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

Abstract

To provide a photosensitive composition which allows for producing a cured film that is superior in terms of developability, pattern formability, and heat resistance.SOLUTION: The above problem is cleared by a photosensitive composition containing a near-infrared absorbing pigment (A), alkali-soluble resin (B), polymerizable compound (C), and photopolymerization initiator (D) containing a compound (D1) represented by general formula (1) below. General Formula (1). In general formula (1), R1 and R2 independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 represents a hydrogen atom or a monovalent substitution group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition containing a near-infrared absorbing dye, and uses thereof. [Background technology]

[0002] Video cameras, digital cameras, smartphones, and the like use solid-state imaging devices for color images, such as CCDs (charge-coupled devices) and CMOSs ​​(complementary metal-oxide semiconductors). The light-receiving sections of these solid-state imaging devices use silicon photodiodes that are sensitive to infrared light, so luminosity correction is required, and an infrared cut filter or the like is provided. The infrared cut filter is manufactured using, for example, a composition containing a near-infrared absorbing dye.

[0003] Conventionally, infrared cut filters have been used as flat films, but in recent years, studies have been conducted to form patterns of infrared cut filters using photolithography. However, near-infrared absorbing dyes used in infrared cut filters and the like have low heat resistance, and there is a problem that their near-infrared absorption ability decreases during heat treatment (post-baking) during pattern formation. On the other hand, films with high heat resistance have problems such as poor developability and pattern formability.

[0004] Therefore, for example, Patent Document 1 discloses a thermosetting resin composition containing two types of cyanine compounds as near-infrared absorbing dyes, an epoxy resin having a specific structure, and an epoxy resin curing agent. Also, Patent Document 2 discloses a photosensitive resin composition for near-infrared absorbing materials containing a phthalocyanine compound having an absorption maximum wavelength in the near-infrared region, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-34252 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-160380 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the composition of Patent Document 1 cannot be used to form a pattern by photolithography, and the composition of Patent Document 2 does not satisfy all of the requirements for developability, pattern formation, and heat resistance.

[0007] An object of the present invention is to provide a photosensitive composition capable of forming a cured film that is excellent in developability, pattern formability, and heat resistance. [Means for solving the problem]

[0008] The present invention provides a photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The photosensitive composition according to the present invention relates to a photosensitive composition in which the photopolymerization initiator (D) comprises a compound (D1) represented by the following general formula (1): General formula (1) [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.) [Effects of the Invention]

[0009] According to the present invention, there is provided a photosensitive composition capable of forming a cured film having excellent developability, pattern formability, and heat resistance. The present invention also provides the cured film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device provided with the cured film of the present invention. [Figure 2]FIG. 2 is a schematic cross-sectional view of a solid-state imaging device provided with the cured film of the present invention. [Figure 3] FIG. 3 shows a schematic cross-sectional view of an infrared sensor provided with the cured film 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 the present invention, 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. Furthermore, "CI" refers to the Color Index (CI; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. The molecular weight of the compound in the present invention is a calculated value or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for low molecular weight compounds whose molecular weight can be specified, and is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent for compounds having a molecular weight distribution. A monomer is a compound that polymerizes to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that forms a resin after polymerization. The polymerizable compound is a compound that forms a coating by polymerization.

[0013] <Photosensitive composition> The photosensitive composition of the present invention is a photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (1). General formula (1) [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.)

[0014] The mechanism by which the photosensitive composition having the above-mentioned structure can solve the problems of the present invention is not clear, but is speculated as follows. Compared to the photopolymerization initiators 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, which have traditionally been widely used in the color filter field, compound (D1) represented by general formula (1) contains a rigid, hydrophobic, and heat-resistant fluorene skeleton, which is believed to result in highly heat-resistant cured films. Furthermore, the π-π interactions between the two benzene rings provide the cured film with adequate cohesion. Therefore, while suppressing pattern chipping during development, the structure of the compound is moderately softened by heat, resulting in adequate thermal sagging during post-baking, which is believed to result in good pattern shape.

[0015] [Near-infrared absorbing dye (A)] The photosensitive composition of the present invention contains a near-infrared absorbing dye (A).

[0016] The near-infrared absorbing colorant (A) is a compound having a maximum absorption in a wavelength range of 700 to 2,000 nm, and may be a pigment (also called a near-infrared absorbing pigment) or a dye (also called a near-infrared absorbing dye). A near-infrared absorbing pigment and a near-infrared absorbing dye may also be used in combination. From the viewpoint of heat resistance, a near-infrared absorbing pigment is preferred. In the present invention, the near-infrared absorbing pigment preferably has a solubility in 100 g of propylene glycol monomethyl ether acetate at 25° C. of less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

[0017] Examples of the near-infrared absorbing dye (A) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, etc. Among these, from the viewpoints of near-infrared absorbing ability and heat resistance, one or more compounds selected from the group consisting of naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferred, and indigo compounds and naphthalocyanine compounds are more preferred.

[0018] Cyanine compounds are disclosed in WO 2006 / 006573, WO 2010 / 073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; phthalocyanine compounds are disclosed in JP 4-23868, JP 06-192584, JP 2000-63691, WO 2016-073857, WO 2016-073857, WO 2016-073857, WO 2016-073857, WO 2016-073504, etc. 2014 / 208514, etc.; naphthalocyanine compounds are disclosed in JP-A-11-152414, JP-A-2000-86919, JP-A-2009-29955, WO 2018 / 186490, etc.; indigo compounds are disclosed in JP-A-2012-224593, JP-A-2013-87233, JP-A-2013-230412, etc.; immonium Compounds are disclosed in JP-A Nos. 2005-336150, 2007-197492, 2008-88426, etc.; anthraquinone compounds are disclosed in JP-A Nos. 62-903 and 1-172458, etc.; pyrrolopyrrole compounds are disclosed in JP-A Nos. 2009-263614, 2010-90313, and 2011-068731; Examples of qualium compounds include those described in JP 2011-132361 A, JP 2016-142891 A, WO 2017 / 135359 A, WO 2018 / 225837 A, JP 2019-001987 A, WO 2020 / 054718 A, etc.; examples of croconium compounds include those described in WO 2019 / 021767 A, etc.

[0019] (Squarylium compounds) The squarylium compound is preferably a compound represented by the following general formula (2). General formula (2) [ka]

[0020] (In general formula (2), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 10 , -COR11 , -COOR 12 , -OCOR 13 , -NR 14 R 15 , -NHCOR 16 , -CONR 17 R 18 , -NHCONR 19 R 20 , -NHCOOR 21 , -SR 22 , -SO2R 23 , -SO2OR 24 , -NHSO2R 25 , -SO2NR 26 R 27 , -B(OR 28 )2, and -NHBR 29 R 30 Represents R 10 ~R 30 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. 12 R 12 When -SO2OR is a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in the form of a salt. 24 R 24 When R is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.

[0021] The "substituent" may be a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 100 , -COR 101 , -COOR 102 , -OCOR 103 , -NR 104 R 105 , -NHCOR 106 , -CONR 107 R108 , -NHCONR 109 R 110 , -NHCOOR 111 , -SR 112 , -SO2R 113 , -SO2OR 114 , -NHSO2R 115 or -SO2NR 116 R 117 Examples include: R 100 ~R 117 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. 102 R 102 When -SO2OR is a hydrogen atom (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in the form of a salt. 114 R 114 When is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in the form of a salt.

[0022] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkynyl group may be linear, branched, or cyclic. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms. The alkyl portion of the aralkyl group is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the aryl group described above. The aralkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, and particularly preferably 7 to 25 carbon atoms. The heteroaryl group is preferably a monocyclic ring or a fused ring, more preferably a monocyclic ring or a fused ring having 2 to 8 rings, and particularly preferably a monocyclic ring or a fused ring having 2 to 4 rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12. The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, and aralkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the "substituents" described above.

[0023] From the viewpoint of light resistance and heat resistance, the squarylium compound is more preferably a compound represented by the following general formula (3). General formula (3) [ka]

[0024] (In general formula (3), R 5 ~R 8 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 50 , -COR 51 , -COOR 52 , -OCOR 53 , -NR 54 R 55 , -NHCOR 56 , -CONR 57 R 58 , -NHCONR 59 R 60 , -NHCOOR 61 , -SR 62 , -SO2R 63 , -SO2OR 64 , -NHSO2R 65 or -SO2NR 66 R 67 , -B(OR68 )2, and -NHBR 69 R 70 Represents R 50 ~R 70 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. 52 R 52 When is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in the form of a salt. 64 R 64 When R is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. 5 and R 6 , R 7 and R 8 may be bonded to each other to form a ring.

[0025] The "substituent" has the same meaning as the "substituent" described above.

[0026] Specific examples of squarylium compounds are shown below, but the present invention is not limited to these.

[0027] [ka]

[0028] [ka]

[0029] (Pyrrolopyrrole compounds) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (4).

[0030] General formula (4) [ka]

[0031] (In general formula (4), R 1x and R 1y each independently represents an alkyl group, an aryl group, or a heteroaryl group; R 2 and R 3 each independently represents a hydrogen atom or a substituent, R 2 and R 3 may be bonded to each other to form a ring, R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4x R 4y or a metal atom, R 4 is R 1x , R 1y and R 3 may be covalently or coordinately bonded to at least one selected from the group consisting of R 4x R 4y each independently represents a substituent. General formula (4) is described in, for example, JP-A Nos. 2009-263614, 2011-68731, and WO 2015 / 166873.

[0032] R 1x and R 1y are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. 1x and R 1y The alkyl group, aryl group, and heteroaryl group represented by may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 etc. R 11 ~R 13 each independently represents a hydrocarbon group or a heteroaryl group. Examples of the substituent include those described in paragraphs 0020 to 0022 of JP-A No. 2009-263614. Among them, examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 is preferred. 1x and R1y The group represented by the formula: is an alkoxy group having a branched alkyl group, or -OCOR 11 It is preferably an aryl group having as a substituent a group represented by the following formula: The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

[0033] R 2 and R 3 At least one of R is preferably an electron-withdrawing group. 2 represents an electron-withdrawing group, and R 3 represents a heteroaryl group. The heteroaryl group is preferably a 5-membered or 6-membered ring. The heteroaryl group is preferably a monocyclic or fused ring, preferably a monocyclic or fused ring having 2 to 8 rings, more preferably a monocyclic or fused ring having 2 to 4 rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 or 2. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. The two R in general formula (4) 2 In addition, the two R 3 They may be the same or different.

[0034] R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or -BR 4x R 4y and is preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by -BR 4x R 4y More preferably, it is a group represented by -BR 4x R 4y It is particularly preferable that R is a group represented by the following formula: 4x R 4y The substituent represented by is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. 4They may be the same or different.

[0035] Specific examples of pyrrolopyrrole compounds are shown below. In the following structural formulas, Me represents a methyl group, and Ph represents a phenyl group. Examples of pyrrolopyrrole compounds include the compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, paragraphs 0037 to 0052 of JP 2011-68731 A, paragraphs 0014 to 0027 of JP 2014-130343 A, and paragraphs 0010 to 0033 of WO 2015 / 166873 A. However, the present invention is not limited thereto.

[0036] [ka]

[0037] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably a compound represented by the following general formula (5).

[0038] General formula (5) [ka] (In general formula (5), X1~X8, Y l Each of Y8 independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonic acid group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. X1 to X8 may also be bonded to each other to form an aromatic ring which may have a substituent. However, any one or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 may be bonded to each other to form an aromatic ring which may have a substituent. Z is a polymer moiety containing a monomer unit represented by the following general formula (6) or a phosphorus compound moiety represented by the following general formula (7), and * represents a bond to Al.

[0039] Examples of the "alkyl group" in the alkyl group which may have a substituent include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, a 2-ethylhexyl group, etc. Examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, a 2,4-dichlorobenzyl group, etc.

[0040] Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0041] Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like. Examples of the "substituted cycloalkyl group" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, and the like.

[0042] Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, etc. Examples of the "heterocyclic group having a substituent" include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, etc.

[0043] Examples of the "alkoxyl group" in the alkoxyl group which may have a substituent include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group. Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

[0044] Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, etc. Examples of the "substituted aryloxy group" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

[0045] Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

[0046] Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

[0047] Examples of the substituent on the aromatic ring which may have a substituent include a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent.

[0048] General formula (6) [ka] (In the general formula (6), X is —CONH—R 25 -,-COO-R 26 -, -CONH-R 27 -O-, -COO-R 28 -O-. R 25 ~R 28 represents an alkylene group or an arylene group in which carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. 31 represents hydrogen or a methyl group.)

[0049] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, a terphenylene group, and an anthrylene group.

[0050] The monomer unit represented by general formula (6) can be obtained by polymerizing a monomer such as (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, (2-(meth)acryloyloxyisopropyl) acid phosphate, etc. Alternatively, it can be obtained by copolymerizing a monomer other than these monomers (hereinafter also referred to as other monomers) in combination.

[0051] Examples of other monomers include (meth)acrylic acid esters, crotonate esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth)acrylonitrile, acid group-containing monomers, and thermally crosslinkable group-containing monomers.

[0052] The weight average molecular weight of the polymer portion is preferably 5,000 to 20,000, and more preferably 8,000 to 15,000. Having an appropriate molecular weight improves the optical properties and heat resistance.

[0053] The glass transition temperature (Tg) of the polymer portion is preferably from −50 to 150° C., more preferably from 20 to 80° C. An appropriate Tg improves the optical properties.

[0054] General formula (7) [ka] (In general formula (7), R 29 and R 30 each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent; R29 and R 30 may be bonded to each other to form a ring.

[0055] Examples of the "alkyl group" of an optionally substituted alkyl group, the "aryl group" of an optionally substituted aryl group, the "alkoxyl group" of an optionally substituted alkoxyl group, and the "aryloxy group" of an optionally substituted aryloxy group are the same as those exemplified in the description of general formula (5) above.

[0056] General formula (7) is R 29 and R 30 At least one of R is preferably an aryl group which may have a substituent or an aryloxy group which may have a substituent, 29 and R 30 are more preferably all aryl groups or aryloxy groups, and R 29 and R 30 More preferably, all of are a phenyl group or a phenoxy group.

[0057] The naphthalocyanine compound is more preferably a compound represented by the following general formula (8).

[0058] General formula (8) [ka] (In general formula (8), Y9~Y 16 , R8~R 21 each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z is a polymer moiety containing a monomer unit represented by general formula (6) or a phosphorus compound moiety represented by general formula (7), and * is a bond to Al.

[0059] The alkyl group which may have a substituent, the aryl group which may have a substituent, the cycloalkyl group which may have a substituent, the heterocyclic group which may have a substituent, the alkoxyl group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, the arylthio group which may have a substituent, the phthalimidomethyl group which may have a substituent, and the sulfamoyl group which may have a substituent are as explained above in relation to general formula (5).

[0060] In general formula (8), Y9~Y 16 , R8~R 21 From the viewpoint of dispersibility and color properties, is preferably a hydrogen atom, a halogen atom, or an alkoxyl group which may have a substituent.

[0061] Specific examples of naphthalocyanine compounds are shown below, but the present invention is not limited to these. [ka] [ka]

[0062] (indigo compounds) The indigo compound is preferably a compound represented by the following general formula (9) or (10).

[0063] [ka] (In the formula, X1~X 40each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted arylalkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an amino group, an optionally substituted alkylamino group, an optionally substituted arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO3H; -COOH; and monovalent to trivalent metal salts of these acidic groups; or alkylammonium salts. M represents a metal atom.

[0064] Examples of the "alkyl group" in the alkyl group which may have a substituent include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, a 2-ethylhexyl group, etc. Examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, a 2,4-dichlorobenzyl group, etc.

[0065] Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0066] Examples of the "alkoxyl group" in the alkoxyl group which may have a substituent include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group. Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

[0067] Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, etc., and examples of the "aryloxy group having a substituent" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

[0068] Examples of the "arylalkyl group which may have a substituent" include a benzyl group, a 2-phenylpropan-yl group, a styryl group, a diphenylmethyl group, and a triphenylmethyl group.

[0069] Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, etc.

[0070] Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

[0071] Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

[0072] Examples of the "alkylamino group" in the alkylamino group optionally having a substituent include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an octadecylamino group, an isopropylamino group, an isopentylamino group, a sec-butylamino group, a tert-butylamino group, a sec-pentylamino group, a tert-pentylamino group, a tert-octylamino group, a neopentylamino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, and a 2-adamantamino group.

[0073] Examples of the "arylamino group" of the arylamino group which may have a substituent include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, a 2-biphenylamino group, a 3-biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

[0074] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0075] Examples of the acidic group include -SO3H and -COOH, and examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, and quaternary alkylammonium salts such as palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium, and distearyldimethylammonium salts.

[0076] Among the above substituents, X1 to X 40 Preferred substituents for include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and -SO3H.

[0077] M represents a metal atom. Examples of the metal atom include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, and Ba. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred.

[0078] Specific examples of indigo compounds are shown below, but the present invention is not limited to these.

[0079] [ka] [ka] [ka] [ka]

[0080] The near-infrared absorbing dye (A) can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use at least two compounds with different maximum absorption wavelengths. This broadens the absorption spectrum waveform compared to when a single near-infrared absorbing dye (A) is used, allowing near-infrared light to be absorbed over a wide wavelength range.

[0081] From the viewpoint of near-infrared absorbing properties, the content of the near-infrared absorbing dye (A) is preferably from 0.5 to 70 mass %, more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0082] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0083] The alkali-soluble resin (B) may be any resin that dissolves in an alkaline developer, and known resins can be used. The alkali-soluble resin (B) can be classified into non-photosensitive alkali-soluble resins and photosensitive alkali-soluble resins. The alkali-soluble resin (B) has an alkali-soluble group such as a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Among these, a carboxyl group is preferred. Examples of non-photosensitive alkali-soluble resins include acrylic resins having acidic groups, α-olefin / maleic anhydride copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic anhydride copolymers. The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. The alkali-soluble resin (B) may contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0084] From the viewpoint of developability, the weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The value of Mw / Mn (number average molecular weight) is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and solubility in development.

[0085] The acid value of the alkali-soluble resin (B) is preferably from 30 to 200 mgKOH / g, more preferably from 50 to 180 mgKOH / g. A suitable acid value improves adhesion to a substrate and solubility in development.

[0086] The content of the alkali-soluble resin (B) is preferably from 1 to 80% by mass, more preferably from 5 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0087] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0088] (Alkali-soluble resin (B1)) From the viewpoints of developability, pattern formation, and heat resistance, the photosensitive composition of the present invention preferably contains an alkali-soluble resin (B1) having a glass transition temperature of 0 to 150°C as the alkali-soluble resin (B).

[0089] The alkali-soluble resin (B1) may be any resin having a glass transition temperature of 0 to 150° C. and soluble in an alkali developer, and known resins can be used.

[0090] The glass transition temperature of the alkali-soluble resin (B1) is preferably from 5 to 120°C, more preferably from 10 to 80°C, from the viewpoints of developability, pattern formation, and heat resistance.

[0091] The glass transition temperature (hereinafter also referred to as Tg) can be a measured Tg obtained by actual measurement. Specifically, the measured Tg can be a value measured by differential scanning calorimetry (DSC). However, if measurement is difficult due to decomposition of the resin, etc., the calculated Tg obtained by the following formula is applied. 1 / Tg=W1 / Tg1+W2 / Tg2+······+W n / Tg n Here, the resins to be calculated are W1 to W n Suppose n kinds of monomer components up to W are copolymerized. n is the weight fraction of the nth monomer, Tg n is the glass transition temperature (absolute temperature) of the homopolymer of the nth monomer. The glass transition temperature of the homopolymer of each monomer (hereinafter also referred to as homopolymer) is the value shown in "Polymer Handbook, Third Edition, John Wiley & Sons, 1989" edited by Brandrup, J. Immergut, EH.

[0092] From the viewpoints of pattern formation and heat resistance, the alkali-soluble resin (B1) preferably contains an alicyclic hydrocarbon-containing monomer unit (b1) and an aromatic ring-containing monomer unit (b2) whose homopolymer has a glass transition temperature of 80°C or higher.

[0093] [Alicyclic hydrocarbon-containing monomer units (b1) having a homopolymer glass transition temperature of 80°C or higher] Examples of monomers forming alicyclic hydrocarbon-containing monomer units (b1) having a homopolymer glass transition temperature of 80° C. or higher include isobornyl acrylate, isobornyl methacrylate, adamantyl acrylate, adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, etc. Among these, isobornyl methacrylate, adamantyl methacrylate, and dicyclopentanyl methacrylate are preferred.

[0094] [Aromatic ring-containing monomer unit (b2) having a homopolymer glass transition temperature of 80°C or higher] Examples of the monomer that forms the aromatic ring-containing monomer unit (b2) having a homopolymer glass transition temperature of 80° C. or higher include styrene, α-methylstyrene, vinylnaphthalene, etc. Among these, styrene and α-methylstyrene are preferred.

[0095] From the viewpoints of pattern formation and heat resistance, the total content of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is preferably 10 to 70 mol %, more preferably 20 to 60 mol %, of all structural units of the alkali-soluble resin (B1).

[0096] The molar ratio of the alicyclic hydrocarbon-containing monomer unit (b1) to the aromatic ring-containing monomer unit (b2) is preferably 40:60 to 90:10, more preferably 50:50 to 80:20, from the viewpoints of pattern formation and heat resistance.

[0097] [Polymerizable unsaturated group-containing monomer unit (b3)] From the viewpoints of pattern formation and heat resistance, the alkali-soluble resin (B1) preferably contains a polymerizable unsaturated group-containing monomer unit (b3).

[0098] The alkali-soluble resin (B1) can be made to contain the polymerizable unsaturated group-containing monomer unit (b3) by, for example, the following methods (i) to (iii).

[0099] <Method (i)> There is a method (i) in which a carboxyl group of a carboxyl group-containing monomer is added to an epoxy group of an epoxy group-containing monomer unit contained in the alkali-soluble resin (B1).

[0100] Examples of the monomer that forms the epoxy group-containing monomer unit include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0101] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0102] From the viewpoint of developability, a moiety obtained by reacting an acid anhydride with a product obtained by adding a carboxyl group of a carboxyl group-containing monomer to an epoxy group of an epoxy group-containing monomer unit is also useful as the polymerizable unsaturated group-containing monomer unit (b3).

[0103] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0104] <Method (ii)> There is a method (ii) in which an epoxy group of an epoxy group-containing monomer is added to a carboxyl group of a carboxyl group-containing monomer unit contained in the alkali-soluble resin (B1).

[0105] <Method (iii)> There is a method (iii) in which the hydroxyl group of the hydroxyl group-containing monomer unit contained in the alkali-soluble resin (B1) is reacted with the isocyanate group of the isocyanate group-containing monomer.

[0106] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate.

[0107] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0108] From the viewpoints of pattern formation and heat resistance, the content of the polymerizable unsaturated group-containing monomer unit (b3) is adjusted so that the double bond equivalent of the alkali-soluble resin (B1) is preferably 200 to 1,000, more preferably 200 to 800, and particularly preferably 200 to 700. The double bond equivalent is the weight per mole of the ethylenically unsaturated double bond in the resin, and can be calculated by the following formula. Double bond equivalent weight = weight of resin (g) / amount of ethylenically unsaturated double bonds in resin (mol)

[0109] [Other monomer units (b4)] The alkali-soluble resin (B1) can contain other monomer units (b4) in addition to (b1) to (b3).

[0110] Examples of the monomers forming the other monomer units (b4) include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate; Polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid); epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 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-substituted maleimides such as 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, and 9-maleimidoacridine; Examples include phosphate group-containing (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0111] From the viewpoints of pattern formation and heat resistance, the content of the alkali-soluble resin (B1) is preferably from 40 to 100 mass %, more preferably from 60 to 100 mass %, based on 100 mass % of the alkali-soluble resin (B).

[0112] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0113] The weight average molecular weight (Mw) of the alkali-soluble resin (B1) is preferably from 5,000 to 40,000, more preferably from 5,000 to 30,000, from the viewpoint of heat resistance.

[0114] The acid value of the alkali-soluble resin (B1) is preferably from 30 to 200 mgKOH / g, more preferably from 50 to 180 mgKOH / g, from the viewpoint of developability.

[0115] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that forms a coating film upon curing.

[0116] The polymerizable compound (C) may be a monomer or oligomer having a polymerizable unsaturated group. Examples of the high-molecular-weight polymerizable unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group having an ethylenically unsaturated double bond. The weight-average molecular weight or formula weight of the polymerizable compound (C) is preferably less than 2,000.

[0117] Examples of the polymerizable compound (C) include lactone-modified polymerizable compounds, polymerizable compounds having an acid group, polymerizable compounds having a urethane bond, polymerizable compounds having a fluorene skeleton, and other polymerizable compounds.

[0118] (Lactone-modified polymerizable compound (C1)) The lactone-modified polymerizable compound (C1) is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound (C1) 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. The lactone-modified polymerizable compound (C1) is preferably a compound represented by the following general formula (11):

[0119] General formula (11) [ka]

[0120] In general formula (11), all six R's are groups represented by the following general formula (12), or one to five of the six R's are groups represented by the following general formula (12), and the remaining are groups represented by the following general formula (13).

[0121] General formula (12) [ka]

[0122] In general formula (11), R 1 represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond bonding to the oxygen atom of general formula (11).

[0123] General formula (13) [ka]

[0124] In general formula (13), R 1 represents a hydrogen atom or a methyl group, and * represents a bond to the oxygen atom in general formula (11).

[0125] The lactone-modified polymerizable compound (C1) is commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd., and is DPCA-20 (in the above general formulas (11) to (13), m=1, the number of groups represented by general formula (12)=2, R 1 are all hydrogen atoms), DPCA-30 (in the above general formulas (11) to (13), m=1, the number of groups represented by general formula (12)=3, R 1 are all hydrogen atoms), DPCA-60 (in the above general formulas (11) to (13), m=1, the number of groups represented by general formula (12)=6, R 1are all hydrogen atoms), DPCA-120 (in the above general formulas (11) to (13), m=2, the number of groups represented by general formula (12)=6, R 1 are all hydrogen atoms).

[0126] From the viewpoint of coating film resistance, the lactone-modified polymerizable compound (C1) is a compound represented by the general formulas (11) to (13) in which m=1, the number of groups represented by the general formula (12)=2 to 6, R 1 are all hydrogen atoms, and in the above general formulas (11) to (13), m=1, the number of groups represented by general formula (12)=2 or 3, R 1 A compound in which all are hydrogen atoms is more preferred.

[0127] From the viewpoint of heat resistance, the content of the lactone-modified polymerizable compound (C1) is preferably from 5 to 80 mass %, more preferably from 10 to 70 mass %, in 100 mass % of the polymerizable compound (C).

[0128] (Polymerizable compound (C2) having an acid group) From the viewpoint of developability and pattern formation, the photosensitive composition of the present invention preferably contains a polymerizable compound (C2) having an acid group. Examples of the acid group of the polymerizable compound (C2) having an acid group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0129] Examples of the polymerizable compound (C2) having an acid group include esters of dicarboxylic acids and free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids and monohydroxyalkyl (meth)acrylates. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like. Examples of polycarboxylic acids 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.

[0130] Commercially available products of the polymerizable compound (C2) having an acid group include Viscoat #2500P manufactured by Osaka Organic Chemicals, and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

[0131] The content of the polymerizable compound (C2) having an acid group is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, in 100 mass % of the polymerizable compound (C) from the viewpoint of developability and pattern formation.

[0132] From the viewpoint of heat resistance, the polymerizable compound (C2) having an acid group is more preferably a compound represented by the following general formula (14).

[0133] General formula (14) [ka] (In general formula (14), each R1 independently represents a hydrogen atom or a methyl group, and L represents a divalent linking group.)

[0134] The method for producing the compound represented by general formula (14) is not particularly limited, and any known method can be used. For example, (meth)acrylic acid and pentaerythritol are heated and stirred in the presence of an acidic catalyst to obtain a precursor having a hydroxyl group. Examples of the acid catalyst include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, etc. The reaction temperature may be appropriately set, but is preferably 70 to 140°C.

[0135] In the reaction, it is preferable to use an organic solvent that has low solubility in the water produced in the esterification reaction, and to promote dehydration while azeotropically distilling water off the organic solvent. Examples of the organic solvent include toluene, benzene, xylene, hexane, methyl ethyl ketone, and cyclohexanone.

[0136] The compound represented by general formula (14) can be produced by reacting the precursor with an acid anhydride in the presence of a catalyst at 60 to 110° C. for 1 to 20 hours.

[0137] In general formula (14), L is a divalent linking group, specifically a residue of an acid anhydride obtained by removing the carboxyl group.

[0138] Examples of acid anhydrides include succinic anhydride, dodecenylsuccinic anhydride, octenylsuccinic anhydride, maleic anhydride, glutamic anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Among these, succinic anhydride, octenylsuccinic anhydride, maleic anhydride, and phthalic anhydride are preferred, and succinic anhydride and octenylsuccinic anhydride are more preferred. Examples of the catalyst include N,N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, and benzyltrimethylammonium chloride.

[0139] Specific examples of the compound represented by formula (14) are shown below, but the present invention is not limited to these.

[0140] [ka]

[0141] From the viewpoint of heat resistance, the content of the compound represented by general formula (14) is preferably from 55 to 100 mass %, more preferably from 65 to 100 mass %, in 100 mass % of the polymerizable compound (C).

[0142] (Polymerizable compound (C3) having a urethane bond) When the photosensitive composition of the present invention contains a black colorant (F) described below, it preferably contains a polymerizable compound (C3) having a urethane bond from the viewpoint of pattern formation.

[0143] Examples of the polymerizable compound (C3) having a urethane bond include urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group 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 (meth)acrylate having a hydroxyl group.

[0144] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0145] 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; alicyclic diisocyanate such as isophorone diisocyanate; and biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts thereof.

[0146] From the viewpoint of developability, the polymerizable compound (C3) having a urethane bond preferably further has an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0147] The acid group can be introduced into the polymerizable compound (C3) having a urethane bond by, for example, first reacting the (meth)acrylate having a hydroxyl group with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0148] 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.

[0149] The number of polymerizable unsaturated groups in the polymerizable compound (C3) having a urethane bond is preferably 3 to 15, more preferably 5 to 12, from the viewpoint of pattern formation.

[0150] From the viewpoint of pattern formation, the content of the polymerizable compound (C3) 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).

[0151] (Polymerizable compound (C4) having a fluorene skeleton) When the photosensitive composition of the present invention contains a black colorant (F) described below, it preferably contains a polymerizable compound (C4) having a fluorene structure from the viewpoint of pattern formation. The polymerizable compound (C4) having a fluorene structure is preferably a compound represented by the following general formulas (19) to (21).

[0152] General formula (19) [ka] (In general formula (19), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, and m and n each independently represent an integer of 1 to 10.)

[0153] General formula (20) [ka] (In general formula (20), R5 and R6 each independently represent a hydrogen atom or a methyl group.)

[0154] General formula (21) [ka] (In general formula (21), R7 and R8 each independently represent a hydrogen atom or a methyl group.)

[0155] Commercially available polymerizable compounds (C4) having a fluorene structure include OGSOL EA-0200, EA-0300, GA-5060P, and GA-2800 manufactured by Osaka Gas Chemicals Co., Ltd., and Miramer HR6060, HR6100, and HR6200 manufactured by Miwon Specialty Chemical Co., Ltd.

[0156] (Other polymerizable compounds (C5)) Examples of other polymerizable compounds (C5) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Examples of the acrylic acid esters include acrylic acid esters and methacrylic acid esters such as methylolated melamine, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, and epoxy (meth)acrylate; styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0157] Other commercially available polymerizable compounds (C5) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, and D-330 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, and M-404 manufactured by Toagosei Co., Ltd. , M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Co., Ltd., NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL40, 130, 140, 145 manufactured by Daicel-Allnex Co., Ltd., and AH-600 and AT-600 manufactured by Kyoeisha Chemical Co., Ltd.

[0158] The polymerizable compound (C) can be used alone or in combination of two or more kinds.

[0159] The content of the polymerizable compound (C) is preferably from 1 to 60 mass %, more preferably from 2 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0160] [Photopolymerization initiator (D)] (Compound (D1) represented by general formula (1)) The photosensitive composition of the present invention contains a compound (D1) represented by general formula (1) as a photopolymerization initiator (D). The photopolymerization initiator (D) is a compound that can be cleaved by ultraviolet light to initiate radical polymerization.

[0161] General formula (1) [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.)

[0162] 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, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-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, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Of these, from the viewpoints of suppressing water stains and pattern shape, 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.

[0163] R3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy; 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. Substituents that the benzoyl group or thenoyl group 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.

[0164] Examples of methods for producing the compound (D1) represented by general formula (1) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0165] Specific examples of the compound (D1) represented by general formula (1) are shown below, but the present invention is not limited to these.

[0166] [ka]

[0167] Chemical formula (24) [ka]

[0168] Among the compounds of chemical formulas (22) to (24), the compound of chemical formula (22) is preferred from the viewpoints of pattern formability and heat resistance.

[0169] The compound (D1) represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0170] The content of the compound (D1) represented by general formula (1) is preferably from 10 to 100% by mass, more preferably from 20 to 90% by mass, based on 100% by mass of the photopolymerization initiator (D).

[0171] (Photopolymerization initiator (D2) other than the compound (D1) represented by general formula (1)) From the viewpoints of pattern formation and heat resistance, the photosensitive composition of the present invention preferably contains, as the photopolymerization initiator (D), a photopolymerization initiator (D2) other than the compound (D1) represented by general formula (1) (hereinafter, also referred to as other photopolymerization initiator (D2)).

[0172] The photopolymerization initiator (D2) is not particularly limited as long as it is a compound that can initiate polymerization of the polymerizable compound (C) by light, and known photopolymerization initiators can be used.

[0173] Specific examples of other photopolymerization initiators (D2) include acetophenone compounds 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, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis Examples of biimidazole compounds include (o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; and titanocene compounds. Among these, from the viewpoint of pattern formation and heat resistance, it is preferable to contain one or more compounds selected from the group consisting of acetophenone compounds, acylphosphine oxide compounds, and oxime compounds.

[0174] Commercially available acetophenone compounds include Omnirad 907, 369, and 379EG manufactured by IGM Resins. Commercially available acylphosphine oxide compounds include Omnirad819 and TPO manufactured by IGM Resins. Commercially available oxime compounds include IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan Ltd., ADEKA ARKULES N-1919, NCI-730, 831, and 930 manufactured by ADEKA Corporation, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., OMNIRAD1312, 1314, and 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemix Co., Ltd.

[0175] When the photosensitive composition of the present invention contains a colorant (F) described below, it preferably contains an oxime compound as an additional photopolymerization initiator (D2).

[0176] Examples of the oxime compound include the following compounds, but the present invention is not limited to these.

[0177] [ka] [ka]

[0178] The method for producing the compounds of chemical formulas (25) to (31) is not particularly limited, and known methods can be used. For example, methods described in JP-T-2004-534797, JP-A-2008-80068, JP-T-2012-526185, WO 2015 / 036910, WO 2015 / 152153, JP-T-2016-504270, JP-T-2017-512886, JP-T-2017-523465, JP-A-2021-011486, etc. can be mentioned.

[0179] From the viewpoints of pattern formation and heat resistance, the oxime compound is more preferably one or more selected from the group consisting of compounds of chemical formulas (25) to (31), and particularly preferably one or more selected from the group consisting of compounds of chemical formulas (27) to (29).

[0180] The other photopolymerization initiators (D2) can be used alone or in combination of two or more.

[0181] The content of the photopolymerization initiator (D) is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0182] [Sensitizer (E)] The photosensitive composition of the present invention may contain a sensitizer (E) from the viewpoint of pattern formation.

[0183] Examples of the sensitizer (E) include chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and polymethine dyes such as oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples of the compound include compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds. Among these, thioxanthone compounds (E1) and benzophenone compounds (E2) are preferred from the viewpoint of pattern formation.

[0184] (Thioxanthone compounds (E1)) Examples of the thioxanthone compound (E1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

[0185] (Benzophenone compounds (E2)) Examples of the benzophenone compound (E2) include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0186] The sensitizer (E) can be used alone or in combination of two or more kinds.

[0187] From the viewpoint of pattern formation, the content of the sensitizer (E) is preferably from 5 to 400 parts by mass, more preferably from 10 to 300 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D).

[0188] Colorant (F) The photosensitive composition of the present invention may contain a colorant (F), which makes it possible to control the transmittance of the cured film in each wavelength region, thereby improving color separation and shielding properties.

[0189] The colorant (F) may be either a pigment or a dye, and these may be used in combination.

[0190] (pigment) The pigment is preferably a compound classified as a pigment in the Color Index. 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. Among these, from the viewpoints of heat resistance, light fastness, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are more preferred.

[0191] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0192] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 1,152, 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, JP 2012-226110 A, JP 2017-171912 A, JP 2017-171913 A, JP 2017-171914 A, JP 2017-171915 A, and the like. Among these, CI Pigment Yellows 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110 are preferred.

[0193] 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. Among these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0194] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0195] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0196] Specific examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, 31, and 32. Other examples include compounds described in JP-A Nos. 2010-534726, 2012-515233, and 2012-515234, JP-A Nos. 1-170601, and 2-34664.

[0197] When the photosensitive composition of the present invention is used in an infrared transmission filter, it preferably contains, as colorant (F), two or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments, and violet pigments, and exhibits a black color.

[0198] Examples of combinations that produce a black color include the following: (1) Contains yellow pigment and purple pigment. (2) Contains red pigment, yellow pigment, and purple pigment. (3) Contains red pigment, yellow pigment, and blue pigment. (4) Contains red pigment, yellow pigment, and green pigment. (5) Contains yellow pigment, blue pigment, and purple pigment. (6) Contains red pigment, yellow pigment, blue pigment, and purple pigment.

[0199] A specific example of the above embodiment (1) is an embodiment containing at least one selected from CI Pigment Yellow 139, 185, 231, and 233 as the yellow pigment and CI Pigment Violet 23 as the purple pigment. A specific example of the above embodiment (2) is an embodiment containing at least one selected from CI Pigment Red 177, 254, 291, 295, and 296 as the red pigment, at least one selected from CI Pigment Yellow 139, 185, 231, and 233 as the yellow pigment, and CI Pigment Violet 23 as the purple pigment. A specific example of the above embodiment (3) is an embodiment containing at least one red pigment selected from CI Pigment Red 177, 254, 291, 295, and 296, at least one yellow pigment selected from CI Pigment Yellow 139, 185, 231, and 233, and at least one blue pigment selected from CI Pigment Blue 15:3, 15:4, and 15:6. A specific example of the above embodiment (4) is an embodiment containing at least one red pigment selected from CI Pigment Red 177, 254, 291, 295, and 296, at least one yellow pigment selected from CI Pigment Yellow 139, 185, 231, and 233, and at least one green pigment selected from CI Pigment Green 7, 36, 58, 59, and 63. A specific example of the above embodiment (5) is an embodiment containing at least one selected from CI Pigment Yellow 139, 185, 231, and 233 as the yellow pigment, at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6 as the blue pigment, and CI Pigment Violet 23 as the violet pigment. A specific example of the above embodiment (6) is an embodiment containing at least one selected from CI Pigment Red 177, 254, 291, 295, and 296 as the red pigment, at least one selected from CI Pigment Yellow 139, 185, 231, and 233 as the yellow pigment, at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6 as the blue pigment, and CI Pigment Violet 23 as the purple pigment.

[0200] Among the above embodiments (1) to (6), the above embodiment (5) is preferred from the viewpoint of light-blocking properties.

[0201] Among the above embodiments (5), it is more preferable to contain CI Pigment Yellow 139 as the yellow pigment, CI Pigment Blue 15:6 as the blue pigment, and CI Pigment Violet 23 as the violet pigment.

[0202] Table 1 shows the preferred mass ratios (mass %) of each organic pigment in each embodiment.

[0203] [Table 1]

[0204] Among the pigments, examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, 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.

[0205] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are derivatives of these dyes and lake pigments obtained by converting dyes into lakes.

[0206] The acid dye preferably has an acidic group such as a sulfonic acid or carboxylic acid. Also preferred are salt-forming compounds that are salts of an acid dye with 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 an acid dye with a resin component having these functional groups. Furthermore, the salt-forming compounds can be sulfonamidated to modify them into sulfonic acid amide compounds, which makes it easier to obtain photosensitive compositions 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.

[0207] Although basic dyes can be used as they are, salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof 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 that acts as a counterion 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 with a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. Furthermore, the resistance of salt-forming compounds is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0208] 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.

[0209] Among these, from the viewpoint of color properties such as hue, color separation ability, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0210] The colorant (F) can be used alone or in combination of two or more kinds.

[0211] The content of the colorant (F) is preferably from 5 to 70 parts by mass, more preferably from 10 to 60 parts by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0212] (Fine pigments) 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.

[0213] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heat using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0214] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the standpoint of both treatment efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0215] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred for safety reasons. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0216] A resin may be added to the salt milling treatment as needed. 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 and insoluble in water are preferred, and those that are partially soluble in the 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.

[0217] [Dispersion resin (G)] The photosensitive composition of the present invention may contain a dispersing resin (G).

[0218] The dispersing resin (G) is preferably a resin having an adsorptive group that has high affinity for the near-infrared absorbing dye (A). The adsorptive group preferably has at least one of a basic group and an acidic group.

[0219] 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.

[0220] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0221] Examples of resin types for the dispersing resin (G) 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 phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl 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.

[0222] Examples of the structure of the dispersing resin (G) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, the block structure or the comb structure is preferred from the viewpoint of dispersion stability.

[0223] Commercially available dispersion resins (G) 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, 2095, 2150, 2155, 2163, and 2164 manufactured by BYK-Chemie Japan, or Anti-Terra-U203 and 204, or BYK-P 104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000 manufactured by Lubrizol Japan ,76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF Japan, and Ajisu manufactured by Ajinomoto Fine-Techno Co., Ltd. Examples include resins described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, WO 2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, and the like.

[0224] The dispersing resin (G) can be used alone or in combination of two or more kinds.

[0225] From the viewpoint of dispersion stability, the content of the dispersing resin (G) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the near-infrared absorbing dye (A).

[0226] [Dye derivative (H)] The photosensitive composition of the present invention may contain a dye derivative (H).

[0227] The dye derivative (H) is not particularly limited, and examples thereof include dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of the dye derivative (H) 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.

[0228] Specifically, diketopyrrolopyrrole dye derivatives are disclosed in JP 2001-220520 A, WO 2009 / 081930 A, WO 2011 / 052617 A, WO 2012 / 102399 A, and JP 2017-156397 A; phthalocyanine dye derivatives are disclosed in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and anthraquinone dye derivatives are disclosed in JP 63-264 A. 674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325, as quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, as dioxazine dye derivatives, JP-A-2011-162662, as thiazine indigo dye derivatives, JP-A-2007-314785, as triazine Examples of benzoisoindole dye derivatives include those disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; examples of benzoisoindole dye derivatives include those disclosed in JP-A-2009-57478; and examples of quinophthalone dye derivatives include those disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226 Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those known in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc.In these documents, the dye derivative is sometimes referred to as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0229] The dye derivative (H) can be used alone or in combination of two or more kinds.

[0230] The content of the dye derivative (H) is preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass, relative to 100 parts by mass of the near-infrared absorbing dye (A).

[0231] [Thermosetting compound (I)] The photosensitive composition of the present invention may contain a thermosetting compound (I), which reacts in the heating step to increase the crosslink density and improve the heat resistance.

[0232] The thermosetting compound (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (I) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0233] (Epoxy compound (I1)) Examples of the epoxy compound (I1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0234] Commercially available products 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 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 the like.

[0235] From the viewpoint of heat resistance of the cured film, the content of the epoxy compound (I1) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0236] (Oxetane compound (I2)) The oxetane compound (I2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0237] Examples of monofunctional oxetane compounds 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, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0238] Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0239] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 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, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(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, and the like.

[0240] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0241] Examples of trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0242] From the viewpoint of heat resistance of the cured film, the content of the oxetane compound (I2) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0243] The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easier to obtain just the right amount of heat resistance.

[0244] Examples of commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0245] Among these, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 manufactured by Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred in terms of increasing crosslink density.

[0246] The thermosetting compound (I) can be used alone or in combination of two or more kinds.

[0247] [Curing agent (curing accelerator)] The photosensitive composition of the present invention can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound (I). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples of suitable amines include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.).

[0248] The curing agents can be used alone or in combination of two or more.

[0249] The content of the curing agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound (I).

[0250] [Thiol-based chain transfer agents (J)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (J). When the thiol chain transfer agent (J) is used in combination with the photopolymerization initiator (D), it generates thiyl radicals that are resistant to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive composition.

[0251] The thiol chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0252] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include erythritol tetrakisthiopropionate, 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. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0253] The thiol chain transfer agent (J) can be used alone or in combination of two or more kinds.

[0254] The content of the thiol chain transfer agent (J) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, per 100 parts by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0255] [Polymerization inhibitor (K)] The photosensitive composition of the present invention may contain a polymerization inhibitor (K).

[0256] Examples of the polymerization inhibitor (K) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; alkylresorcinol compounds such as 4-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucin.

[0257] The content of the polymerization inhibitor (K) is preferably 0.01 to 0.4% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0258] [Ultraviolet absorber (L)] The photosensitive composition of the present invention may contain an ultraviolet absorber (L).

[0259] The ultraviolet absorber (L) is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0260] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl octyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0261] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0262] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0263] Examples of commercially available products include KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adekastab LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0264] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0265] Examples of commercially available products include KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0266] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0267] The content of the ultraviolet absorber (L) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[0268] [Antioxidant (M)] The photosensitive composition of the present invention can contain an antioxidant (M). The antioxidant (M) prevents yellowing of the photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive coloring composition due to oxidation during the thermal process of thermal curing or ITO annealing. In particular, when the concentration of the near-infrared absorbing dye (A) in the photosensitive composition is high, the content of the polymerizable compound (C) is relatively reduced, and if the amount of the photopolymerization initiator (D) is increased or a thermosetting compound is added to address this, the cured film is likely to yellow. Therefore, the inclusion of an antioxidant prevents yellowing of the cured film due to oxidation during the heating process. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

[0269] Examples of the antioxidant (M) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0270] Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4 ,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-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.

[0271] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0272] Examples of the hindered amine antioxidant 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-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol and 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.

[0273] 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.

[0274] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-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-t-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'-isopropylidene Diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0275] 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.

[0276] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0277] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0278] The antioxidant (M) can be used alone or in combination of two or more kinds.

[0279] 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. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[0280] [Leveling Agent (N)] The photosensitive composition of the present invention can contain a leveling agent (N). This further improves the wettability to the substrate during application and the drying property. Examples of the leveling agent (N) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0281] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0282] Commercially available products 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., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0283] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0284] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0285] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

[0286] Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation. S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0287] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0288] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0289] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0290] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0291] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; and alkylamine oxides such as lauryldimethylamine oxide.

[0292] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0293] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0294] The content of the leveling agent (N) is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[0295] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O). This stabilizes the viscosity of the photosensitive composition over time. Examples of the storage stabilizer (O) include 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 t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0296] The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the near-infrared absorbing dye (A).

[0297] [Adhesion improver (P)] The photosensitive composition of the present invention may contain an adhesion promoter (P), which improves the adhesion between the cured film and the substrate and also makes it easier to form narrow patterns by photolithography.

[0298] Examples of the adhesion improver (P) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0299] The adhesion improver (P) can be used alone or in combination of two or more kinds.

[0300] The content of the adhesion improver (P) is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, relative to 100 parts by mass of the near-infrared absorbing dye (A).

[0301] [Organic solvent (Q)] The photosensitive composition of the present invention may contain an organic solvent (Q).

[0302] Examples of the organic solvent (Q) include 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, 3-methoxy- 3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyro Lactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples of the alkyl esters include 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. Among these, from the viewpoints of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0303] The organic solvent (Q) can be used alone or in combination of two or more kinds.

[0304] [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.

[0305] When the total amount of the specific metal elements in the photosensitive composition is within the above range, the composition exhibits excellent dispersion stability and sensitivity even after storage over time. Furthermore, a cured product prepared using the photosensitive composition having the total amount of the specific metal elements within the above range exhibits excellent heat resistance and generates little foreign matter even when heated.

[0306] The total amount of the specific metal elements contained in the photosensitive composition is more preferably 300 ppm by mass or less, particularly preferably 200 ppm by mass or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more.

[0307] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0308] From the viewpoints of storage stability and suppression of generation of foreign matter, it is preferable that the content of metal elements other than the specific metal elements is also reduced in the photosensitive composition of the present invention. Examples of metals other than the specific metal elements include Mn, Cs, Ti, Co, Ni, Si, and Pd.

[0309] [Water content] The photosensitive composition of the present invention preferably contains water in an amount of 2.0% by mass or less.

[0310] When the water content of the photosensitive composition is within the above range, the composition exhibits excellent dispersion stability and sensitivity even after storage over time.

[0311] The water content in the photosensitive composition is more preferably 1.8% by mass or less, particularly preferably 1.6% by mass or less. The lower limit of the water content is preferably as low as possible, and there is no particular restriction. Within the above range, the dispersion stability and sensitivity are excellent even after storage.

[0312] The water content can be measured by a known method such as the Karl Fischer method.

[0313] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced by, for example, preparing a dispersion by adding a near-infrared absorbing dye (A), a dispersing resin (G), an organic solvent (Q), and the like and performing a dispersion treatment. The dispersion can then be mixed with an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and the like. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0314] 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.

[0315] The average dispersed particle size (secondary particle size) of the near-infrared absorbing dye (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A suitable particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

[0316] 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.

[0317] 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 any dust particles that have been mixed in, 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.

[0318] <Cured film> The cured film of the present invention is a cured product of the photosensitive composition of the present invention. Curing is carried out by subjecting the film formed by coating to a treatment such as exposure to light.

[0319] [Method of manufacturing cured film] The method for producing the cured film is not particularly limited, and the cured film can be produced, for example, by carrying out the following steps: step (1) of applying a photosensitive composition onto a substrate to form a layer of the composition; step (2) of exposing the layer to light in a pattern through a mask; step (3) of developing the unexposed portions with an alkali to form a patterned cured film; and step (4) of heat-treating (post-baking) the pattern.

[0320] The method for producing the cured film will be described in detail below. (Process (1)) In the step (1) of forming a composition layer, the photosensitive composition is applied to a substrate by, for example, rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (prebaked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, a hot plate, or the like, as needed. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an imaging element such as a CCD or a CMOS formed on its surface. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface. The thickness of the layer is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

[0321] (Process (2)) In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0322] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an alkaline aqueous solution, leaving only the cured areas, thereby obtaining a patterned cured film. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developer is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses pattern roughening and peeling, and improves the remaining film rate after development.

[0323] 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.

[0324] (Step (4)) The heat treatment (post-baking) is performed by heating the patterned cured film obtained in step (3) to sufficiently cure it. The heating temperature for post-baking is preferably 100 to 300° C., more preferably 150 to 250° C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

[0325] <Optical filters> The cured film of the present invention can be used for an optical filter. The optical filter is preferably, for example, an infrared cut filter or an infrared transmission filter. The optical filter of the present invention can be produced by the same method as for the cured film described above.

[0326] <Image display device> The cured film of the present invention can be used in an image display device. The form in which it is used in an image display device is not particularly limited, and it can be used as a color filter or a black matrix. Examples of the black matrix include a black border provided on the periphery of an image display device such as a solid-state imaging device or a liquid crystal display device, a grid-like and / or stripe-like black portion between red, blue, and green pixels, and a dot-like and / or linear black pattern for TFT light shielding.

[0327] An example of an image display device of the present invention will be described. The image display device comprises the cured film of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFL) and white LEDs, but in the present invention, it is preferable to use white LEDs because they broaden the red reproduction range. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an image display device comprising the cured film of the present invention. The image display device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 arranged at a distance from each other, with a liquid crystal LC sealed between them.

[0328] A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0329] On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. Red, green, and blue filter segments that constitute the color filter 22 are separated by a black matrix (not shown).

[0330] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0331] A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0332] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), or OCB (Optically Compensated Birefringence). A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizer 15 is formed on the outer surface of the transparent substrate 11.

[0333] On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. Red, green, and blue filter segments that constitute the color filter 22 are separated by a black matrix (not shown).

[0334] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0335] A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0336] The white LED light source includes a blue LED with a fluorescent filter formed on the surface, and a blue LED with a fluorescent material contained in the resin package, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity becomes maximum, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity becomes maximum, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity becomes maximum, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. Therefore, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum in the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity in the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0337] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0338] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0339] <Solid-state imaging element> The cured film of the present invention can be used in a solid-state imaging device. The form of the solid-state imaging device used is not particularly limited, but examples include a substrate having a plurality of photodiodes constituting the light-receiving area of ​​the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor) and a light-receiving element made of polysilicon or the like, and the cured film of the present invention on the side where the light-receiving element is formed or on the side opposite to the side where the light-receiving element is formed. Figure 2 is a schematic cross-sectional view showing an example of the configuration of a solid-state imaging device provided with the cured film of the present invention.

[0340] As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging element 201 and a transparent cover glass 203 that is held above the solid-state imaging element 201 and seals the solid-state imaging element 201. Furthermore, a lens layer 211 is provided on the cover glass 203 via a spacer 104. The lens layer 211 is composed of a support 213 and a lens material 212. When stray light enters the peripheral region of the lens layer 211, the light diffusion weakens the light-collecting effect of the lens material 212, thereby reducing the amount of light that reaches the imaging unit 202. Furthermore, noise due to the stray light also occurs. Therefore, the peripheral region of the lens layer 211 is provided with a cured film 214 of the present invention to shield it from light.

[0341] The solid-state imaging element 201 photoelectrically converts an optical image formed on an imaging section 202, which serves as its light-receiving surface, and outputs the converted image signal. The solid-state imaging element 201 includes a laminated substrate 205 formed by laminating two substrates. The laminated substrate 205 is made up of a rectangular chip substrate 206 and a circuit substrate 207 of the same size, with the circuit substrate 207 laminated on the back surface of the chip substrate 206.

[0342] An imaging unit 202 is provided in the center of the surface of the chip substrate 206. Furthermore, if stray light is incident on the peripheral region of the imaging unit 202, a dark current (noise) is generated from the circuit in this peripheral region, and therefore, this peripheral region is provided with a cured film (light-shielding) 215 of the present invention to shield it from light.

[0343] A plurality of electrode pads 208 are provided on the edge of the surface of the chip substrate 206. The electrode pads 208 are electrically connected to the imaging unit 202 via signal lines (not shown) provided on the surface of the chip substrate 206.

[0344] External connection terminals 209 are provided on the rear surface of the circuit board 207 at positions approximately below the electrode pads 208. Each external connection terminal 209 is connected to each electrode pad 208 via a through electrode 210 that vertically penetrates the laminated substrate 205. Each external connection terminal 209 is also connected via wiring (not shown) to a control circuit that controls the driving of the solid-state imaging element 201, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging element 201, and the like.

[0345] <Infrared sensor> The cured film of the present invention can be used in an infrared sensor. Fig. 3 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor including the cured film of the present invention. The infrared sensor 300 shown in Fig. 3 includes a solid-state imaging element 310.

[0346] The imaging area provided on the solid-state imaging device 310 is configured by combining an infrared cut filter 311 and a color filter 312 . The infrared cut filter 311 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 1300 nm). The color filter 312 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.

[0347] Between the infrared transmission filter 313 and the solid-state imaging element 310, a resin film 314 that is capable of transmitting light of the wavelength that has passed through the infrared transmission filter 313 is disposed. The infrared transmission filter 313 is a filter that has visible light blocking properties and transmits infrared light of a specific wavelength, and can use the cured film of the present invention that contains the near-infrared absorbing dye (A) described above and two or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments, and violet pigments as the colorant (F). 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 1300 nm, for example.

[0348] A microlens 315 is disposed on the incident light side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.

[0349] In the embodiment shown in FIG. 3, the resin film 314 is disposed, but instead of the resin film 314, an infrared transmission filter 313 may be formed.

[0350] The cured film of the present invention can be used as a light-shielding film for the edge and / or side surfaces of the surface of the infrared cut filter 311, and when used on the inner wall of an infrared sensor, it can prevent internal reflection and / or the incidence of unwanted light into the light-receiving section, thereby improving sensitivity.

[0351] 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.

[0352] The cured film of the present invention can also be used as a colored spacer. For example, when a spacer is used in a TFT-type LCD, light incident on the TFT may cause the TFT to malfunction as a switching element, and the colored spacer is used to prevent this. The colored spacer can be formed in the same manner as the black matrix described above, except that a mask for the colored spacer is used.

[0353] The cured film of the present invention can also be used in applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, the cured film can be suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as for members that impart light-blocking and anti-reflection properties. Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

[0354] The cured film of the present invention can also be used in applications such as quantum dot displays. Although not particularly limited, it can be suitably used for optical filters and optical films used in quantum dot displays, as well as for members that impart light-blocking properties and anti-reflection properties. [Example]

[0355] 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 to stand in an oven at 280°C for 30 minutes.

[0356] Before describing the examples, each measurement method will be explained.

[0357] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and glass transition temperature (Tg) of the resin are measured as follows.

[0358] (average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation). Two separation columns were connected in series, with both columns packed with TSK-GEL SUPER HZM-N. 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 wt% of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0359] (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.

[0360] (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.

[0361] (glass transition temperature of resin) The glass transition temperature of the resin was measured using a differential scanning calorimeter by weighing 5 mg of sample into a sample pan and heating from −20 to 200° C. at a rate of 10° C. / min under a nitrogen stream. (Measurement of specific metal elements) The contents of Li, Na, K, Mg, Ca, Fe, and Cr contained in the photosensitive composition were measured using an ICP emission spectrometer (Shimadzu Corporation, ICPE-9800).

[0362] (Water content measurement) The water content in the photosensitive composition was measured using a Karl Fischer titrator (volumetric titration water content measuring device Model KF-06 manufactured by Mitsubishi Chemical Corporation).

[0363] <Production of near-infrared absorbing dye (A)> (Near-infrared absorbing dye (A-1)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the toluene was distilled to obtain a dark brown solid, which was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled off, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting dark brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain near-infrared absorbing dye (A-1) represented by the following chemical formula (32). 50 parts of the resulting near-infrared absorbing dye (A-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 12 hours. The kneaded mixture was then poured into warm water and stirred for 1 hour while heated to approximately 80°C to form a slurry. The mixture was then filtered and washed with water to remove the sodium chloride and diethylene glycol. The mixture was then dried overnight at 80°C and pulverized to obtain finely divided near-infrared absorbing dye (A-1).

[0364] Chemical formula (32) [ka]

[0365] (Near-infrared absorbing dye (A-2)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 50.1 parts of 2-hydroxy-9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the toluene was distilled to give a dark brown solid, which was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, to which 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and the resulting reaction mixture was stirred and 200 parts of hexane was added. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorbing dye (A-2) represented by the following chemical formula (33). A finely divided near-infrared absorbing dye (A-2) was obtained in the same manner as in the near-infrared absorbing dye (A-1).

[0366] Chemical formula (33) [ka]

[0367] (Near-infrared absorbing dye (A-3)) In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts of aluminum trichloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of ion-exchanged water while stirring, yielding a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain compound a. Next, in a reaction vessel, 140 parts of compound a was added to 1,500 parts of concentrated sulfuric acid in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and washed with water again, and then dried to obtain compound b. Five parts of diphenyl phosphate were added to 200 parts of N-methylpyrrolidone, thoroughly stirred, and then heated to 50°C. 10 parts of compound b were gradually added to this solution, and the mixture was stirred at 90°C for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto filter paper and determining when no bleeding occurred. Subsequently, this reaction solution was poured into 2,000 parts of ion-exchanged water, and the resulting precipitate was filtered, washed with water, and dried to obtain a near-infrared absorbing dye (A-3), which is a mixture of compounds represented by the following chemical formula (34) (mixing ratio: n1:n2:n3:n4=7:19:59:15).

[0368] Chemical formula (34) [ka]

[0369] (Near-infrared absorbing dye (A-4)) According to the description in WO 2019 / 058882, a near-infrared absorbing dye (A-4) represented by the following chemical formula (35) was obtained. A finely divided near-infrared absorbing dye (A-4) was obtained in the same manner as in the near-infrared absorbing dye (A-1).

[0370] Chemical formula (35) [ka]

[0371] (Near-infrared absorbing dye (A-5)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / L toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo was added and refluxed for 10 hours. After the reaction was completed, methanol was added and the mixture was filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated to 40°C and stirred for 5 hours. The reaction solution was cooled to 30°C while still stirring, and then poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, then washed with 500 parts of water, and dried to obtain near-infrared absorbing dye (A-5), which is a mixture of compounds represented by the following chemical formula (36) (mixing ratio: dimer: trimer: tetramer = 81:17:2).

[0372] Chemical formula (36) [ka]

[0373] <Production of alkali-soluble resin (B)> (Alkali-soluble resin (B1-1) solution) A reaction vessel was prepared by attaching a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer to a separable four-neck flask. 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed in the reaction vessel, and the vessel was heated to 120°C while injecting nitrogen gas into it. At the same temperature, a mixture of 5.2 parts of styrene (hereinafter, St), 35.5 parts of glycidyl methacrylate (hereinafter, GMA), 41.0 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 17.0 parts of acrylic acid (hereinafter referred to as AA) was charged with 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone, and the mixture was reacted for 5 hours at 120°C. This caused the epoxy group of GMA to react with the carboxyl group of AA, and polymerizable unsaturated group-containing monomer unit (b3) (hereinafter referred to as GMA+AA) was introduced. Further, 30.4 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours. This caused an esterification reaction between the hydroxyl groups of GMA + AA and TPHA, introducing polymerizable unsaturated group-containing monomer units (b3) (hereinafter referred to as GMA + AA + TPHA). Then, PGMAc was added so that the nonvolatile content became 20%, and an alkali-soluble resin (B1-1) solution was prepared.

[0374] (Alkali-soluble resins (B1-2) to (B1-6), and (B2-1), (B2-2) solutions) The types and amounts of the ingredients were changed to achieve the composition / molar percentage ratios shown in Table 2, and alkali-soluble resins (B1-2) to (B1-6) and alkali-soluble resins (B2-1) and (B2-2) were synthesized. PGMAc was added to adjust the non-volatile content to 20%.

[0375] [Table 2]

[0376] MAA+GMA in Table 2 represents a polymerizable unsaturated group-containing monomer unit (b3) in which the epoxy group of glycidyl methacrylate is added to the carboxyl group of methacrylic acid (MAA), which is a monomer unit contained in an alkali-soluble resin.

[0377] The Tg ranges of the alkali-soluble resins listed in Table 2 are as follows: A: 10℃ or more and 80℃ or less B: 0℃ or higher but lower than 10℃, or higher than 80℃ but lower than 150℃ C: Below 0°C or above 150°C

[0378] <Production of polymerizable compound (C)> (Polymerizable compound (C3-1) having a urethane bond) A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, thermometer, and dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The mixture was heated to 70°C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise over 2 hours. After the addition, the mixture was allowed to react for 8 hours at a temperature of 50-70°C, and a peak was observed at 2180cm- by IR. 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 polymerizable compound (C3-1) having an average of 9 polymerizable unsaturated groups and urethane bonds was obtained.

[0379] <Production of Colorant (F)> (Finely divided green pigment (F-1)) 100 parts of CI Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3,000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heated to 70° C. to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried overnight at 80° C. and pulverized to obtain a finely divided green pigment (F-1).

[0380] (Finely divided red pigment (F-2)) 100 parts of CI Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60°C. Next, the kneaded mixture was poured into warm water, and while heated to approximately 80°C, it was stirred for 1 hour using a high-speed mixer to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol. After that, it was dried overnight at 80°C and pulverized to obtain a finely divided red pigment (F-2).

[0381] (Finely divided blue pigment (F-3)) 100 parts of CI Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50°C. This mixture was poured into 3,000 parts of warm water, and while heated to about 70°C, the mixture was stirred in a high-speed mixer for about 1 hour to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, then dried at 80°C for 24 hours and pulverized to obtain a finely divided blue pigment (F-3).

[0382] (Finely divided yellow pigment (F-4)) 100 parts of CI Pigment Yellow 138, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70° C. This mixture was poured into 3,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heated to about 70° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, then dried overnight at 80° C. and pulverized to obtain a finely divided yellow pigment (F-4).

[0383] (Finely divided purple pigment (F-5)) 100 parts of CI Pigment Violet 23, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70° C. This mixture was poured into 3,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heated to about 70° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, then dried overnight at 80° C. and pulverized to obtain a finely divided purple pigment (F-5).

[0384] <Production of Dispersion Resin (G)> (Dispersion resin (G-1) 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. The reaction solution was then cooled to room temperature to terminate the polymerization. GPC analysis revealed that the polymer had a mass-average molecular weight of 20,000, a molecular weight distribution (Mw / Mn) of 1.4, and a reaction conversion rate of 98.5%. In this way, a dispersion resin (G-1) with an amine value per nonvolatile content of 169.8 mg KOH / g was obtained. After cooling to room temperature, approximately 2 g was sampled and dried at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to obtain a dispersion resin (G-1) solution with a nonvolatile content of 30% by mass.

[0385] (Dispersion resin (G-2) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, a sample of the polymerization solution was taken and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as the second block (A block) monomer were added to the reactor, and the reaction was continued with stirring at 110 °C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. The conversion rate of the second block (A block) was confirmed to be 98% or higher based on the nonvolatile content. The reaction solution was then cooled to room temperature to terminate the polymerization. The nonvolatile content was then adjusted to 30% by dilution with PGMAc, yielding a dispersion resin (G-2) solution with an amine value of 57 mg KOH / g and a number-average molecular weight (Mn) of 4,500.

[0386] (Dispersion resin (G-3) solution) A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc, and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile and 90 parts PGMAc was added while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% reaction had occurred. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued for 7 hours at 100°C. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to dilute the solution so that the nonvolatile content reached 30% by measuring the nonvolatile content, yielding a dispersion resin (G-3) solution with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0387] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan, "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 organic solvent (Q-1) was PGMAc. Near-infrared absorbing dye (A-1): 15.0 parts Dispersion resin (G-1) solution: 20.0 parts Organic solvent (Q-1): 65.0 parts

[0388] (Dispersion 2~10) Dispersions 2 to 10 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 3 were changed.

[0389] [Table 3]

[0390] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. The contents of the specific metal element and water in Photosensitive Composition 1 were 39 ppm and 1.2 mass %, respectively. Dispersion 3: 35.0 parts Alkali-soluble resin (B1-1) solution: 30.0 parts Polymerizable compound (C2-1) having an acid group: 7.0 parts Compound (D1-1) represented by general formula (1): 0.5 parts Benzophenone compound (E2-1): 0.25 parts Leveling agent (N): 1.0 part Organic solvent (Q): 26.25 parts

[0391] [Examples 2 to 45, Comparative Examples 1 to 4] (Photosensitive compositions 2-49) Photosensitive compositions 2 to 49 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 4-1 to 4-5. The contents of the specific metal elements and water in each photosensitive composition were 200 mass ppm or less and 1.6 mass % or less, respectively.

[0392] [Table 4-1]

[0393] [Table 4-2]

[0394] [Table 4-3]

[0395] [Table 4-4]

[0396] [Table 4-5]

[0397] The raw materials listed in Tables 4-1 to 4-5 are as follows:

[0398] [Polymerizable compound (C)] (Lactone-modified polymerizable compound (C1)) C1-1: KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd.)

[0399] (Polymerizable compound (C2) having an acid group) C2-1: Compound of the above chemical formula (15) C2-2: Compound of the above chemical formula (18) C2-3: Aronix M-521 (manufactured by Toagosei)

[0400] (Polymerizable compound (C4) having a fluorene skeleton) C4-1: OGSOL EA-0200 (Osaka Gas Chemicals)

[0401] (Other polymerizable compounds (C5)) C5-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

[0402] [Photopolymerization initiator (D)] (Compound (D1) represented by general formula (1)) D1-1: Compound of the above chemical formula (22) D1-2: Compound of the above chemical formula (23) D1-3: Compound of the above chemical formula (24)

[0403] (Other photopolymerization initiators (D2)) D2-1: Omnirad 907 (IGM Resins, acetophenone compound) D2-2: Omnirad TPO (IGM Resins, acylphosphine oxide compound) D2-3: Compound of the above chemical formula (25) D2-4: Compound of the above chemical formula (26) D2-5: Compound of the above chemical formula (27) D2-6: Compound of the above chemical formula (28) D2-7: Compound of the above chemical formula (29)

[0404] [Sensitizer (E)] (Thioxanthone compounds (E1)) E1-1: 2,4-diethylthioxanthone (Benzophenone compounds (E2)) E2-1: 4,4'-bis(diethylamino)benzophenone

[0405] [Leveling Agent (N)] N-1: BYK-330 (BYK-Chemie) N-2: Megafac F-551 (DIC) One part each of (N-1) and (N-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution, which was used as a leveling agent (N).

[0406] [Organic solvent (Q)] Q-1: Propylene glycol monomethyl ether acetate 30 parts Q-2: 30 parts cyclohexanone Q-3: 10 parts of ethyl 3-ethoxypropionate Q-4: Propylene glycol monomethyl ether 10 parts Q-5: Cyclohexanol acetate 10 parts Q-6: Dipropylene glycol methyl ether acetate 10 parts The above (Q-1) to (Q-6) were mixed in the above-mentioned parts by mass to obtain organic solvent (Q).

[0407] <Evaluation of Photosensitive Composition> The resulting photosensitive compositions 1 to 49 (Examples 1 to 45, Comparative Examples 1 to 4) were evaluated for developability, pattern formability, and heat resistance by the following methods. The evaluation results are shown in Table 5.

[0408] [Development residue evaluation] The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dry film thickness was 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp through a photomask with a 100 μm wide stripe pattern at an illuminance of 30 mW / cm. 2 , 50mJ / cm 2 The substrate was then cooled to room temperature, spray-developed using an organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was post-baked in a clean oven at 200°C for 20 minutes to form a striped pattern on the substrate. The pattern was observed under an optical microscope, and the amount of residue remaining in the unexposed areas was evaluated by binarizing the image. The evaluation criteria are as follows, with a score of 2 or higher being practical. 3: Development residue is less than 1.5% of the unexposed area 2: Development residue is 1.5% or more but less than 3% of the unexposed area 1: Development residue is 3% or more of the unexposed area

[0409] [Pattern formation evaluation (1): Adhesion] 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 70°C for 1 minute. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to apply a stripe pattern of 5 to 25 μm widths at 5 μm intervals to the substrate at an illumination intensity of 30 mW / cm. 2 , 50 mJ / cm 2The substrate was then spray-developed using an organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 200°C for 20 minutes. Spray development was carried out for the shortest time possible to form a pattern without leaving any residual development residue on the coating of each photosensitive composition. The resulting patterns on the substrates with widths of 5, 10, 15, 20, and 25 μm were observed with an optical microscope to confirm the minimum line width of the remaining patterns. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: 25 μm fine lines remain. 1: No fine lines remain.

[0410] [Pattern formation evaluation (2): Linearity] The substrate prepared in the pattern formation evaluation (1) was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with a score of 3 or higher being practical. 5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0411] [Pattern formation evaluation (3): surface wrinkles] The pattern surface of the substrate prepared in the pattern formation evaluation (1) was observed using an optical microscope (Olympus Optical Co., Ltd. "BX-51", magnification: 200 times). The evaluation criteria are as follows, with 3 or more being practical. 5: No wrinkles are observed on the pattern surface 4: Very slight wrinkles are observed on the pattern surface 3: Slight wrinkles are observed on the pattern surface 2: Wrinkles are observed on the pattern surface 1: Severe wrinkles are observed on the pattern surface

[0412] [Pattern formation evaluation (4): Cross-sectional shape] The photosensitive composition thus obtained 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 70° C. for 1 minute. After cooling the substrate to room temperature, the substrate was irradiated with a high-pressure mercury lamp at an illumination intensity of 30 mW / cm through a photomask with a 100 μm-wide stripe pattern. 2 , 50 mJ / cm 2 The substrate was then spray-developed using an organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 200°C for 20 minutes. Spray development was carried out for the shortest time possible to form a pattern without leaving any residual development residue on the coating of each photosensitive composition. The cross-sectional shape of the pattern was confirmed using a scanning electron microscope (Hitachi High-Tech "S-3000H"). Evaluation was performed by capturing an SEM image of the cross section of a 100 μm wide stripe pattern and measuring the taper angle between the substrate and the edge of the pattern cross section. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Taper angle between 40 degrees and 50 degrees 4: Taper angle between 50 degrees and 60 degrees 3: Taper angle between 30 degrees and 40 degrees, or between 60 degrees and 70 degrees 2: Taper angle is between 20 degrees and 30 degrees, or between 70 degrees and 90 degrees 1: Taper angle less than 20 degrees or more than 90 degrees

[0413] [Heat resistance 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 dry film thickness was 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, the coating was heated with a high-pressure mercury lamp at an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2 to obtain a substrate for evaluating heat resistance. The transmittance of the obtained substrate for heat resistance evaluation to light with wavelengths of 400 to 1200 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and this was recorded as the initial value.The substrate for heat resistance evaluation was then heated to 210°C for 20 minutes, cooled, and then the transmittance was measured again, and this was recorded as the value after the heat resistance test. Within the range of 400 to 1200 nm, the change in transmittance at the wavelength at which the change in transmittance before and after heating was greatest was calculated using the following formula: The evaluation criteria are as follows, with 3 or more being practical. Change in transmittance = |Transmittance after heat resistance test - initial transmittance| 5: Transmittance change is less than 2% 4: Transmittance change is 2% or more but less than 4% 3: Transmittance change is 4% or more but less than 6% 2: Transmittance change is 6% or more but less than 8% 1: Transmittance change is 8% or more

[0414] [Table 5] [Explanation of symbols]

[0415] 10 Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC liquid crystal 200 Solid-state imaging device 201 Solid-state imaging device 202 Imaging unit 203 Cover Glass 204 Spacer 205 Laminated Board 206 Chip Substrate 207 Circuit Board 208 Electrode Pads 209 External connection terminal 210 Through electrode 211 Lens Layer 212 Lens material 213 Support 214 Cured film 215 Cured film 300 Infrared Sensor 310 Solid-state imaging device 311 Infrared cut filter 312 Color Filter 313 Infrared transmission filter 314 Resin Film 315 Microlens 316 Flat membrane

Claims

1. A photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having a glass transition temperature of 0 to 150°C, the alkali-soluble resin (B1) comprising an alicyclic hydrocarbon-containing monomer unit (b1) and an aromatic ring-containing monomer unit (b2), the glass transition temperature of which in the form of a homopolymer is 80°C or higher; The photosensitive composition, wherein the photopolymerization initiator (D) comprises a compound (D1) represented by the following general formula (1): General formula (1) 【Chemical 1】 (In general formula (1), R １ , R ２ R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ３ represents a hydrogen atom or a monovalent substituent.

2. A photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having a glass transition temperature of 0 to 150°C, the alkali-soluble resin (B1) comprises a polymerizable unsaturated group-containing monomer unit (b3), The photosensitive composition, wherein the photopolymerization initiator (D) comprises a compound (D1) represented by the following general formula (1): General formula (1) 【Chemistry 2】 (In general formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R 3 represents a hydrogen atom or a monovalent substituent.)

3. 3. The photosensitive composition according to claim 2, wherein the alkali-soluble resin (B1) contains an alicyclic hydrocarbon-containing monomer unit (b1) and an aromatic ring-containing monomer unit (b2), each of which has a homopolymer glass transition temperature of 80°C or higher.

4. 4. The photosensitive composition according to claim 1, wherein the total content of the alicyclic hydrocarbon-containing monomer unit (b1) and the aromatic ring-containing monomer unit (b2) is 10 to 70 mol % of all structural units of the alkali-soluble resin (B1).

5. The photosensitive composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (D) includes a photopolymerization initiator (D2) other than the compound (D1) represented by the general formula (1).

6. 6. The photosensitive composition according to claim 5, wherein the photopolymerization initiator (D2) comprises at least one compound selected from the group consisting of an acetophenone compound, an acylphosphine oxide compound, and an oxime compound.

7. The photosensitive composition according to any one of claims 1 to 6, which further comprises a sensitizer (E).

8. The photosensitive composition according to any one of claims 1 to 7, further comprising a colorant (F).

9. 9. The photosensitive composition according to claim 8, wherein the colorant (F) comprises two or more pigments selected from the group consisting of a red pigment, a yellow pigment, a blue pigment, a green pigment, and a violet pigment.

10. A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 9.

11. An optical filter comprising the cured film according to claim 10.

12. An image display device comprising the cured film according to claim 10.

13. A solid-state imaging device comprising the cured film according to claim 10.

14. An infrared sensor comprising the cured film according to claim 10.

Images