion selected from the group consisting of mono-, di-, tri-, and tetra-anions of azo compounds represented by the following general formula (5) and azo compounds having tautomeric structures 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 (6):

[0028] [ka]

[0029] In general formula (5), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group.

[0030] In general formula (5), two R2s each independently represent -OH or -NH2.

[0031] [ka]

[0032] In general formula (6), three R3s each independently represent a hydrogen atom or an alkyl group.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0037] Other examples include inorganic pigments such as silica, talc, titanium oxide, zinc oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

[0038] Other examples include fluorescent pigments and near-infrared absorbing pigments.

[0039] The pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the micronized 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 diameter is more preferably 10 to 70 nm.

[0040] A resin may be added to the salt milling treatment as needed. By adding a resin, the pigment is coated with the resin, improving stability, light resistance, and the like. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature, insoluble in water, and partially soluble in organic solvents are preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0041] (dye) From the viewpoint of brightness, the colorant (A) preferably contains a dye.

[0042] The dye is not particularly limited and may contain known compounds. Examples include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, fluorescent dyes, and near-infrared absorbing dyes. Also included are derivatives, lakes, salt-forming compounds, and polymers of these dyes.

[0043] The acid dye preferably has an acidic group such as a sulfonic acid or carboxylic acid. The direct dye preferably forms an inorganic salt of the acid dye, or a salt-forming compound formed between 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 the acid dye and a resin component having these functional groups. Furthermore, the salt-forming compound can be sulfonamidated to modify it into a sulfonic acid amide compound, which makes it easy to obtain a photosensitive 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 preferred because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0044] Although basic dyes can be used as they are, salt-forming compounds formed with organic acids, perchloric acid, or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in the salt-forming compounds of basic dyes, the anion component acting as a counter ion is preferably an organic sulfonic acid, organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-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. Furthermore, the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

[0045] The chemical structure of the dye may be, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azido dyes, ... Examples of the dye structure include dyes derived from dyes selected from the group consisting of quinone dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0046] Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

[0047] From the viewpoint of smoothness, the dye is preferably a salt-forming compound of a dye and a resin that forms a salt with the dye.

[0048] From the viewpoint of smoothness, the dye is preferably a compound having a xanthene skeleton. It is presumed that the fluorene skeleton of the polymerization initiator (D1) interacts with the xanthene skeleton to suppress elution during development and aggregation during post-baking.

[0049] Compounds having a xanthene skeleton include CI Acid Violet 9, 30, 102, CI Basic Violet 10, 11, 25, CI Acid Red 51, 52, 87, 92, 94, 289, 388, 463, JP 2012-013758 A, JP 2012-208452 A, JP 2013-033194 A, WO 2016 / 031442, WO 2016 / 121194, JP 2019-109490 A, and compounds described in WO 2019 / 031292, etc. Among these, CI Acid Red 52,289,463 is preferred.

[0050] The resin that forms a salt with the dye (hereinafter simply referred to as the salt-forming resin) is not particularly limited as long as it is a resin that can form a salt with the dye. In this specification, the salt-forming resin is preferably a resin having a repeating unit represented by the following general formula (7):

[0051] [ka]

[0052] In the general formula (7), R1 represents a hydrogen atom or a methyl group.

[0053] In general formula (7), R2 to R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Two or more of R2 to R4 may be bonded to each other to form a cyclic structure.

[0054] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or a combination thereof. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl. Among these, methyl, ethyl, propyl, and butyl groups are preferred.

[0055] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, etc. Among these, a phenyl group is preferred.

[0056] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group, etc. Among these, a benzyl group and a phenethyl group are preferred.

[0057] The alkyl group, aryl group, or aralkyl group of R2 to R4 may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, and a benzoyl group.

[0058] The cyclic structure formed by two or more of R2 to R4 bonding to each other includes a 5- to 7-membered nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle include the following cyclic structures: R in the following formula is any of R2 to R4.

[0059] [ka]

[0060] These cyclic structures may have a substituent, such as a halogen atom, an alkoxy group, or a hydroxyl group.

[0061] In the general formula (7), L1 represents a divalent linking group.

[0062] Examples of the divalent linking group in L1 in general formula (7) include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R5-, or -COO-R6- (wherein R5 and R6 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms). Among these, -COO-R6- in which R6 is an alkylene group having 1 to 3 carbon atoms is preferred.

[0063] In general formula (7), Y1 - represents a counter anion.

[0064] Y1 in general formula (7) - The counter anion in - , Br - , I - , ClO4 - , BF4 - , CH3COO - , PF6 - , SO3 - , aromatic dicarboxylic acid imide anion, aromatic sulfonic acid anion, aromatic phosphonic acid anion, aromatic carboxylic acid anion, etc.

[0065] Examples of the repeating unit represented by general formula (7) include repeating units derived from alkyl (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl triethyl ammonium chloride, (meth)acryloyloxyethyl dimethyl benzyl ammonium chloride, and (meth)acryloyloxyethyl methyl morpholino ammonium chloride, alkyl (meth)acryloyl amide-based quaternary ammonium salts such as (meth)acryloyl aminopropyl trimethyl ammonium chloride, (meth)acryloyl aminoethyl triethyl ammonium chloride, and (meth)acryloyl aminoethyl dimethyl benzyl ammonium chloride, dimethyl diallyl ammonium methyl sulfate, and trimethyl vinyl phenyl ammonium chloride. These may be used alone or in combination of two or more.

[0066] The repeating unit represented by formula (7) preferably accounts for 1 to 70 mol %, more preferably 1 to 60 mol %, of all repeating units in the salt-forming resin.

[0067] The salt-forming resin may contain repeating units other than the repeating unit represented by general formula (7) (hereinafter also referred to as other repeating units). Examples of other repeating units 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-methylpropional, and the like. -Hydroxyethyl phthalate, 4-hydroxyphenyl (meth)acrylate, 4-vinylphenol, 4-isopropenylphenol, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic anhydride, Acrylic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, oxiranyl (meth)acrylate, glycerin 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, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 8 -(Meth)acryloyloxyoctyltrimethoxysilane, malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-Diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, dimethyl-2,2'-[oxybis(methyl) Examples of repeating units include those derived from di(n-propyl)-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, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These can be used alone or in combination of two or more.

[0068] The salt-forming resin may contain a repeating unit having an ethylenically unsaturated group, such as a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, or a (meth)acryloylamide group.

[0069] Examples of the repeating unit having an ethylenically unsaturated group include units produced by reaction of a hydroxyl group, a carboxyl group, or an epoxy group present in the salt-forming resin with a compound having a reactive functional group and an ethylenically unsaturated group. Examples of the compound having a reactive functional group and an ethylenically unsaturated group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexyl hydrophthalic acid, β-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 2-ethylglycidyl (meth)acrylate.

[0070] Examples of the structure of the salt-forming resin include a random structure, a block structure, a graft structure, a comb structure, and a star structure.

[0071] The weight average molecular weight of the salt forming resin is preferably 3,000 to 50,000, more preferably 4,000 to 40,000.

[0072] The salt forming resins can be used alone or in combination of two or more kinds.

[0073] The method for producing the salt-forming compound of a dye and a salt-forming resin is not limited, and any known method can be used, such as those described in paragraphs 0360 to 0371 of JP-A No. 2015-28587 and paragraph 0135 of JP-A No. 2018-172542.

[0074] The content of the salt-forming compound of the dye and the salt-forming resin is preferably from 0.5 to 100% by mass, more preferably from 1 to 80% by mass, in 100% by mass of the colorant (A).

[0075] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0076] The alkali-soluble resin (B) is a resin that dissolves in an alkaline developer. Examples of the alkali-soluble resin (B) include (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamide-imide resins, cyclic olefin resins, and polysiloxane resins.

[0077] The alkali-soluble resin (B) preferably has an alkali-soluble group. Examples of the alkali-soluble group include acidic groups such as a carboxy group, a phosphate group, and a sulfonic acid group. Among these, a carboxy group is more preferred from the viewpoint of developability.

[0078] Examples of the structure of the alkali-soluble resin (B) include a random structure, a block structure, a graft structure, a comb structure, a star structure, etc. Among these, the random structure is preferred from the viewpoint of film resistance.

[0079] The weight average molecular weight of the alkali-soluble resin (B) is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000.

[0080] The acid value of the alkali-soluble resin (B) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0081] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0082] The content of the alkali-soluble resin (B) is preferably from 1 to 95 mass %, more preferably from 3 to 80 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0083] (Alkali-soluble resin (B1) having a repeating unit represented by general formula (4)) From the viewpoint of suppressing water stains, the alkali-soluble resin (B) preferably contains an alkali-soluble resin (B1) (hereinafter simply referred to as alkali-soluble resin (B1)) having a repeating unit represented by the following general formula (4): The general formula (4) has a long alkyl chain in R4, which results in low surface tension and high hydrophobicity. Therefore, it is presumed that the highly hydrophobic moieties orient on the film surface, suppressing water stains.

[0084] [ka]

[0085] In the general formula (4), R1 represents a hydrogen atom or a methyl group.

[0086] In general formula (4), R2 represents an alkyl group having 4 to 22 carbon atoms. The alkyl group may be linear, branched, cyclic, or a combination thereof. Among these, linear or branched groups are preferred from the viewpoint of suppressing water stains. The number of carbon atoms is preferably 5 to 20, more preferably 6 to 18, from the viewpoint of suppressing water stains. Examples of alkyl groups having 4 to 20 carbon atoms include butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, isooctyl, docosyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl groups. Among these, hexyl, 2-ethylhexyl, octyl, nonyl, isononyl, isodecyl, dodecyl, octadecyl, and isooctadecyl groups are preferred.

[0087] Examples of the repeating unit represented by general formula (4) include repeating units derived from n-butyl(meth)acrylate, isobutyl(meth)acrylate, n-pentyl(meth)acrylate, isopentyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, 2-octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, isononyl(meth)acrylate, isodecyl(meth)acrylate, dodecyl(meth)acrylate, octadecyl(meth)acrylate, isooctadecyl(meth)acrylate, docosyl(meth)acrylate, etc. These may be used alone or in combination of two or more. Among these, hexyl (meth)acrylate, octyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, and isooctadecyl (meth)acrylate are preferred.

[0088] The content of the repeating unit represented by formula (4) is preferably from 1 to 50 mol %, more preferably from 5 to 40 mol %, of all repeating units in the alkali-soluble resin (B1).

[0089] From the viewpoint of film smoothness, the alkali-soluble resin (B1) preferably further contains a repeating unit represented by the following general formula (8). The repeating unit represented by general formula (8) can initiate polymerization reactions at two active radicals: the addition of an active radical generated by cleavage of the polymerization initiator (D1) to the ethylenically unsaturated group in general formula (8), and the abstraction of a hydrogen atom from the carbon atom in the L1 moiety adjacent to the oxygen atom in general formula (8) by the polymerization initiator (D2). Therefore, it is believed that the film is more likely to have a high molecular weight and a high crosslink density, improving the durability of the film surface.

[0090] [ka]

[0091] In the general formula (8), R1 and R2 each independently represent a hydrogen atom or a methyl group.

[0092] In the general formula (8), L1 represents a trivalent hydrocarbon group. The trivalent hydrocarbon group includes a trivalent aliphatic hydrocarbon group. The trivalent hydrocarbon group may be linear, branched, cyclic, or a combination thereof, and may be substituted with an alkoxy group, an aryloxy group, an aryloxythio group, a halogen atom, or the like. The trivalent aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the trivalent aliphatic hydrocarbon group include a group represented by the following formula (L1-1) and a group represented by the following formula (L1-2).

[0093] [ka]

[0094] In the formula (L1-1) and the formula (L1-2), * represents a bond to the oxygen atom of the general formula (8).

[0095] In the general formula (8), R3 represents a hydrogen atom or a group represented by the following general formula (9).

[0096] [ka]

[0097] In the general formula (9), L2 represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon ring group. The divalent aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof, and may be substituted with an alkoxy group, a carboxy group, a halogen atom, or the like. The divalent aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the divalent aliphatic hydrocarbon group include an ethylene group, a propylene group, an ethenylene group, a cyclohex-4-ene-1,2-diyl group, and a cyclohexa-1,2-diyl group. The divalent aromatic hydrocarbon ring group is a monocyclic or condensed ring, and can be substituted with an alkoxy group, a carboxy group, a halogen atom, or the like. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a pyrene ring, and a fluorene ring.

[0098] In the general formula (9), * represents a bond to the oxygen atom in the general formula (8).

[0099] The content of the repeating unit represented by formula (8) is preferably from 5 to 85 mol %, more preferably from 15 to 75 mol %, of all repeating units in the alkali-soluble resin (B1).

[0100] The repeating unit represented by general formula (8) can be synthesized by adding an unsaturated monobasic acid (modifying compound) such as (meth)acrylic acid to at least a portion of the epoxy groups contained in the alkali-soluble resin (B1) to form a repeating unit in which R3 in general formula (8) is a hydrogen atom.Furthermore, a polybasic acid anhydride (modifying compound) can be added to some of the hydroxyl groups generated by the addition to synthesize a repeating unit in which R3 in general formula (8) is represented by general formula (9). Furthermore, a repeating unit in which R3 in general formula (8) is a hydrogen atom can be synthesized by adding a (meth)acrylate (modifying compound) having an epoxy group to some of the carboxyl groups contained in the alkali-soluble resin (B1). Furthermore, a polybasic acid anhydride (modifying compound) can be added to some of the hydroxyl groups generated by the addition to obtain a repeating unit in which R3 in general formula (8) is represented by general formula (9). Specifically, the repeating unit can be synthesized by the methods described in JP-A-2001-089533, JP-A-2008-088394, etc.

[0101] The alkali-soluble resin (B1) may contain a repeating unit other than the repeating unit represented by general formula (4) and the repeating unit represented by general formula (8). Examples of the repeating unit include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, and maleic acid. , monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate , 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, 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, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6]Decan-9-yl (meth)acrylate, 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 2-(acetoacetoxy)ethyl (meth)acrylate, 3-(meth)acrylo Acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, Malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of para-cumylphenol, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, p-Chlorostyrene, vinylnaphthalene, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmorpholine, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimide N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-Dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, dimethyl-2,2'-[oxybis(methylene)]bis-2-propionate Examples of repeating units include those derived from di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These can be used alone or in combination of two or more.

[0102] The weight average molecular weight of the alkali-soluble resin (B1) is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000.

[0103] The acid value of the alkali-soluble resin (B1) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0104] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0105] The content of the alkali-soluble resin (B1) is preferably from 10 to 100 mass %, more preferably from 15 to 100 mass %, based on 100 mass % of the alkali-soluble resin (B).

[0106] (Alkali-soluble resin (B2) other than alkali-soluble resin (B1)) The alkali-soluble resin (B) can contain an alkali-soluble resin (B2) other than the alkali-soluble resin (B1) (hereinafter, also simply referred to as other alkali-soluble resin (B2)).

[0107] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0108] The polymerizable compound (C) is a polymerizable compound, and examples thereof include a monomer or oligomer having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a styryl group.

[0109] Examples of the polymerizable compound (C) include a polymerizable compound (C1) having an amine structure, a polymerizable compound (C2) having a urethane bond, and other polymerizable compounds (C3).

[0110] The polymerizable compound (C) can be used alone or in combination of two or more kinds.

[0111] The content of the polymerizable compound (C) is preferably from 1 to 80 mass %, more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0112] (Polymerizable compound (C1) having an amine structure) The use of a polymerizable compound (C1) with an amine structure improves the smoothness of the film. In addition to the polymerization reaction initiated by the active radical generated by the cleavage of the polymerization initiator (D1) and its addition to the ethylenically unsaturated group, the polymerizable compound (C1) with an amine structure contains a highly electronegative nitrogen atom in its molecule, which facilitates the abstraction of a hydrogen atom from the carbon atom adjacent to the nitrogen atom by the polymerization initiator (D2), thereby initiating a polymerization reaction initiated by the active radical. Therefore, the use of a polymerizable compound (C1) with an amine structure is thought to reduce the susceptibility to polymerization inhibition by oxygen, improving the durability of the film surface.

[0113] The amine structure of the polymerizable compound (C1) having an amine structure may be a primary amine, a secondary amine, or a tertiary amine. Of these, a secondary amine or a tertiary amine is preferred. However, the amine structure of the polymerizable compound (C1) having an amine structure does not include an amide structure, an imide structure, a urethane structure, or a cyclic amine structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0114] 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).

[0115] 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, and diglycerides thereof. Examples of the alkylene oxide-modified tri(meth)acrylate include lin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerin 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.

[0116] The (meth)acrylate compound (X) can be used alone or in combination of two or more kinds.

[0117] Examples of the amine compound (Y) include n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, ethanolamine, butanolamine, diethylene glycolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminobenzyl alcohol, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-butyl-4-hydroxybutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0118] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0119] The Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) can be produced by any known method without any limitation, such as those described in International Publication No. 2006 / 075754, JP-A No. 2008-545859, and JP-A No. 2017-066347.

[0120] The polymerizable compound (C1) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of methods for introducing the acidic group and / or the hydroxyl group include a method 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.

[0121] 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, CN371NS, 372, 374, 383 and 386 manufactured by Arkema, and Photomer 4250, 4771, 4775, 4967 and 5006 manufactured by IGM Resins.

[0122] The polymerizable compound (C1) having an amine structure preferably further contains a urethane bond. This allows for the formation of a chemical crosslinked structure through polymerization, as well as a physical crosslinked structure due to intermolecular hydrogen bonds between the urethane bonds and between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds at the urethane bond site is greater than the cohesive energy of other organic structures, such as ether bonds. Therefore, it is believed that the interaction between the urethane bonds makes the film flexible and strong.

[0123] The urethane bond can be introduced, for example, by a method of producing the polymer 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).

[0124] 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, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatomethyl)benzene. Further, biuret, isocyanurate, adduct, allophanate and the like of these compounds may also be used.

[0125] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0126] The method for the urethane reaction between the precursor and the polyisocyanate compound (Z) is not limited, and known methods can be used, such as those described in JP-A-2018-517797.

[0127] An example of a commercially available polymerizable compound (C1) having an amine structure and a urethane bond is CN9906NS manufactured by Arkema.

[0128] The polymerizable compound (C1) having an amine structure can be used alone or in combination of two or more kinds.

[0129] The content of the polymerizable compound (C1) having an amine structure is preferably from 0.1 to 80 mass %, more preferably from 0.5 to 60 mass %, in 100 mass % of the polymerizable compound (C).

[0130] (Polymerizable compound (C2) having a urethane bond) The use of a polymerizable compound (C2) with a urethane bond improves the smoothness of the film. The physical cross-linking structure formed by intermolecular hydrogen bonds at the urethane bond provides moderate flexibility, which is thought to suppress the occurrence of wrinkles due to cure shrinkage during exposure. Note that the polymerizable compound (C2) with a urethane bond is not included in the polymerizable compound (C1) with an amine structure.

[0131] Examples of the polymerizable compound (C2) 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 resulting mixture with a hydroxyl group-containing (meth)acrylate.

[0132] 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, glycerol tri(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.

[0133] 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 derivatives, isocyanurates, and trimethylolpropane adducts thereof.

[0134] The polymerizable compound (C2) having a urethane bond preferably has 3 to 15 ethylenically unsaturated groups, and more preferably 5 to 12 ethylenically unsaturated groups.

[0135] The molecular weight of the polymerizable compound (C2) having a urethane bond is preferably from 500 to 5,000, more preferably from 500 to 3,000.

[0136] The polymerizable compound (C2) having a urethane bond may further have an acidic group from the viewpoint of developability. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0137] The acidic group can be introduced into the polymerizable compound (C2) having a urethane bond by, for example, first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the reaction product.

[0138] 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.

[0139] Alternatively, the polyfunctional isocyanate may be reacted with a diol compound having a carboxy group to synthesize a precursor having isocyanate groups at both ends, followed by reacting the precursor with the hydroxyl group-containing (meth)acrylate.

[0140] Examples of the diol compound having a carboxy group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, and 2,2-dimethylolhexanoic acid.

[0141] Commercially available polymerizable compounds (C2) 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.

[0142] The polymerizable compound (C2) having a urethane bond can be used alone or in combination of two or more kinds.

[0143] The content of the polymerizable compound (C2) having a urethane bond is preferably from 5 to 80 mass %, more preferably from 10 to 70 mass %, in 100 mass % of the polymerizable compound (C).

[0144] (Other polymerizable compounds (C3)) The other polymerizable compound (C3) is a polymerizable compound other than the polymerizable compound (C1) having an amine structure and the polymerizable compound (C2) having a urethane bond. Examples of other polymerizable compounds (C3) include polymerizable compounds having a hydroxyl group, polymerizable compounds having an acidic group, lactone-modified polymerizable compounds, and polymerizable compounds having a dendrimer structure or a hyperbranched structure.

[0145] Examples of the polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and isocyanuric acid EO or P. Examples of the acrylic acid ester include O-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, and dipentaerythritol caprolactone-modified penta(meth)acrylate; and epoxy (meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxy group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, isocyanuric acid EO- or PO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0146] Examples of commercially available polymerizable compounds having a hydroxyl group include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., Aronix M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, and 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.

[0147] Examples of polymerizable compounds having an acidic group include esters of dicarboxylic acids with poly(meth)acrylates containing free hydroxyl groups formed from polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates.

[0148] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0149] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0150] Examples of the polycarboxylic 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.

[0151] Commercially available polymerizable compounds having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel Allnex Corporation.

[0152] The lactone-modified polymerizable compound is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0153] Commercially available lactone-modified polymerizable compounds include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0154] A polymerizable compound with a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting a core (hereinafter also referred to as the core portion), and polymerizable unsaturated groups are bonded to the ends of the branches, and has a spherical, highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

[0155] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer 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), and CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER Co., Ltd., and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials Corporation.

[0156] Examples of other polymerizable compounds (C3) other than those mentioned above 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, glycerol tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylol Other examples include propane EO- or PO-modified tri(meth)acrylate, isocyanuric acid 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, (meth)acrylic acid ester of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0157] The other polymerizable compounds (C3) can be used alone or in combination of two or more.

[0158] [Polymerization initiator (D)] The photosensitive composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) contains a polymerization initiator (D1) represented by general formula (1) and a glyoxylate-based polymerization initiator (D2).

[0159] (Polymerization initiator (D1) represented by general formula (1)) The polymerization initiator (D1) represented by the general formula (1) is a compound having the following structure.

[0160] [ka]

[0161] In the general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkyl group may be substituted with a halogen atom, a cyano group, an amino group, an alkoxy group, or the like. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Among these, from the viewpoint of suppressing water stains, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0162] In general formula (1), R3 represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Examples of the substituents that the benzoyl and thenoyl groups may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0163] The polymerization initiator (D1) can be synthesized by any known method without any particular limitation, for example, the methods described in JP-A-2019-507108 and JP-A-2019-528331.

[0164] Specific examples of the polymerization initiator (D1) include compounds (D1-1) to (D1-6), which are listed below, but the present invention is not limited thereto.

[0165] [ka]

[0166] The polymerization initiator (D1) can be used alone or in combination of two or more kinds.

[0167] The content of the polymerization initiator (D1) is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, based on 100 mass % of the polymerization initiator (D), from the viewpoint of suppressing water stains and suppressing line width variation.

[0168] (Glyoxylate-based polymerization initiator (D2)) Examples of the glyoxylate polymerization initiator (D2) include methylphenyl glyoxylate, ethylphenyl glyoxylate, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester, polybutylene glycol-bis-phenyl glyoxylate, and compounds described in JP-T-2001-511137, JP-T-2002-540243, JP-T-2010-505977, WO 2020 / 015966, WO 2022 / 238591, WO 2022 / 207945, and the like.

[0169] Commercially available glyoxylate polymerization initiators (D2) include, for example, Omnirad MBF,754 and Omnipol 2712 manufactured by IGM Resins.

[0170] [Polymerization initiator (D2-1) represented by general formula (2)] The glyoxylate polymerization initiator (D2) is preferably a polymerization initiator (D2-1) represented by the following general formula (2).

[0171] [ka]

[0172] In the general formula (2), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkyl group may be substituted with a halogen atom, a cyano group, an amino group, an alkoxy group, or the like. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be an aryl group substituted with a halogen atom, a cyano group, an amino group, an alkoxy group, etc. Among these, R1 and R2 are preferably alkyl groups having 1 to 20 carbon atoms, and more preferably alkyl groups having 1 to 10 carbon atoms.

[0173] In the general formula (2), n represents 0 or 1. However, when X1 described later has a structure represented by the following general formula (11), n ​​is 0.

[0174] X1 represents a structure represented by the following general formula (3), a structure represented by the following general formula (10), or a structure represented by the following general formula (11).

[0175] [ka]

[0176] In the general formula (3), Y2 represents an oxygen atom or a sulfur atom. Among these, Y2 is preferably a sulfur atom, which can shift the absorption spectrum to the long wavelength side, increase reactivity when exposed to an ultra-high pressure mercury lamp often used in the manufacture of color filters, and improve smoothness.

[0177] In the general formula (3), R3 represents a monovalent substituent. Examples of the monovalent substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl ester group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 4 to 20 carbon atoms, an amino group, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyl group, a nitro group, a cyano group, an optionally substituted benzoyl group, an optionally substituted thenoyl group, etc. Examples of the substituent that the benzoyl group or thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, etc., and the substituent may be in the range of 1 to 3. Among these, the monovalent substituent is preferably a benzoyl group which may have a substituent, from the viewpoint of reactivity, which improves smoothness.

[0178] In the general formula (3), m represents an integer of 0 to 3. Among these, m is preferably 0 or 1, and 1 is more preferable.

[0179] In general formula (3), *1 and *2 represent bonds to the carbon atom in general formula (2), provided that when n in general formula (2) is 0, the bond is *1.

[0180] In general formula (10), Y3 represents an oxygen atom, a sulfur atom, -C(R4R5)-, or -N(R6)-, and R4 to R6 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms has the same meaning as the alkyl group explained for R1 and R2 in general formula (2). Among these, Y3 is preferably -C(R4R5)-, more preferably -CH2-.

[0181] In the general formula (10), Z3 represents a single bond, an oxygen atom, a carbon atom, or a sulfur atom. Among these, Z3 is preferably a single bond.

[0182] In general formula (10), *1 and *2 represent bonds to the carbon atom in general formula (2). However, when n in general formula (2) is 0, the bond is either *1 or *2.

[0183] In general formula (11), R7~R 10 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or -N(R 12 R 13 ), or -SR 14 represents R 12 ~R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 10 Adjacent groups may be bonded to each other to form an aromatic ring. The alkyl group having 1 to 20 carbon atoms has the same meaning as the alkyl group explained for R1 and R2 in general formula (2). Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentoxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, a 2-ethylhexyloxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, etc. The alkoxy group can be substituted with a halogen atom, a nitro group, etc.

[0184] In general formula (11), R7~R 10Examples of the aromatic ring formed by bonding adjacent groups include hydrocarbon aromatic rings and heteroaromatic rings. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring. The aromatic ring can be substituted with a halogen atom, an alkoxy group, a hydroxyl group, or the like.

[0185] In general formula (11), R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms has the same meaning as the alkyl group explained for R1 and R2 in general formula (2).

[0186] In general formula (11), *1 represents a bond to the carbon atom of general formula (2).

[0187] X1 is preferably a structure represented by general formula (3), which allows the absorption spectrum to be shifted to the long wavelength side, thereby increasing the reactivity upon exposure to an ultra-high pressure mercury lamp and improving smoothness.

[0188] The polymerization initiator (D2-1) represented by general formula (2) can be synthesized by any known method without limitation. For example, methods described in WO 2018 / 041935, WO 2021 / 070152, WO 2022 / 238592, etc. can be mentioned.

[0189] Specific examples of the polymerization initiator (D2-1) represented by general formula (2) are shown below, including compounds (D2-1-1) to (D2-1-33), although the present invention is not limited thereto.

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] The polymerization initiator (D2-1) represented by general formula (2) is preferably at least one compound selected from the group consisting of compounds (D2-1-1) to (D2-1-10).

[0194] The polymerization initiator (D2) can be used alone or in combination of two or more kinds.

[0195] From the viewpoint of smoothness, the content of the polymerization initiator (D2) is preferably from 10 to 80% by mass, more preferably from 15 to 60% by mass, based on 100% by mass of the polymerization initiator (D).

[0196] The mass ratio of the polymerization initiator (D1) to the polymerization initiator (D2) is preferably from 95:5 to 5:95, more preferably from 80:20 to 20:80. The total content of the polymerization initiator (D1) and the polymerization initiator (D2) is preferably from 30 to 90% by mass, more preferably from 40 to 80% by mass, based on 100% by mass of the polymerization initiator (D).

[0197] (Other polymerization initiators (D3)) The polymerization initiator (D) preferably contains a polymerization initiator (D3) other than the polymerization initiator (D1) and the polymerization initiator (D2).

[0198] Examples of the other polymerization initiator (D3) include acetophenone-based polymerization initiators, acylphosphine-based polymerization initiators, oxime-based polymerization initiators, thioxanthone-based polymerization initiators, and benzophenone-based polymerization initiators. Examples of these polymerization initiators include acetophenone-based polymerization initiators such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2,2-dimethoxy-2-phenylacetophenone; Oxime polymerization initiators 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); acylphosphine polymerization initiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; thioxanthone-based polymerization initiators such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone; benzophenone-based polymerization initiators such as benzophenone, 4-methylbenzophenone, 4-[4-methylphenylthio]benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone; triazine-based polymerization initiators 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 initiator include quinone-based polymerization initiators such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone. Among these, oxime-based polymerization initiators, thioxanthone-based polymerization initiators, and benzophenone-based polymerization initiators are preferred.

[0199] From the viewpoint of suppressing water stains, the oxime-based polymerization initiator preferably contains a polymerization initiator represented by the following general formula (12).

[0200] [ka]

[0201] In the general formula (12), R1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, or 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 tert-butyl group, an amyl group, an isoamyl 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. A methyl group or an ethyl group is preferred.

[0202] In the general formula (12), R2 represents a hydrogen atom, a nitro group, a group having an ether bond, or a group exhibiting aromaticity. When R2 is a group exhibiting aromaticity, the structure of the cyclic portion thereof may be a monocyclic ring or a fused ring. Furthermore, in terms of composition, it may be a carbocyclic ring or a heterocyclic ring. The polymerization initiator represented by general formula (12) is particularly preferably a structure in which R2 has a carbonyl group and the rings are bonded to each other via the carbonyl group. Examples of the group exhibiting aromaticity include a benzene ring, a furan ring, a thiophene ring, a naphthalene ring, a benzofuran ring, a benzothiophene ring, and an indole ring. Among these, a hydrogen atom or a nitro group is preferred, and a hydrogen atom is more preferred.

[0203] In the general formula (12), n represents an integer of 1 to 8. n is preferably 1 to 4.

[0204] In the general formula (12), m represents an integer of 1 to 5. m is preferably 1 or 2.

[0205] The polymerization initiator represented by general formula (12) can be produced by any known method without any particular limitation, for example, the method described in JP-A-2012-526185.

[0206] Specific examples of the polymerization initiator represented by general formula (12) are shown below, but the present invention is not limited to these.

[0207] [ka]

[0208] The benzophenone-based polymerization initiator is preferably a benzophenone-based polymerization initiator having an amino group. It is presumed that the benzophenone-based polymerization initiator having an amino group can not only initiate polymerization by itself by abstracting hydrogen from other components, but also can supply hydrogen when used in combination with the polymerization initiator (D2), thereby efficiently promoting the polymerization reaction.

[0209] The other polymerization initiators (D3) can be used alone or in combination of two or more.

[0210] The content of the other polymerization initiator (D3) is preferably from 50 to 400% by mass, more preferably from 60 to 300% by mass, relative to 100% by mass of the polymerization initiator (D2).

[0211] The polymerization initiator (D) may be a photopolymerization initiator or a thermal polymerization initiator. As explained above, the photopolymerization initiator is a polymerization initiator that generates radicals mainly by light, and generates radicals in response to light ranging from ultraviolet rays to visible light. The thermal polymerization initiator is a polymerization initiator that generates radicals mainly by heat, but may also generate radicals by the action of heat and light.

[0212] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol-based compounds such as silane, 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 peroxide 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.

[0213] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0214] The content of the polymerization initiator (D) is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0215] [Dye derivative (E)] The photosensitive composition of the present invention may contain a dye derivative (E).

[0216] The dye derivative (E) is a compound having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of the dye derivative (E) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0217] When the solubility of the dye derivative (E) is low, it can be added when the colorant (A) is micronized or when the colorant (A) is dispersed. The average primary particle size of the dye derivative (E) is preferably 5 to 200 nm.

[0218] The dye derivative (E) can be used alone or in combination of two or more kinds.

[0219] The content of the dye derivative (E) is preferably from 1 to 20 parts by mass, more preferably from 2 to 15 parts by mass, relative to 100 parts by mass of the colorant (A).

[0220] [Dispersion resin (F)] The photosensitive composition of the present invention may contain a dispersing resin (F).

[0221] The dispersing resin (F) is preferably a resin having an adsorptive group that has a high affinity for the colorant (A). The adsorptive group preferably has at least one of a basic group and an acidic group.

[0222] 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.

[0223] Examples of the acidic group include a carboxy group, a phosphate group, and a sulfonic acid group.

[0224] Examples of resin types for the dispersion resin (F) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxy groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0225] Examples of the structure of the dispersing resin (F) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, the block structure, the graft structure, and the comb structure are preferred from the viewpoint of dispersion stability.

[0226] The dispersing resin (F) preferably has a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, and a blocked isocyanate group.

[0227] Examples of the dispersion resin (F) include resins described in JP-A-2008-029901, resins described in JP-A-2009-155406, resins described in JP-A-2010-185934, resins described in JP-A-2011-157416, resins described in WO 2008 / 007776, resins described in JP-A-2008-029901, resins described in JP-A-2009-155406, resins described in JP-A-2010-185934, resins described in JP-A-2011-157416, resins described in JP-A-2009-251481, resins described in JP-A-2007-23195, and resins described in JP-A-1996-1436 Resins described in WO 2013 / 175978, paragraphs 0122 to 0155 of the resins described in JP-A-2019-78878, paragraphs 0317 to 0321 of the resins described in JP-A-2019-78878, paragraphs 0167 to 0191 of the resins described in WO 2018 / 139534, paragraphs 0167 to 0191 of the resins described in WO 2019 / 163505, paragraphs 0299 ​​to 0310 of the resins described in WO 2021 / 131927, paragraphs 0080 to 0085 of the resins described in WO 2022 / 102367, paragraphs 0099 to 0109 of the resins described in WO 2022 / 172607, and the like.

[0228] Commercially available dispersion resins (F) 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 209 manufactured by BYK Japan. 5, 2150, 2155, 2163, 2164, Anti-Terra-U203, 204, BYK-P104, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 2600 manufactured by Lubrizol Japan 0, 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, 452, 452, 460 ... 401, 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 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0229] The dispersing resin (F) can be used alone or in combination of two or more kinds.

[0230] From the viewpoint of dispersion stability, the content of the dispersing resin (F) is preferably from 3 to 200 parts by mass, more preferably from 5 to 150 parts by mass, relative to 100 parts by mass of the colorant (A).

[0231] [Hydrogen donor (G)] The photosensitive composition of the present invention may contain a hydrogen donor (G).

[0232] The hydrogen donor (G) is a compound that supplies hydrogen atoms to the glyoxylate-based polymerization initiator (D2), and can improve photocurability.

[0233] Examples of the hydrogen donor (G) include a compound represented by the following general formula (13) and a compound represented by the following general formula (14).

[0234] [ka]

[0235] In the general formula (13), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0236] In the general formula (13), R3 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, and a 2-ethylhexyl group.

[0237] In the general formula (14), R4 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms has the same meaning as the alkyl group explained for R1 and R2 in general formula (13).

[0238] In the general formula (14), R8 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms has the same meaning as the alkyl group explained for R3 in general formula (13).

[0239] Commercially available hydrogen donor agents (G) include, for example, Omnirad DMB, EDB, EHA, IADB, Esacure A198, and Omnipol ASA manufactured by IGM Resins, and Speedcure 7040 manufactured by Lambson.

[0240] The content of the hydrogen donor (G) is preferably from 10 to 200 parts by mass, more preferably from 30 to 150 parts by mass, relative to 100 parts by mass of the polymerization initiator (D2).

[0241] [Thermal crosslinkable compound (H)] The photosensitive composition of the present invention may contain a thermally crosslinkable compound (H).

[0242] The thermally crosslinkable compound (H) is a compound having a thermally crosslinkable group, and examples thereof include 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, and a compound having a phenol group.

[0243] The thermally crosslinkable compound (H) can be used alone or in combination of two or more kinds.

[0244] The content of the thermally crosslinkable compound (H) is preferably from 0.5 to 40 mass %, more preferably from 1 to 30 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0245] (compounds having epoxy groups) The epoxy group is a group having a three-membered cyclic ether structure, including an alicyclic epoxy group. Examples of compounds 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, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone; Examples include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0246] Commercially available compounds 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, Ltd., 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, Ltd., 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.

[0247] (Compounds with blocked isocyanate groups) The compound 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 deblocking temperature of the blocking agent for the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 100°C.

[0248] The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and particularly preferably active methylene compounds. The elimination temperature of the active methylene compounds or the temperature of the transesterification reaction is low, at 80 to 110°C, and the reaction is sufficient.

[0249] 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 isocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and compounds having an aromatic structure such as bis(isocyanatomethyl)benzene. Further examples include biuret, isocyanurate, adduct and allophanate forms of these compounds, and reaction products of these compounds with polyols.

[0250] 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.

[0251] Examples of commercially available compounds having an aliphatic structure and a blocked isocyanate group 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.

[0252] (Compounds containing an oxetanyl group) Examples of the compound having an oxetanyl group include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3- oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, etc.

[0253] Examples of commercially available compounds having an oxetanyl group include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 121, 212, and 221 manufactured by Toagosei Co., Ltd., and OXBP and OXTP manufactured by Ube Industries, Ltd.

[0254] [Thiol-based chain transfer agents (I)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (I).

[0255] Examples of the thiol chain transfer agent (I) include 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.

[0256] The thiol chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0257] The content of the thiol chain transfer agent (I) is preferably 0.5 to 10% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0258] [Silane coupling agent (J)] The photosensitive composition of the present invention may contain a silane coupling agent (J).

[0259] The silane coupling agent (J) 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 a hydrolysis reaction and a condensation reaction. 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, a methoxy group or an ethoxy group is preferred as the alkoxy group. The silane coupling agent (J) 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.

[0260] The silane coupling agent (J) is not 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, Examples of suitable silanes include 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, and tris(trimethoxysilylpropyl)isocyanate.

[0261] Commercially available silane coupling agents (J) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, 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.

[0262] The silane coupling agent (J) may also be a polymer type, such as a polysiloxane type or an organic polymer type.

[0263] 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.

[0264] The organic polymer type is a silane coupling agent (J) in which the hydrolyzable group is bonded to an organic polymer whose main chain has 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.

[0265] The silane coupling agent (J) can be used alone or in combination of two or more kinds.

[0266] The content of the silane coupling agent (J) is preferably 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0267] [Ultraviolet absorber (K)] The photosensitive composition of the present invention may contain an ultraviolet absorber (K).

[0268] The ultraviolet absorber (K) is not limited and any known compound can be used. For example, a compound having a maximum absorption wavelength in the wavelength range of 300 to 400 nm is preferred, and examples thereof include benzophenone compounds, benzotriazole compounds, triazine compounds, conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, and salicylate compounds.

[0269] Commercially available benzophenone compounds include, for example, Uvinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan Ltd., and Adekastab 1413 manufactured by ADEKA Corporation.

[0270] Commercially available benzotriazole compounds include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT manufactured by BASF Japan Ltd., and Adekastab LA-31RG and LA-31G manufactured by ADEKA Corporation.

[0271] Commercially available triazine compounds include, for example, Tinuvin 400, 405, 406, 477, and 479 manufactured by BASF Japan Ltd., and Adekastab LA-46 and LA-F70 manufactured by ADEKA Corporation.

[0272] The ultraviolet absorbers (K) can be used alone or in combination of two or more.

[0273] The content of the ultraviolet absorber (K) is preferably 0.01 to 5% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0274] [Polymerization inhibitor (L)] The photosensitive composition of the present invention may contain a polymerization inhibitor (L).

[0275] The polymerization inhibitor (L) is not limited and known compounds can be used. Examples include phenol compounds, hydroquinone compounds, benzoquinone compounds, phenothiazine compounds, catechol compounds, nitrobenzene compounds, nitroso compounds, amine compounds, hindered amine compounds, and phosphorus compounds. Among these, it is preferable to include a hydroquinone compound from the viewpoints of developability after storage and line width stability after storage.

[0276] The polymerization inhibitor (L) can be used alone or in combination of two or more kinds.

[0277] The content of the polymerization inhibitor (L) is preferably 0.01 to 0.5% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0278] [Antioxidant (M)] The photosensitive composition of the present invention may contain an antioxidant (M).

[0279] The antioxidant (M) is not limited and known compounds can be used. Examples include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. Among these, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred.

[0280] Examples of hindered phenolic compounds 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 ion of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester methyl methyl ether salt, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-trimethyl-4-hydroxyphenyl]propionate Examples include 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), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol.

[0281] 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 Chemicals, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan, and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical.

[0282] Examples of the hindered amine compound include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 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, 1,2,2,6,6-pentamethyl methyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation polymer 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-pi Ester of peridineethanol 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 N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl ...Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

[0283] 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; Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0284] Examples of the phosphorus-based compound 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 to 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 diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl 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 suitable phosphate compounds 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.

[0285] 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, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0286] Examples of sulfur-based compounds 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.

[0287] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0288] The antioxidant (M) can be used alone or in combination of two or more kinds.

[0289] The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0290] [Leveling Agent (N)] The photosensitive composition of the present invention preferably contains a leveling agent (N) from the viewpoints of suppressing water stains and achieving smoothness.

[0291] The leveling agent (N) is not limited, and any known leveling agent can be used, such as a silicone-based leveling agent, a fluorine-based leveling agent, an acrylic-based leveling agent, or an acetylene diol-based leveling agent.

[0292] Commercially available silicone leveling agents include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd.; FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Toray Dow Corning Co., Ltd.; Examples of such products include X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Gakushu Kogyosha; TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik; and MEGAFACE EFS-131, EFS-321, EFS-521, and EFS-801 manufactured by DIC Corporation.

[0293] Commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, and RS-72-K manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Ftergent 602A manufactured by Neos Corporation.

[0294] Examples of commercially available acrylic leveling agents include BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie, and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical.

[0295] 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.

[0296] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0297] The content of the leveling agent (N) is preferably 0.001 to 2.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0298] (Leveling agent (N1) having a repeating unit represented by general formula (15) and a repeating unit represented by general formula (16)) From the viewpoint of suppressing water stains, the leveling agent (N) preferably contains a leveling agent (N1) (hereinafter also simply referred to as the leveling agent (N1)) having a repeating unit represented by the following general formula (15) and a repeating unit represented by the following general formula (16):

[0299] [ka]

[0300] In the general formula (15), R1 is a hydrogen atom or a methyl group.

[0301] In general formula (15), R2's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (wherein R5's are each independently an alkyl group having 1 to 3 carbon atoms). From the viewpoint of smoothness, R2 is preferably a methyl group or a trimethylsiloxy group.

[0302] In the general formula (15), each R3 is independently an alkyl group having 1 to 6 carbon atoms. From the viewpoint of smoothness, R3 is preferably a methyl group.

[0303] In the general formula (15), R4 is an alkyl group having 1 to 6 carbon atoms. From the viewpoint of smoothness, R4 is preferably an alkyl group having 1 to 4 carbon atoms.

[0304] In general formula (15), L1 is a divalent organic group or a single bond. Among these, L1 is preferably a divalent organic group, more preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms. Examples of the alkylene group having 1 to 50 carbon atoms include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, a tetramethylethylene group, etc. Among these, a methylene group, an ethylene group, an n-propylene group, and an isopropylene group are preferred. Examples of the alkyleneoxy group having 1 to 50 carbon atoms include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, and a heptyleneoxy group.

[0305] A portion of the -CH2- in the alkylene group having 1 to 50 carbon atoms or the alkyleneoxy group having 1 to 50 carbon atoms may be substituted with a carbonyl group, a phenylene group, an amide bond or a urethane bond, and a hydroxyl group or the like may further be substituted on the carbon atom.

[0306] In the general formula (15), n is an integer of 1 to 70. n is preferably an integer of 2 to 50 from the viewpoint of smoothness.

[0307] Examples of the repeating unit represented by general formula (15) include repeating units derived from α-(3-methacryloyloxy)propylpolydimethylsiloxane, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, etc. Further examples include repeating units derived from Silaplane FM-0711, FM-0721, FM-0725, FM-0701T manufactured by JNC Corporation, and X-22-174ASX, X-22-174BX, X-22-2426, X-22-2404 manufactured by Shin-Etsu Chemical Co., Ltd.

[0308] The repeating unit represented by formula (15) can be used alone or in combination of two or more kinds.

[0309] From the viewpoint of smoothness, the content of the repeating unit represented by the general formula (15) is preferably from 30 to 95 mass %, more preferably from 40 to 85 mass %, of all repeating units in the leveling agent (N1).

[0310] In the general formula (16), R6 is a hydrogen atom or a methyl group.

[0311] In the general formula (16), R7 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic and polycyclic alicyclic hydrocarbon groups. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include an isobornyl group, a norbornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentanyl group, a dicyclopentenyl group, a tricyclopentenyl group, a tricyclopentadiene group, and a dicyclopentadiene group. The alicyclic hydrocarbon group having 3 to 20 carbon atoms may have a substituent, such as an alkyl group, a hydroxyl group, a nitro group, an amino group, an alkoxy group, a halogen atom, or a combination thereof. Among these, from the viewpoint of suppressing water stains, polycyclic alicyclic hydrocarbon groups are preferred, isobornyl groups, dicyclopentanyl groups and adamantyl groups are more preferred, and adamantyl groups are even more preferred.

[0312] In the general formula (16), L2 is a divalent organic group or a single bond. Examples of the divalent organic group include an alkylene group having 1 to 50 carbon atoms and an alkyleneoxy group having 1 to 50 carbon atoms. The alkylene group having 1 to 50 carbon atoms has the same meaning as the alkylene group explained for L1 in general formula (15). The alkyleneoxy group having 1 to 50 carbon atoms has the same meaning as the alkyleneoxy group described for L1 in general formula (15). Among these, L2 is preferably a single bond.

[0313] Examples of the repeating unit represented by general formula (16) include repeating units derived from cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, and dimethyladamantyl (meth)acrylate.

[0314] The repeating unit represented by formula (16) can be used alone or in combination of two or more kinds.

[0315] From the viewpoint of suppressing water stains, the content of the repeating unit represented by the general formula (16) is preferably from 5 to 70 mol %, more preferably from 15 to 60 mol %, of all repeating units in the leveling agent (N1).

[0316] The structure of the leveling agent (N1) may be, for example, a random structure, a block structure, or a graft structure, as long as it contains a repeating unit represented by general formula (15) and a repeating unit represented by general formula (16). Among these, the block structure is preferred from the viewpoints of suppressing water stains and achieving smoothness.

[0317] When the leveling agent (N1) has a block structure, the number and arrangement of each block are not limited. For example, when block A is made up of repeating units represented by general formula (15) and block B is made up of repeating units represented by general formula (16), the leveling agent (N1) may have an AB block structure, an ABA block structure, a BAB block structure, or the like.

[0318] The method for producing the block structure is not particularly limited, and known methods can be used, such as living polymerization methods such as living radical polymerization and living anionic polymerization. Living radical polymerization is described, for example, in Japanese Patent Application Laid-Open No. 9-62002 and Japanese Patent Application Laid-Open No. 2002-31713, and in P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Migite and Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura and Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989), M. Kuroki and T. Aida, J. Am. Chem. Soc., 109, 4737 (1987), Takuzo Aida and Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473 (1987), etc. Among these, reversible addition-fragmentation chain transfer polymerization (hereinafter referred to as RAFT), atom transfer radical polymerization (hereinafter referred to as ATRP), living radical polymerization using iodine compounds, and living radical polymerization using organotellurium compounds (hereinafter referred to as TERP) are preferred. Specifically, the leveling agent (N1) can be synthesized by a method described in, for example, WO 2021 / 131726, WO 2022 / 050062, WO 2022 / 244586, etc.

[0319] The leveling agent (N1) may contain repeating units other than the repeating unit represented by general formula (15) and the repeating unit represented by general formula (16) (hereinafter also referred to as other repeating units).

[0320] The other repeating units are not limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and the like. Allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytrimethylene glycol Cholesterol mono(meth)acrylate, Polytetramethylene glycol mono(meth)acrylate, Poly(ethylene glycol / propylene glycol) mono(meth)acrylate, Polyethylene glycol / polypropylene glycol mono(meth)acrylate, Poly(ethylene glycol / tetramethylene glycol) mono(meth)acrylate, Polyethylene glycol / polytetramethylene glycol mono(meth)acrylate, Poly(propylene glycol / tetramethylene glycol) mono(meth)acrylate, Polypropylene glycol / poly Tetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(tetramethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polytetraethylene glycol·poly1,2-Butylene glycol mono(meth)acrylate, poly 1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, polyethylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, poly(1,2-butylene glycol·trimethylene glycol) mono(meth)acrylate, poly 1,2-butylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(1,2-butylene glycol·tetramethylene glycol) mono(meth)acrylate, poly 1,2-butylene glycol Examples of repeating units include those derived from ethylene glycol-polytetramethylene glycol mono(meth)acrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, acroylmorpholine, methylmaleimide, ethylmaleimide, propylmaleimide, and butylmaleimide. The term "poly(ethylene glycol-propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polyethylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol. These can be used alone or in combination.

[0321] The weight average molecular weight of the leveling agent (N1) is preferably 5,000 to 40,000.

[0322] The number average molecular weight of the leveling agent (N1) is preferably 2,000 to 20,000.

[0323] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the leveling agent (N1) is preferably 1.0 to 3.0.

[0324] The leveling agent (N1) can be used alone or in combination of two or more kinds.

[0325] The content of the leveling agent (N1) is preferably from 5 to 100 mass %, more preferably from 10 to 90 mass %, based on 100 mass % of the leveling agent (N).

[0326] (Other leveling agents (N2)) From the viewpoint of smoothness, the leveling agent (N) preferably contains a leveling agent (N2) other than the leveling agent (N1).

[0327] Other examples of the leveling agent (N2) include the above-mentioned silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, acetylene diol-based leveling agents, etc. Among these, silicone-based leveling agents and acrylic-based leveling agents are preferred.

[0328] The other leveling agents (N2) can be used alone or in combination of two or more.

[0329] The mass ratio of the leveling agent (N1) to the other leveling agent (N2) is preferably 10:90 to 90:10, more preferably 20:80 to 90:10.

[0330] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0331] The storage stabilizer (O) is not limited and any known compound can be used, for example, 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 tetraphenylphosphine, phosphites, etc.

[0332] The content of the storage stabilizer (O) is preferably 0.05 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0333] [Organic solvent (P)] The photosensitive composition of the present invention may contain an organic solvent (P).

[0334] The organic solvent (P) is not limited and known compounds can be used, such as 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, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, and 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,Examples of the esters include 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, and dibasic acid esters.

[0335] From an environmental viewpoint, 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.

[0336] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0337] The content of the organic solvent (P) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 to 60 mass %.

[0338] [Other ingredients (Q)] The photosensitive composition of the present invention may contain components other than those described above (hereinafter simply referred to as other components (Q)). Examples of other components (Q) include sensitizers, surfactants, acid generators, salt generators, curing catalysts, quenchers, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, and insulating materials. The content of the other components can be appropriately set within a range that can solve the problems of the present invention.

[0339] [Specific metal element content] The photosensitive composition of the present invention preferably contains Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) in a total content of 500 mass ppm or less.

[0340] A photosensitive composition in which the total amount of the specific metal elements is within the above range has excellent stability and sensitivity even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0341] [Water content] The photosensitive composition of the present invention preferably contains water in an amount of 2.0% by mass or less.

[0342] A photosensitive composition having a water content within the above range has excellent stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0343] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced by mixing the above-mentioned components. During production, the components may be mixed together, or the components may be dissolved or dispersed in the polymerizable compound (B) or the organic solvent (P) and then mixed sequentially. When a component with low solubility, such as a pigment, is used as the colorant (A), it is preferable to perform a dispersion treatment. For example, a dispersion is produced by adding a colorant (A), a dispersing resin (F), an organic solvent (P), etc., and performing 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. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0344] 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.

[0345] The average dispersed particle size (secondary particle size) of the particles in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particles have an appropriate size, a photosensitive composition with high dispersion stability is easily obtained.

[0346] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac 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 the D50 particle size set to the average size. The dilution solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to provide results with little variation.

[0347] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and more preferably coarse particles of 0.5 μm or larger, as well as contaminated dust, by means of centrifugation, filtration through a sintered filter or membrane filter, etc. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0348] The photosensitive composition of the present invention is preferably used for forming a pattern by photolithography, although the present invention is not limited thereto.

[0349] <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 can also be used as a flat film without forming a pattern.

[0350] [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 photosensitive composition of the present invention onto a substrate and a step of drying the composition.

[0351] [Coating process] Examples of the substrate include substrates made of glass, resin, silicone, etc. 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. Furthermore, an imaging device such as a CCD or CMOS may be formed on the substrate. Furthermore, an undercoat layer may be provided on the substrate, if necessary, to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0352] The coating method is not particularly limited, and known methods can be used, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0353] The thickness of the film can be adjusted appropriately depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0354] [Drying process] The method for drying the film coated on the substrate is not particularly limited, and known methods 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 the like, and a combination of these methods.

[0355] The drying temperature and drying time can be adjusted as appropriate. The drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 5 seconds to 5 minutes.

[0356] Next, a pattern is formed. Examples of a method for forming a pattern include photolithography and dry etching. Among these, photolithography is preferred. Note that when the film is used as a flat film, the step of forming a pattern does not need to be performed.

[0357] [Exposure process] In the exposure step, 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 harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). When using light with a specific wavelength, an optical filter can also be used. The exposure may be performed by continuous irradiation with light, or by repeated irradiation and pause in a short cycle (for example, milliseconds or less) (pulse exposure). Furthermore, a plurality of active energy rays may be used in combination, or exposure may be performed in multiple steps.

[0358] [Development process] Next, an alkaline development treatment is carried out, whereby the unexposed portions of the layer are dissolved in the alkaline developer, leaving only the hardened portions, thereby obtaining a patterned film. Examples of alkaline developers 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, and 1,8-diazabicyclo-[5.4.0]-7-undecene. 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, pattern roughening and peeling are suppressed, and the remaining film rate after development is improved. Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0359] [Post-baking process] After development, a heat treatment (post-baking) is performed, which improves the film resistance. The temperature is preferably 70 to 300° C., more preferably 80 to 240° C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element as the light-emitting layer is used, or from the viewpoint of reducing the environmental load, the temperature is preferably 180°C or less, more preferably 150°C or less, and particularly preferably 130°C or less.

[0360] <Color filter> The color filter of the present invention has the above-mentioned film. The color filter of the present invention can be produced by the same method as the above-mentioned film.

[0361] <Solid-state imaging element> The solid-state imaging device of the present invention has the above color filter. The solid-state imaging device is not particularly limited as long as it has the color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

[0362] The present invention is configured to include a substrate having a plurality of photodiodes constituting the light-receiving area of ​​a solid-state imaging device (e.g., a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like; a light-shielding film formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed; a device protective 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 portions of the photodiodes; and a color filter of the present invention on the device protective film. Furthermore, the present invention may also be configured to include a light-focusing means (e.g., a microlens, etc.; the same applies hereinafter) on the device protective film below the color filter (closer to the substrate), or a light-focusing means on the color filter. The color filter may also have a structure in which a cured film forming each color pixel is embedded in spaces partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a low refractive index relative to the color pixels. An imaging device including the 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.

[0363] <Image display device> The image display device of the present invention has the above color 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 configurations can be mentioned.

[0364] A 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 TN, IPS, OCB, and MVA. The counter substrate can be appropriately selected depending on the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropies, or mixtures thereof, depending on the driving method.

[0365] 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 Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0366] <Infrared sensor> The infrared sensor of the present invention has the above color filter. The form of the infrared sensor is not particularly limited as long as it has the color filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0367] A substrate has a plurality of photodiodes constituting the light receiving area of ​​a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film, which is open only in the light receiving portions of the photodiodes, is placed on the photodiodes and transfer electrodes. A device protective film is placed on this light-shielding film, and the color filter of the present invention is placed on this device protective film. Furthermore, the device protective film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protective film and below the color filter (on the side closer to the substrate), or the light-collecting means may be placed on the optical filter.

[0368] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with a color filter of the present invention. The infrared sensor 100 shown in FIG.

[0369] 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 .

[0370] The infrared cut filter 111 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared range (for example, light with a wavelength of 800 to 1,300 nm).

[0371] The color filter 112 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range, and for example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

[0372] 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.

[0373] 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.

[0374] 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 to cover the microlens 115.

[0375] 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.

[0376] This infrared sensor can simultaneously capture image information, enabling motion sensing that recognizes the movement of an object. Furthermore, this infrared sensor can also acquire 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. [Example]

[0377] 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 nonvolatile content or nonvolatile content concentration refers to the mass remaining after leaving the sample in an oven at 110°C for 3 hours.

[0378] Before describing the examples, each measurement method will be explained.

[0379] The weight average molecular weight (Mw) of the resin, the number average molecular weight (Mn) of the resin, the acid value (mgKOH / g) of the resin, and the amine value (mgKOH / g) of the resin are measured as follows.

[0380] (Molecular Weight of Resin) Number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured using gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation). Two separation columns were connected in series, with both columns packed with "TSK-GEL SUPER HZM-N" in series. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0381] (resin acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mg KOH / g). The acid value per unit of nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0382] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content.

[0383] <Production of Colorant (A)> (Colorant (A-6)) A four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75 ° C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized and then charged into a dropping funnel. The mixture was attached to a four-neck separable flask and added dropwise over two hours to carry out the reaction. After the addition was completed, the reaction was continued for two hours, and then sampling was performed. The polymerization yield was confirmed to be 98% or higher based on the nonvolatile content, and the weight average molecular weight was confirmed to be 6,830. The mixture was then cooled to 50 ° C. Next, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and reacted for 2 hours to obtain a salt-forming resin 1. Next, 30 parts of salt-forming resin 1 (based on nonvolatile content) was added to 2,000 parts of water, thoroughly stirred, and then heated to 60°C. Separately, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water. This solution was added dropwise to the salt-forming resin 1 solution. After the addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. The reaction endpoint was confirmed by dropping the reaction solution onto filter paper. The point at which no bleeding occurred was considered to be the end point, and the salt-forming compound was determined to have been obtained. After cooling to room temperature while stirring, the mixture was subjected to suction filtration. After washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture, yielding a salt-forming compound of CI Acid Red 52 and salt-forming resin 1. The content of components derived from CI Acid Red 52 in the salt-forming compound was 25% by mass.

[0384] (Colorant (A-7)) Colorant (A-7) was produced in the same manner as Colorant (A-6), except that CI Acid Red 52 was changed to CI Acid Red 289. In this case, the content of the component derived from CI Acid Red 289 in the salt-forming compound was 25 mass%.

[0385] (Colorant (A-8)) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 18.2 parts of methyl methacrylate, 14.8 parts of n-butyl methacrylate, 14.8 parts of 2-ethylhexyl methacrylate, 10.0 parts of methacrylic acid, 15.0 parts of 3-ethyl-3-methacryloxymethyloxetane, and 15.0 parts of tert-butyl methacrylate. The mixture was stirred at 50 ° C for 1 hour under a nitrogen stream, and the atmosphere in the reactor was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was raised to 100 ° C under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured. The polymerization conversion rate was confirmed to be 98% or higher based on the nonvolatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as the second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining the temperature at 100°C under a nitrogen atmosphere. Two hours after adding the dimethylaminoethyl methacrylate methyl chloride salt, a sample of the polymerization solution was taken and the nonvolatile content was measured. Converting from the nonvolatile content, it was confirmed that the polymerization conversion rate of the second block was 98% or more. After cooling to 50°C, methanol was added to obtain salt-forming resin 2. Next, 30 parts of salt-forming resin 2 (based on nonvolatile content) was added to 2,000 parts of water, thoroughly stirred, and then heated to 60°C. Separately, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 463 in 90 parts of water. This solution was added dropwise to the salt-forming resin 2 solution. After the addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. The reaction endpoint was confirmed by dropping the reaction solution onto filter paper. The point at which no bleeding occurred was considered to be the end point, and the salt-forming compound was determined to have been obtained. After cooling to room temperature while stirring, the mixture was subjected to suction filtration. After washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture, yielding a salt-forming compound of CI Acid Red 463 and salt-forming resin 2. The content of components derived from CI Acid Red 463 in the salt-forming compound was 25% by mass.

[0386] <Production of alkali-soluble resin (B)> (Solution of alkali-soluble resin (B1-1) having a repeating unit represented by general formula (4)) A reaction vessel equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer was charged with 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc), and the reaction vessel was heated to 120°C while injecting nitrogen gas into it. At the same temperature, a mixture of 53.5 parts of 2-ethylhexyl acrylate, 99.5 parts of glycidyl methacrylate, 2.2 parts of dicyclopentanyl methacrylate, tert-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours. After the dropwise addition was completed, the mixture was stirred for an additional 2 hours at 120°C to obtain a precursor. The atmosphere in the reaction vessel was then replaced with air, and 50.8 parts of acrylic acid as a modifying compound, 0.6 parts of triphenylphosphine as catalysts, and 0.2 parts of methylhydroquinone were added, followed by a reaction at 110°C for 10 hours. This caused the epoxy group of glycidyl methacrylate to react with the carboxyl group of acrylic acid, introducing a repeating unit represented by general formula (8). Next, 17.0 parts of succinic anhydride was added as a modifying compound and reacted at 110°C for 4 hours. This allowed some of the hydroxyl groups generated by the reaction of glycidyl methacrylate and acrylic acid to react with succinic anhydride. PGMAc was then added to a non-volatile content of 40% by mass to prepare a solution of alkali-soluble resin (B1-1) having a repeating unit represented by general formula (4). The acid value was 38 mg KOH / g and the weight-average molecular weight was 12,000. The amounts in Table 1 are expressed in moles.

[0387] (Alkali-soluble resin (B1-2) to (B1-8) solutions) Alkali-soluble resins (B1-2) to (B1-8) having a repeating unit represented by general formula (4) were synthesized in the same manner as for alkali-soluble resin (B1-1), except that the formulation of alkali-soluble resin (B1-1) was changed as shown in Table 1. PGMAc was added to each resin to adjust the non-volatile content to 40% by mass.

[0388] [Table 1]

[0389] (Other alkali-soluble resin (B2-1) solutions) 150 parts of PGMAc were placed in a reaction vessel fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer, and the temperature was raised to 100°C while nitrogen gas was injected into the reaction vessel. Thereafter, a mixture of 70.5 parts of benzyl methacrylate, 43.0 parts of methacrylic acid, 22.0 parts of dicyclopentanyl methacrylate, azobisisobutyronitrile as a polymerization initiator, and 136 parts of PGMAc was added dropwise from the dropping tube into the reaction vessel over 2 hours to carry out a reaction. After the dropwise addition was completed, stirring was continued for an additional 5 hours at 100°C. Next, the atmosphere in the reaction vessel was replaced with air, and 35.5 parts of glycidyl methacrylate, 0.9 parts of the catalyst trisdimethylaminomethylphenol, and 0.1 parts of hydroquinone were added to the reaction vessel and reacted at 110°C for 6 hours. PGMAc was then added to adjust the nonvolatile content to 40% by mass to prepare a solution of other alkali-soluble resin (B2-1). The acid value was 80 mgKOH / g and the weight-average molecular weight was 13,000.

[0390] In the production of the alkali-soluble resin (B), the amount of the polymerization initiator added was appropriately adjusted so as to achieve the weight average molecular weight of each resin.

[0391] <Production of polymerizable compound (C)> (Polymerizable compound (C2-1) solution having a urethane bond) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 112 parts of hexamethylene diisocyanate and 112 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the reaction mixture was analyzed by IR at 2,180 cm -1 PGMAc was added so that the nonvolatile content was 50% by mass, to obtain a solution of a polymerizable compound (C2-1) having an average of 6 polymerizable unsaturated groups and urethane bonds.

[0392] (Polymerizable compound (C2-2) solution having a urethane bond) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the FTIR was measured at 2,180 cm. -1PGMAc was added so that the nonvolatile content was 50% by mass, to obtain a solution of a polymerizable compound (C2-2) having an average of 10 polymerizable unsaturated groups and urethane bonds.

[0393] (Polymerizable compound (C2-3) solution having a urethane bond) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the FTIR reading was 2,180 cm. -1 The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted for 6 hours at a temperature of 50 to 60°C. The nonvolatile content was adjusted to 50% by mass, and a solution of a polymerizable compound (C2-3) having an average of 9 polymerizable unsaturated groups and an acidic group and a urethane bond was obtained.

[0394] <Production of Polymerization Initiator (D)> (Polymerization initiator (D1-1) represented by general formula (1)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 120 parts of dichloromethane, 35.5 parts of fluorene, and 30.1 parts of chloroisobutyryl chloride. After cooling to below 0°C, aluminum trichloride was added in 10 batches and the mixture was stirred at 10°C for 6 hours to allow the reaction to proceed. Next, 50 parts of hydrochloric acid and 200 parts of ice water were added and the mixture was stirred for 3 hours. 150 parts of dichloromethane was added to the reaction mixture, and the resulting organic layer was separated and concentrated. 150 parts of methanol was added and the mixture was cooled. The resulting crystals were filtered and dried to obtain 2-methyl-1-fluorenyl-2-chloro-1-propanone. Next, 27 parts of the obtained 2-methyl-1-fluorenyl-2-chloro-1-propanone, 1.76 parts of calcium oxide, and 7.0 parts of sodium methoxide were charged into a reaction vessel equipped with a thermometer, a dropping tube, a reflux condenser, and a stirrer, and the mixture was reacted at 68°C for 6 hours. After cooling to 50°C, 68 parts of morpholine was added, and the mixture was reacted for 14 hours. Thereafter, the mixture was decolorized with activated carbon and filtered, and further refluxed in a mixed solvent of toluene and methanol to obtain 2-methyl-1-fluorenyl-2-morpholino-1-propanone. A reaction vessel equipped with a thermometer, dropping tube, reflux condenser, and stirrer was charged with 20 parts of 2-methyl-1-fluorenyl-2-morpholino-1-propanone, 34 parts of chlorobutane, and 0.6 parts of tetrabutylammonium bromide. After heating to 78°C, 72 parts of a 50% aqueous solution of NaOH was added dropwise, and the reaction was carried out at 82°C for 4 hours. 50 parts of toluene and 50 parts of water were added to the reaction mixture, and the organic and aqueous layers were separated. The separated organic layer was decolorized with activated carbon and filtered. After toluene and methanol were added, the mixture was crystallized, filtered, and dried to obtain the compound (D1-1) described above.

[0395] (Polymerization initiator (D1-2) represented by general formula (1)) The above-mentioned compound (D1-2) was obtained in the same manner as in the polymerization initiator (D1-1) represented by general formula (1), except that chlorobutane was replaced with chloropropane.

[0396] (Polymerization initiator (D2-1-1) represented by general formula (2)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 120 parts of dichloromethane, 10.00 parts of diphenyl sulfide, and 7.92 parts of benzoyl chloride and cooled on ice. 7.87 parts of anhydrous aluminum chloride were added in small portions, and the mixture was stirred at room temperature for 2 hours and then cooled on ice. Next, 9.53 parts of ethyl chlorooxoacetate and 10.88 parts of anhydrous aluminum chloride were added in small portions, followed by stirring at room temperature for 2 hours and then cooling. Next, 1.47 parts of ethyl chlorooxoacetate and 1.65 parts of anhydrous aluminum chloride were added in small portions, followed by stirring at room temperature for 2 hours and then adding 400 parts of ice water. Dichloromethane was added to the reaction mixture, and the organic and aqueous layers were separated. The separated organic layer was washed twice with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was removed by distillation under reduced pressure, and the mixture was purified by recrystallization from ethanol to obtain the compound (D2-1-1) described above.

[0397] (Polymerization initiator (D2-1-2) represented by general formula (2)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 120 parts of dichloromethane, 10.00 parts of diphenyl sulfide, and 7.33 parts of ethyl chlorooxoacetate, and cooled with ice. Next, 7.16 parts of anhydrous aluminum chloride was added portionwise to the reaction vessel, and the mixture was stirred at room temperature for 3 hours. Dichloromethane was added to the reaction mixture, and the organic and aqueous layers were separated. The separated organic layer was washed twice with saturated brine, then dried over anhydrous sodium sulfate and filtered. The solvent was removed by distillation under reduced pressure, and the mixture was purified by recrystallization from ethanol to obtain the compound (D2-1-2) described above.

[0398] (Polymerization initiator (D2-1-3) represented by general formula (2)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 120 parts of dichloromethane, 10.00 parts of diphenyl sulfide, and 13.20 parts of methyl chlorooxoacetate, and cooled with ice. Next, 14.31 parts of anhydrous aluminum chloride was gradually added to the reaction vessel, and the mixture was stirred at room temperature for 3 hours. Dichloromethane was added to the reaction mixture, and the organic and aqueous layers were separated. The separated organic layer was washed twice with saturated brine, then dried over anhydrous sodium sulfate and filtered. The solvent was removed by distillation under reduced pressure, and the mixture was purified by recrystallization from ethanol to obtain the compound (D2-1-3) described above.

[0399] (Polymerization initiator (D2-1-4) represented by general formula (2)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 120 parts of dichloromethane, 10.00 parts of diphenyl ether, and 8.26 parts of benzoyl chloride and cooled on ice. 7.87 parts of anhydrous aluminum chloride were added in small portions, and the mixture was stirred at room temperature for 2 hours and then cooled on ice. Next, 9.53 parts of ethyl chlorooxoacetate and 10.88 parts of anhydrous aluminum chloride were added in small portions, in that order, and the mixture was stirred at room temperature for 2 hours and then cooled. An additional 1.47 parts of ethyl chlorooxoacetate and 1.65 parts of anhydrous aluminum chloride were added in small portions, in that order, and the mixture was stirred at room temperature for 2 hours. 400 parts of ice water was then added. Dichloromethane was added to the reaction mixture, and the organic and aqueous layers were separated. The separated organic layer was washed twice with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was removed by distillation under reduced pressure, and the mixture was purified by recrystallization from ethanol to obtain the compound (D2-1-4) described above.

[0400] (Polymerization initiator (D2-1-11) represented by general formula (2)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 200 parts of 1,2-dichloroethane, 1.10 parts of sulfolane, and 37.2 parts of ethyl chlorooxoacetate, and cooled with ice. 42.10 parts of anhydrous aluminum chloride were added in small portions. Next, a solution of 15.00 parts of fluorene dissolved in 80 parts of 1,2-dichloroethane was slowly added to the reaction vessel, and after stirring at room temperature for 5 hours, 200 parts of 8% aqueous hydrochloric acid was added. The organic and aqueous layers were separated, and the separated organic layer was washed twice with saturated brine, followed by the addition of anhydrous sodium sulfate, drying, and filtration. The solvent was removed by distillation under reduced pressure, and the resulting mixture was purified by column chromatography to obtain the compound (D2-1-11) described above.

[0401] (Polymerization initiator (D2-1-24) represented by general formula (2)) A reaction vessel equipped with a thermometer, dropping tube, and stirrer was charged with 6.35 parts of 1,4-dimethyl(2E)-2-(piperidin-1-yl)butene-2-dioate and 4.50 parts of 4-ethoxy-2-hydroxybenzaldehyde, and the mixture was melted at 80°C with stirring. Next, 7.00 parts of acetic acid was added to the reaction vessel, and the mixture was stirred at 110°C for 2 hours. After cooling to 30°C, 200 parts of dichloromethane and 400 parts of water were added, and the organic and aqueous layers were separated. The separated organic layer was washed twice with water, then dried over anhydrous sodium sulfate, and filtered. The solvent was removed by distillation under reduced pressure, and the resulting mixture was purified by recrystallization from toluene to obtain the compound (D2-1-24) described above.

[0402] <Production of Dispersion Resin (F)> (Dispersion resin (F-1) solution) A reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 4 parts trimellitic anhydride, 2 parts 3-mercapto-1,2-propanediol, 50 parts PGMAc, and 0.1 parts dimethylbenzylamine. After purging with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, followed by 2 hours at 80°C. Further, 30 parts tert-butyl acrylate, 20 parts (3-ethyloxetan-3-yl)methyl methacrylate (Ube Industries, Ltd., "ETERNACOLL® OXMA"), 5 parts methacrylic acid, 40 parts ethyl acrylate, and 10 parts PGMAc were charged. While maintaining the reaction vessel at 80°C, 0.2 parts 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. One hour after the final addition, the nonvolatile content was measured, confirming that 95% had reacted. PGMAc was added so that the nonvolatile content was 30% by mass, to obtain a dispersion resin (F-1) solution with a comb structure, which had an acid value of 55 mg KOH / g and a weight-average molecular weight of 15,000.

[0403] (Dispersion resin (F-2) solution) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin (IV) oxide as a catalyst. After purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride had been half-esterified. Next, 160 parts of the compound obtained in the first step (based on nonvolatile 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 into a reaction vessel, which was heated to 80°C. 2,2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator, and the reaction proceeded for 12 hours (second step). Measurement of the nonvolatile content confirmed that 95% 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 analysis revealed a 2,270 cm3 NMR spectrum 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 nonvolatile content was 30% by mass, and a dispersion resin (F-2) solution with a comb structure was prepared. The acid value was 68 mg KOH / g and the weight average molecular weight was 13,000.

[0404] (Dispersion resin (F-3) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst. The mixture was stirred at 50 °C for 1 hour under a nitrogen stream, and the system was then purged 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. The temperature was raised to 110 °C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, a sample was taken of the polymerization solution and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethyl benzyl dimethyl ammonium chloride were added to the reactor. The reaction was continued at 110 °C under a nitrogen atmosphere with stirring. Two hours after addition, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or higher. After cooling, PGMAc was added to bring the nonvolatile content to 30% by mass, and a solution of a dispersed resin (F-3) with a chain block structure was prepared. The amine value was 169.8 mg KOH / g.

[0405] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, 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 nonvolatile content was 22.00 mass%. Colorant (A-1): 15.00 parts Dye derivative (E-1): 1.00 parts Dispersion resin (F-1) solution: 10.00 parts Dispersion resin (F-2) solution: 10.00 parts Organic solvent (P-1): 64.00 parts

[0406] (Dispersion 2~5) Dispersions 2 to 5 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 2 were changed.

[0407] [Table 2]

[0408] The components listed in Table 2 are as follows:

[0409] [Colorant (A)] A-1: CI Pigment Blue 15:6 A-2: CI Pigment Red 254 A-3: CI Pigment Red 177 A-4: CI Pigment Yellow 150 A-5: CI Pigment Green 58

[0410] Each of the colorants (A-1) to (A-5) was pulverized by salt milling, thoroughly washed with ion-exchanged water so that the photosensitive composition had the specific metal content described above, and then dried before use.

[0411] [Dye derivative (E)] [ka]

[0412] [Organic solvent (P)] P-1:PGMAc

[0413] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and the mixture was filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. The nonvolatile content was 16.50% by mass. Dispersion 1: 17.00 parts Colorant (A-6): 1.70 parts Solution of alkali-soluble resin (B1-1) having a repeating unit represented by general formula (4): 11.00 parts Polymerizable compound (C1-1) having an amine structure: 0.50 parts Polymerizable compound (C2-1) solution having a urethane bond: 2.00 parts Polymerizable compound (C2-3) solution having a urethane bond: 2.00 parts Other polymerizable compounds (C3-1): 2.00 parts Polymerization initiator (D1-1) represented by general formula (1): 0.65 parts Polymerization initiator (D2-1-1) represented by general formula (2): 0.30 parts Other polymerization initiator (D3-1): 0.25 parts Other polymerization initiator (D3-3): 0.30 parts Thermal crosslinkable compound (H-1): 0.30 part Silane coupling agent (J-1): 0.20 parts Antioxidant (M-1): 0.14 parts Leveling agent (N1-1) having a repeating unit represented by general formula (15) and a repeating unit represented by general formula (16): 1.00 part Other leveling agent (N2-1): 1.00 parts Organic solvent (P): 59.66 parts

[0414] [Examples 2 to 34 and Comparative Examples 1 and 2] (Photosensitive composition 2-36) Photosensitive compositions 2 to 36 were prepared in the same manner as in Example 1, except that the raw materials and amounts of photosensitive composition 1 in Example 1 were changed to those shown in Tables 3-1 to 3-4.

[0415] [Table 3-1]

[0416] [Table 3-2]

[0417] [Table 3-3]

[0418] [Table 3-4]

[0419] The raw materials listed in Tables 3-1 to 3-4 are as follows: In the table, the alkali-soluble resin (B1) having a repeating unit represented by general formula (4) is referred to as alkali-soluble resin (B1). The polymerization initiator (D2-1) represented by general formula (2) is referred to as polymerization initiator (D2-1). Other polymerization initiators are glyoxylate-based polymerization initiators (D2) other than the polymerization initiator (D2-1) represented by general formula (2). The leveling agent (N1) having a repeating unit represented by general formula (15) and a repeating unit represented by general formula (16) is referred to as leveling agent (N1).

[0420] [Polymerizable compound (C)] (Polymerizable compound (C1) having an amine structure) C1-1: CN9906NS (Arkema, a multifunctional acrylate having an amine structure and a urethane bond) C1-2: Aronix MT-3041 (manufactured by Toagosei Co., Ltd., a multifunctional acrylate with an amine structure)

[0421] (Other polymerizable compounds (C3)) C3-1: Aronix M-306 (manufactured by Toagosei Co., Ltd.; a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, containing 65-70% pentaerythritol triacrylate) C3-2: KAYARAD DPCA-20 (Nippon Kayaku Co., Ltd., lactone-modified hexafunctional acrylate)

[0422] [Polymerization initiator (D)]

[0423] (Glyoxylate-based polymerization initiator (D2) other than the polymerization initiator (D2-1) represented by general formula (2)) D2-2-1: Omnirad MBF (IGM Resin, methyl phenylglyoxylate)

[0424] (Other polymerization initiators (D3)) D3-1: Compound (12-1) D3-2: Omnirad EMK (IGM Resin, 4,4'-bis(diethylamino)benzophenone) D3-3: Omnirad DETX (IGM Resin, 2,4-diethylthioxanthone) D3-4: Omnirad 907 (IGM Resin, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one)

[0425] [Thermal crosslinkable compound (H)] H-1: EHPE-3150 (manufactured by Daicel Corporation, a compound having an epoxy group)

[0426] [Silane coupling agent (J)] J-1: 3-glycidoxypropyltriethoxysilane

[0427] [Antioxidant (M)] M-1: Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)

[0428] [Leveling Agent (N)] (Leveling agent (N1) having a repeating unit represented by general formula (15) and a repeating unit represented by general formula (16)) N1-1: 1% PGMAc solution of a block copolymer (n:m=50:50 (mol%)) having the following structure:

[0429] [ka]

[0430] (Other leveling agents (N2)) N2-1: MEGAFACE EFS-801 (DIC) in 1% PGMAc solution.

[0431] [Organic solvent (P)] P-1:PGMAc P-2: Propylene glycol monomethyl ether P-3: 3-methoxy-1-butanol P-4: Ethyl 3-ethoxypropionate The organic solvent (P) was prepared by mixing P-1, P-2, P-3, and P-4 in a mass ratio of 80:10:5:5.

[0432] <Evaluation of Photosensitive Composition> The obtained photosensitive compositions 1 to 36 were evaluated as follows. The evaluation results are shown in Table 4.

[0433] [Water stain evaluation] The photosensitive composition thus obtained was applied by spin coating onto a glass substrate (Corning Eagle 2000) measuring 100 mm long x 100 mm wide and 0.7 mm thick, so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 90°C for 2 minutes. 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 through a photomask with a 100 μm wide stripe pattern. 2 , exposure dose 50mJ / cm 2 Thereafter, the substrate was developed by immersing it in an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23°C for 40 seconds, and then washed with pure water. The pattern surface of the obtained evaluation substrate was observed using a Nikon ECLIPSE LV100POL Model optical microscope, and the degree of discoloration was evaluated. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: There were no water stains. 4: Water stains accounted for less than 10% of the total area. 3: Water stains accounted for 10% or more but less than 20% of the total. 2: Water stains accounted for 20% or more but less than 30% of the total. 1: Water stains accounted for 30% or more of the total area.

[0434] [Smoothness evaluation] The photosensitive composition thus obtained was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm long x 100 mm wide and 0.7 mm thick, so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. After cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm through a photomask with a 20 μm square pattern. 2 , exposure dose 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 230°C for 30 minutes. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development residue for each photosensitive composition coating, and this was defined as the appropriate development time. The film thickness was measured using an optical film thickness meter (F50) manufactured by Filmetrics. The evaluation was performed by calculating the difference in film thickness between the thinnest part and the thickest part (hereinafter referred to as film thickness difference). The evaluation criteria are as follows, with a score of 3 or higher being practical. 5: Film thickness difference is 0.02 μm or less 4: The difference in film thickness is greater than 0.02 μm and less than 0.03 μm 3: The difference in film thickness is greater than 0.03 μm and less than 0.04 μm 2: The difference in film thickness is greater than 0.04 μm and less than 0.05 μm 1: The difference in film thickness is greater than 0.05 μm

[0435] [Linewidth stability] 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 dried film thickness would be 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm. 2 , exposure dose 50mJ / cm 2 and 100 mJ / cm2 The substrate was exposed to light through a photomask with a 100 μm wide stripe pattern at two levels. The substrate was then spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, then washed with ion-exchanged water and air-dried. The resulting substrate was post-baked in a clean oven at 230°C for 30 minutes. Spray development was carried out 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 100mJ / 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 6 μm or more

[0436] [Table 4] [Explanation of symbols]

[0437] 100 Infrared Sensor 110 Solid-state imaging device 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 photosensitive composition, wherein the polymerization initiator (D) comprises a polymerization initiator (D1) represented by the following general formula (1) and a glyoxylate-based polymerization initiator (D2): 【Chemistry 1】 (In general formula (1), R １ , and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ３ represents a hydrogen atom or a monovalent substituent.

2. 2. The photosensitive composition according to claim 1, wherein the mass ratio of the polymerization initiator (D1) represented by the general formula (1) to the glyoxylate-based polymerization initiator (D2) is 95:5 to 5:

95.

3. The photosensitive composition according to claim 1 , wherein the glyoxylate-based polymerization initiator (D2) comprises a polymerization initiator represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), R １ , and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. X １ represents a structure represented by the following general formula (3). n represents 0 or 1. 【Transformation 3】 (In general formula (3), Y ２ represents an oxygen atom or a sulfur atom. R ３ represents a monovalent substituent. m represents an integer of 0 to 3; *1 and *2 represent bonds to the carbon atom in general formula (2). However, when n in general formula (2) is 0, the bond is either *1 or *2.

4. 2. The photosensitive composition according to claim 1, wherein the polymerization initiator (D) further comprises a polymerization initiator (D3) other than the polymerization initiator (D1) represented by the general formula (1) and the glyoxylate-based polymerization initiator (D2).

5. The alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a repeating unit represented by the following general formula (4):

2. The photosensitive composition according to claim 1, wherein the content of the repeating unit represented by the general formula (4) is 1 to 50 mol % of all repeating units in the alkali-soluble resin (B1). 【Chemistry 4】 (In general formula (4), R １ represents a hydrogen atom or a methyl group. R ２ represents an alkyl group having 4 to 22 carbon atoms.

6. 2. The photosensitive composition according to claim 1, wherein the colorant (A) comprises a salt-forming compound of a dye and a resin that forms a salt with the dye.

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

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

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

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

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

Images