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 offers superior storage stability and can be used to produce a cured film that exhibits superior resistance in a high-temperature high-humidity environment.SOLUTION: The above challenge is cleared by providing a photosensitive composition containing a near-infrared absorptive pigment (A), polymerizable compound (B), photopolymerization initiator (C), and organic solvent (D), the near-infrared absorptive pigment (A) containing a compound having a π conjugated plane including a monocyclic or condensed aromatic ring, and the organic solvent (D) containing a compound having an aromatic ring, where the content of the compound having the aromatic ring is 0.005-0.5 pts.mass with respect to 100 pts.mass of the compound having the π conjugated plane including the monocyclic or condensed aromatic ring.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition containing a near-infrared absorbing pigment. [Background technology]

[0002] Video cameras, digital cameras, mobile devices with camera functions, and the like use solid-state imaging elements for color images, such as CCDs (charge-coupled devices) and CMOSs ​​(complementary metal-oxide semiconductors). The light-receiving sections of these solid-state imaging elements 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] Traditionally, infrared cut filters have been used as flat films, but in recent years, photolithography has been used to form patterns on infrared cut filters. The photosensitive compositions used to form patterns are typically stored for several weeks to several months after production before use. In this case, differences in the storage environment and storage period can lead to problems such as changes in viscosity and sensitivity and the formation of aggregates. Changes in the viscosity and sensitivity of the photosensitive composition can lead to variations in film thickness, developability, and pattern shape, resulting in a decrease in the quality of the infrared cut filter. In particular, pigments used as near-infrared absorbing dyes are difficult to disperse, and their stability is likely to deteriorate during storage.

[0004] Furthermore, infrared cut filters are sometimes used in high-temperature, high-humidity environments, and are therefore required to have high resistance to high temperatures and high humidity.

[0005] For example, Patent Document 1 discloses a resin composition containing an organic pigment, a resin, and a solvent, and having a Na atom content of 0.01 to 50 ppm by mass relative to the total solid content. Patent Document 2 discloses a resin composition containing a near-infrared absorbing dye, a silane coupling agent having an amino group, and a poly(amide)imide resin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2018 / 142804 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-118772 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the resin compositions described in Patent Documents 1 and 2 were unable to simultaneously satisfy storage stability and resistance under high temperature and humidity conditions.

[0008] An object of the present invention is to provide a photosensitive composition that has excellent storage stability and is capable of forming a cured film that has excellent resistance under high temperature and high humidity conditions. [Means for solving the problem]

[0009] The present invention provides a photosensitive composition comprising a near-infrared absorbing pigment (A), a polymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D), the near-infrared absorbing pigment (A) contains a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring, The photosensitive composition relates to the organic solvent (D) which contains a compound having an aromatic ring, and the content of the compound having an aromatic ring is 0.005 to 0.5 parts by mass relative to 100 parts by mass of the compound having a π-conjugated plane containing a monocyclic or fused aromatic ring. [Effects of the Invention]

[0010] According to the present invention, there is provided a photosensitive composition capable of forming a cured film having excellent storage stability and excellent resistance under high temperature and high humidity conditions. 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]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor provided with a cured film. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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.

[0013] 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. Furthermore, the molecular weight of the compound in the present invention is a calculated value (formula weight) 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.

[0014] <Photosensitive composition> The photosensitive composition of the present invention is a photosensitive composition comprising a near-infrared absorbing pigment (A), a polymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D), the near-infrared absorbing pigment (A) contains a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring, The organic solvent (D) contains a compound having an aromatic ring, and the content of the compound having an aromatic ring is 0.005 to 0.5 parts by mass relative to 100 parts by mass of the compound having a π-conjugated plane containing a monocyclic or fused aromatic ring.

[0015] 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.

[0016] Near-infrared absorbing pigments are difficult to disperse and have poor storage stability. In particular, compounds with π-conjugated planes containing single or fused aromatic rings are prone to association and aggregation due to interactions between the π-conjugated planes, further worsening storage stability. However, it is believed that by including a specific amount of compounds with aromatic rings as an organic solvent, the compounds with aromatic rings are oriented toward compounds with π-conjugated planes containing single or fused aromatic rings, suppressing interactions between the π-conjugated planes and improving storage stability. In addition, it is preferable to control the content of the specific metal and the content of water in the photosensitive composition of the present invention. According to this embodiment, the reaction of the photopolymerization initiator during storage is suppressed, and the generation of aggregates and changes in viscosity and sensitivity are suppressed even after storage.

[0017] [Near infrared absorbing pigment (A)] (Compounds with a π-conjugated plane containing a single or fused aromatic ring) The photosensitive composition of the present invention contains, as the near-infrared absorbing pigment (A), a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring.

[0018] The compound having a π-conjugated plane containing a monocyclic or fused aromatic ring is a compound that has an absorption maximum in a wavelength range of 700 to 2,000 nm, and from the viewpoints of light resistance, heat resistance, and resistance to high temperatures and high humidity, the solubility in 100 g of water and propylene glycol monomethyl ether acetate at 25°C is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

[0019] The π-conjugated plane preferably contains 2 to 100 monocyclic or fused aromatic rings, more preferably 3 to 50, even more preferably 4 to 40, and particularly preferably 5 to 30. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, a quaterrylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a triazole ring, a benzotriazole ring, an oxazole ring, a benzoxazole ring, an imidazoline ring, a pyrazine ring, a quinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, and fused rings having these rings.

[0020] Examples of compounds having a π-conjugated plane containing a monocyclic or fused aromatic ring 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 light resistance, heat resistance, and resistance under high temperature and humidity, it is preferable to include at least one selected from the group consisting of squarylium compounds, pyrrolopyrrole compounds, naphthalocyanine compounds, and indigo compounds, and naphthalocyanine compounds are more preferable.

[0021] 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, Naphthalocyanine compounds are disclosed in JP-A-11-152414, JP-A-2000-86919, JP-A-2009-29955, WO-A-2017 / 002920, WO-A-2018 / 186490, etc.; indigo compounds are disclosed in JP-A-2013-230412, etc.; immonium compounds are disclosed in JP-A-2013-230412, etc. JP-A-2005-336150, JP-A-2007-197492, JP-A-2008-88426, etc.; anthraquinone compounds are disclosed in JP-A-62-903, JP-A-1-172458, etc.; pyrrolopyrrole compounds are disclosed in JP-A-2009-263614, JP-A-2010-90313, JP-A-2011-068731, and squari Examples of the chromium 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 the croconium compounds include those described in WO 2019 / 021767 A, etc.

[0022] (Squarylium compounds) The squarylium compound is preferably a compound represented by the following general formula (1). General formula (1) [ka]

[0023] In general formula (1), 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 , -COR 11 , -COOR12 , -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.

[0024] 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 R 108 , -NHCONR109 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.

[0025] 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.

[0026] From the viewpoint of light resistance and heat resistance, the squarylium compound is more preferably a compound represented by the following general formula (2).

[0027] General formula (2) [ka]

[0028] In general formula (2), 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 R67 , -B(OR 68 )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 -SO2OR 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.

[0029] The "substituent" has the same meaning as the "substituent" described above.

[0030] Specific examples of squarylium compounds are shown below, but the present invention is not limited to these.

[0031] [ka]

[0032] [ka]

[0033] (Pyrrolopyrrole compounds) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (3).

[0034] General formula (3) [ka]

[0035] In general formula (3), 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 (3) is described in, for example, JP-A Nos. 2009-263614, 2011-68731, and WO 2015 / 166873.

[0036] 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 R 1y 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.

[0037] 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 (3) 2 In addition, the two R 3 They may be the same or different.

[0038] 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 4yThe 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. 4 They may be the same or different.

[0039] 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.

[0040] [ka]

[0041] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably a compound having, as a central element, one or more elements selected from the group consisting of Al, Ga, and In. The naphthalocyanine compound is preferably a compound represented by the following general formula (4), for example.

[0042] General formula (4) [ka]

[0043] In general formula (4), X1~X8, Y lEach 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. M1 represents Al, Ga, or In. Z represents a ligand having one or more coordination sites for M1.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] M1 is preferably Al from the viewpoints of near-infrared absorbing ability, storage stability, and resistance under high temperature and humidity conditions.

[0054] The ligand represented by Z may be a ligand having one or more selected from a coordination site that coordinates with an anion to M1 and a coordination site that coordinates with an unshared electron pair to M1. The coordination site that coordinates with an anion may be dissociated or non-dissociated. The ligand may have one coordination site to M1 or two or more coordination sites to M1.

[0055] From the viewpoint of storage stability, Z is preferably a ligand having a phosphorus atom. Also, from the viewpoint of resistance under high temperature and high humidity, Z is preferably a ligand having a hydrophobic group. In particular, Z is more preferably a ligand having a phosphorus atom and a hydrophobic group. The hydrophobic group refers to a group that has low affinity for water. Examples of groups that have low affinity for water include alkyl groups that may have a substituent, aryl groups that may have a substituent, alkoxy groups that may have a substituent, and aryloxy groups that may have a substituent. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 30. The number of carbon atoms in the aryl group and aryloxy group is preferably 6 to 30. Examples of the substituent include a halogen atom, a nitro group, and a nitrile group.

[0056] Z is more preferably a ligand represented by the following general formula (5).

[0057] General formula (5) [ka]

[0058] In general formula (5), R 29 and R 30 each independently represents 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. * represents a bond to M1.

[0059] Examples of the "alkyl group" of an alkyl group which may have a substituent, the "aryl group" of an aryl group which may have a substituent, the "alkoxyl group" of an alkoxyl group which may have a substituent, and the "aryloxy group" of an aryloxy group which may have a substituent are the same as those exemplified in the explanation of general formula (4) above.

[0060] From the viewpoint of resistance under high temperature and high humidity, the general formula (5) is 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 are particularly preferably all phenyl groups or phenoxy groups.

[0061] The naphthalocyanine compound is more preferably a compound represented by the following general formula (6).

[0062] General formula (6) [ka]

[0063] In general formula (6), 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. M2 represents Al, Ga, or In. Z represents a ligand having one or more coordination sites for M2.

[0064] 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 alkoxy 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 (4).

[0065] In general formula (6), Y9~Y 16 , R8~R 21 From the viewpoint of storage stability, is preferably a hydrogen atom, a halogen atom, or an alkoxyl group which may have a substituent.

[0066] M2 is preferably Al from the viewpoints of near-infrared absorbing ability, storage stability, and resistance under high temperature and humidity.

[0067] Z is as explained in the above general formula (4).

[0068] Specific examples of naphthalocyanine compounds are shown below, but the present invention is not limited to these.

[0069] [ka] [ka]

[0070] (indigo compounds) The indigo compound is preferably a compound represented by the following general formula (7) and / or general formula (8).

[0071] [ka]

[0072] In the general formula (7) and the general formula (8), X1 to X 40 each independently represent 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0084] Examples of the acidic group include -SO3H and -COOH. Examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. 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.

[0085] Among the above substituents, X1 to X40 Preferred substituents for include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and -SO3H.

[0086] Examples of M 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.

[0087] Specific examples of indigo compounds are shown below, but the present invention is not limited to these.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] The compound having a π-conjugated plane containing a monocyclic or fused aromatic ring can be used alone or in combination of two or more. When two or more compounds are used in combination, it is preferable to use at least two compounds with different maximum absorption wavelengths. This broadens the waveform of the absorption spectrum compared to when a single compound is used, allowing for absorption of near-infrared light over a wide wavelength range.

[0093] [Other near-infrared absorbing compounds] The photosensitive composition of the present invention can contain a compound having near-infrared absorbing ability other than the near-infrared absorbing pigment (A) (hereinafter also referred to as other near-infrared absorbing compounds). Examples of other near-infrared absorbing compounds include near-infrared absorbing dyes described in JP 2013-076926 A, JP 2015-068945 A, WO 2017 / 135300 A, JP 2019-174813 A, etc., indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, copper, nickel, silver, gold, and other metal oxide particles or metal particles.

[0094] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B), which is a compound that forms a coating upon curing.

[0095] Examples of the polymerizable compound (B) include monomers and oligomers having a polymerizable unsaturated group. The polymerizable compound (B) is preferably a compound having two or more polymerizable unsaturated groups. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Examples of the polymerizable compound (B) include a lactone-modified polymerizable compound, a polymerizable compound having an acidic group, a polymerizable compound having a urethane bond, a polymerizable compound having a tertiary amine structure, a polymerizable compound having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds.

[0096] (Lactone-modified polymerizable compound) The lactone-modified polymerizable compound is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0097] Examples of commercially available lactone-modified polymerizable compounds include KAYARAD DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

[0098] (Polymerizable compound having an acidic group) Examples of polymerizable compounds having an acidic group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids, esters of polycarboxylic acids with monohydroxyalkyl(meth)acrylates, etc. The polymerizable compound having an acidic group is a compound that does not have a urethane bond.

[0099] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0100] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0101] Examples of the polycarboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0102] Commercially available polymerizable compounds having an acidic group include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

[0103] (Polymerizable compound having a urethane bond) Examples of the polymerizable compound having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate.

[0104] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol 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.

[0105] 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.

[0106] The polymerizable compound having a urethane bond may further have an acidic group from the viewpoint of developability. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0107] The acidic group can be introduced into a polymerizable compound having a urethane bond by, for example, first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0108] 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.

[0109] Examples of commercially available polymerizable compounds having a urethane bond include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0110] (Polymerizable compound having a tertiary amine structure) Examples of the polymerizable compound having a tertiary amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0111] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and diglycerides thereof. Examples of the alkylene oxide-modified tri(meth)acrylate include lin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerin alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta-, and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0112] The (meth)acrylate compound (X) can be used alone or in combination of two or more kinds.

[0113] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0114] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0115] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and known methods can be used, such as those described in International Publication No. 2006 / 075754, JP-A No. 2008-545859, and JP-A No. 2017-066347.

[0116] The polymerizable compound having a tertiary amine structure may have an acidic group and / or a hydroxyl group. Examples of methods for introducing the acidic group and / or the hydroxyl group include a method using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0117] Examples of commercially available polymerizable compounds having a tertiary amine structure include Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

[0118] (Polymerizable compound having a dendrimer structure or a hyperbranched structure) A polymerizable compound with a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting a core (hereinafter also referred to as the core portion), and polymerizable unsaturated groups are bonded to the ends of the branches, and has a spherical, highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

[0119] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), and CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER Co., Ltd., and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials Corporation.

[0120] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (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 suitable acrylates include acrylate, 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, epoxy (meth)acrylate, and various acrylic and methacrylic acid esters such as urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile. EO is an abbreviation for ethylene oxide, and PO is an abbreviation for propylene oxide.

[0121] Other commercially available polymerizable compounds 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, and M-350 manufactured by Toagosei Co., Ltd. , M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, MT-3549, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OGSOL manufactured by Osaka Gas Chemicals Co., Ltd. Examples of suitable acrylic acid esters include EA-0200, EA-0300, GA-5060P, and GA-2800, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 40, 130, 140, and 145 manufactured by Daicel-Allnex Corporation.

[0122] The polymerizable compound (B) can be used alone or in combination of two or more kinds.

[0123] The content of the polymerizable compound (B) is preferably from 5 to 70 mass %, more preferably from 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0124] [Photopolymerization initiator (C)] The photosensitive composition of the present invention contains a photopolymerization initiator (C), which allows the photosensitive composition to be cured by irradiation with active energy rays.

[0125] Examples of the photopolymerization initiator (C) include acetophenone-based 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; triazine-based 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; 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); acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0126] Commercially available products include Omnirad 907, 369E, and 379EG manufactured by IGM Resins as acetophenone compounds, Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds, IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan, N-1919, NCI-730, 831, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples include Omnirad 1312, 1314, and 1316 manufactured by Resins Co., Ltd., SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemiks Co., Ltd. Further examples include oxime compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, WO 2021 / 175855, etc.

[0127] (Compound represented by general formula (9)) From the viewpoints of storage stability and resistance under high temperature and humidity, the photosensitive composition of the present invention preferably contains a compound represented by the following general formula (9) as the photopolymerization initiator (C).

[0128] General formula (9) [ka] (In general formula (9), 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.)

[0129] 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 viewpoint of 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.

[0130] 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. Examples of the substituents that the benzoyl or thenoyl groups may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0131] Examples of methods for producing the compound represented by general formula (9) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0132] Specific examples of the compound represented by formula (9) are shown below, but the present invention is not limited to these.

[0133] [ka] [ka]

[0134] Among the compounds of the chemical formulas (10) to (13), the compound of the chemical formula (10) is preferred from the viewpoints of storage stability and resistance to high temperature and high humidity.

[0135] The compound represented by general formula (9) can be used alone or in combination of two or more kinds.

[0136] From the viewpoints of storage stability and resistance under high temperature and humidity, the content of the photopolymerization initiator (C) is preferably 0.5 to 20 mass %, more preferably 1 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0137] [Organic solvent (D)] (Compounds with aromatic rings) The photosensitive composition of the present invention contains, as the organic solvent (D), 0.005 to 0.5 parts by mass of a compound having an aromatic ring relative to 100 parts by mass of a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring.

[0138] Examples of compounds having an aromatic ring include toluene, xylene, benzene, trimethylbenzene, ethylbenzene, propylbenzene, 1-methylbenzene, butylbenzene, 1-phenylhexane, 1,2-diethylbenzene, chlorobenzene, benzyl alcohol, etc. Among these, toluene is preferred from the viewpoint of storage stability.

[0139] The compounds having an aromatic ring can be used alone or in combination of two or more kinds.

[0140] From the viewpoint of storage stability, the content of the compound having an aromatic ring is more preferably 0.01 to 0.1 parts by mass per 100 parts by mass of the compound having a π-conjugated plane containing a monocyclic or fused aromatic ring.

[0141] (Organic solvents other than compounds with aromatic rings) The photosensitive composition of the present invention preferably contains an organic solvent other than the compound having an aromatic ring.

[0142] Examples of organic solvents other than compounds having an aromatic ring 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, and 3-methoxy-3-methyl-1-butanol. , 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-propyl acetate, N-methylpyrrolidone, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin,Examples of suitable esters include 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, 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 diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0143] The organic solvents other than the compounds having an aromatic ring can be used alone or in combination of two or more kinds.

[0144] The content of the organic solvent (D) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 to 40% by mass.

[0145] [Silane coupling agent (E)] The photosensitive composition of the present invention preferably contains a silane coupling agent (E) from the viewpoint of resistance under high temperature and high humidity conditions.

[0146] In the present invention, the silane coupling agent (E) is a compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. The alkoxy group is preferably a methoxy group from the viewpoint of resistance under high temperature and high humidity conditions. Examples of functional groups other than those mentioned above include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, a ureido group, etc. Among these, from the viewpoint of resistance under high temperature and high humidity conditions, an epoxy group, a (meth)acryloyl group, an isocyanurate group, and a mercapto group are preferred, and an epoxy group and a (meth)acryloyl group are more preferred.

[0147] Examples of the silane coupling agent (E) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. hydrochloride thereof, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0148] Commercially available silane coupling agents (E) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, and KBE-585A, all manufactured by Shin-Etsu Silicones Co., Ltd.

[0149] The silane coupling agent (E) may also be a polymer type, such as a polysiloxane type or an organic polymer type.

[0150] Polysiloxane type silane coupling agents are those in which hydrolyzable groups and other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Silicones Co., Ltd.

[0151] The organic polymer type is a silane coupling agent in which a hydrolyzable group and other functional groups are bonded to an organic polymer whose main chain is an organic structure. Commercially available organic polymer type products include X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Silicones Co., Ltd.

[0152] The silane coupling agent (E) can be used alone or in combination of two or more kinds.

[0153] From the viewpoints of storage stability and resistance under high temperature and humidity, the content of the silane coupling agent (E) is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the near-infrared absorbing pigment (A).

[0154] [Alkali-soluble resin (F)] The photosensitive composition of the present invention may contain an alkali-soluble resin (F), which improves the various resistances of the cured film.

[0155] The alkali-soluble resin (F) is not particularly limited, and known resins can be used.

[0156] The alkali-soluble resin (F) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. Examples of the alkali-soluble group include a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group. Among these, a carboxyl group is preferred. The alkali-soluble resin (F) may contain a thermosetting group such as an epoxy group, an oxetanyl group, an isocyanate group, etc. The isocyanate group may be protected with a compound (blocking agent) that is released by heat.

[0157] (Non-photosensitive alkali-soluble resin) Examples of non-photosensitive alkali-soluble resins include acrylic resins having acidic groups, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred.

[0158] (photosensitive alkali-soluble resin) The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. The photosensitive alkali-soluble resin is preferably a resin synthesized by the following method (i) or (ii). When cured with active energy rays, the resin undergoes three-dimensional crosslinking, increasing the crosslink density and improving resistance.

[0159] [Method (i)] In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain a photosensitive alkali-soluble resin.

[0160] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0161] Other monomers include, for example, 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, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy (meth)acrylates such as diethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol; (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; styrene or styrenes such as α-methylstyrene; 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; Cyclohexylmaleimide, 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-trichloroethylene) 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 monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described below with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0162] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0163] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. If necessary, the remaining anhydride groups can be hydrolyzed using a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic anhydride.

[0164] Another method similar to method (i) is to synthesize a polymer of a carboxyl group-containing monomer and other monomers, and then add an epoxy group-containing monomer to some of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin.

[0165] [Method (ii)] In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with the isocyanate group of an isocyanate group-containing monomer.

[0166] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates 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. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition polymerization of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred in terms of their resistance to foreign matter formation in the coating. Furthermore, glycerol mono(meth)acrylate is preferred in terms of photosensitivity.

[0167] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0168] The monocarboxyl group-containing monomer and other monomers that can be used are those described above.

[0169] The raw materials used in the synthesis of the photosensitive alkali-soluble resin can be used either alone or in combination of two or more.

[0170] The alkali-soluble resin (F) can be used alone or in combination of two or more kinds.

[0171] From the viewpoint of resistance, the weight average molecular weight (Mw) of the alkali-soluble resin (F) is preferably 4,000 to 50,000, more preferably 4,000 to 40,000. The Mw / Mn value is preferably not more than 10. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and developability.

[0172] The acid value of the alkali-soluble resin (F) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g. A suitable acid value improves the adhesion to the substrate and the developability.

[0173] The content of the alkali-soluble resin (F) is preferably from 1 to 80 mass %, more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0174] [Dispersion resin (G)] The photosensitive composition of the present invention may contain a dispersing resin (G), which is used for the purpose of stably dispersing the near-infrared absorbing pigment (A) in the photosensitive composition.

[0175] The dispersing resin (G) is preferably a resin having an adsorptive group that has a high affinity for the near-infrared absorbing pigment (A). The adsorptive group preferably has at least one of a basic group and an acidic group.

[0176] 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.

[0177] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0178] 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.

[0179] 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 storage stability.

[0180] 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.

[0181] The dispersing resin (G) can be used alone or in combination of two or more kinds.

[0182] From the viewpoint of storage 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 pigment (A).

[0183] [Dispersing agent (H)] The photosensitive composition of the present invention can contain a dispersing aid (H). Examples of the dispersing aid (H) include compounds having a structure in which a portion of the pigment is substituted with an acidic group, a basic group, a neutral group, a group having a salt structure, or the like. Examples of the dispersing aid (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.

[0184] The dispersing aid (H) preferably has a structure derived from a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring. Examples of the compound having a π-conjugated plane containing a monocyclic or fused aromatic ring include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds.

[0185] Examples of the dispersing aid (H) include compounds described in WO 2016 / 035695, WO 2017 / 146092, WO 2018 / 101189, and the like.

[0186] The dispersing aid (H) can be used alone or in combination of two or more kinds.

[0187] From the viewpoint of storage stability, the content of the dispersing aid (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 pigment (A).

[0188] [Colorant (I)] The photosensitive composition of the present invention may contain a colorant (I), 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 (I) 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, 21, 31, 32, 33, and 34. Other examples include compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, JP-A-1-170601, and JP-A-2-34664.

[0197] When the photosensitive composition of the present invention is used in an infrared transmission filter, it preferably contains, as colorant (I), 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] [Sensitizer (J)] The photosensitive composition of the present invention preferably contains a sensitizer (J).

[0199] Examples of the sensitizer (J) 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 suitable compounds include compounds such as phthalocyanine 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 and benzophenone compounds are preferred from the viewpoint of pattern formation.

[0200] (Thioxanthone compounds) Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

[0201] (benzophenone compounds) Examples of benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0202] The sensitizer (J) can be used alone or in combination of two or more kinds.

[0203] The content of the sensitizer (J) is preferably 5 to 400 parts by mass relative to 100 parts by mass of the photopolymerization initiator (C).

[0204] [Thermosetting compound (K)] The photosensitive composition of the present invention preferably contains a thermosetting compound (K), which crosslinks the thermosetting compound (K) during the heat treatment step, improving resistance to high temperature and high humidity.

[0205] The thermosetting compound (K) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (K) 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, from the viewpoint of resistance under high temperature and high humidity, epoxy compounds and oxetane compounds are preferred, and epoxy compounds are more preferred.

[0206] (epoxy compounds) The epoxy compound preferably has a structure having an aromatic ring and / or an aliphatic ring, and more preferably has a structure having an aliphatic ring from the viewpoint of suppressing the generation of foreign matter. The epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group. Examples of the linking group include an alkyl group, an arylene group, -O-, -NR- (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent), -SO2-, -CO-, -O-, and -S-. In the case of a structure having an aliphatic ring, it is more preferable that the epoxy group is bonded to the aliphatic ring via a single bond.

[0207] The epoxy compound is preferably a compound having 5 to 50 epoxy groups in the molecule, more preferably a compound having 10 to 30 epoxy groups.

[0208] Examples of epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, 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.

[0209] 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.

[0210] The content of the epoxy compound is preferably from 0.5 to 20% by mass, more preferably from 1 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0211] (Oxetane compounds) The oxetane compound is a known compound having an oxetane group, and examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0212] 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.

[0213] 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.

[0214] 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.

[0215] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0216] 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.

[0217] The content of the oxetane compound is preferably from 0.5 to 20% by mass, more preferably from 1 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0218] The thermosetting compound (K) can be used alone or in combination of two or more kinds.

[0219] [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 (K). 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.).

[0220] The curing agents can be used alone or in combination of two or more.

[0221] 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 (K).

[0222] [Thiol-based chain transfer agent (L)] The photosensitive composition of the present invention can contain a thiol chain transfer agent (L). When the thiol chain transfer agent (K) is used in combination with the photopolymerization initiator (C), 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.

[0223] The thiol chain transfer agent (L) 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.

[0224] 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.

[0225] The thiol chain transfer agent (L) can be used alone or in combination of two or more kinds.

[0226] The content of the thiol chain transfer agent (L) is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, based on 100 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.

[0227] [Polymerization inhibitor (M)] The photosensitive composition of the present invention may contain a polymerization inhibitor (M).

[0228] Examples of the polymerization inhibitor (M) 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 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.

[0229] The content of the polymerization inhibitor (M) is preferably 0.01 to 0.4% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0230] [Ultraviolet absorber (N)] The photosensitive composition of the present invention may contain an ultraviolet absorber (N).

[0231] The ultraviolet absorber (N) 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.

[0232] Examples of the benzotriazole compounds include 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 side chain 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0239] The content of the ultraviolet absorber (N) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator (C) and the ultraviolet absorber (N).

[0240] [Antioxidants (O)] The photosensitive composition of the present invention may contain an antioxidant (O).

[0241] The antioxidant (O) prevents the photopolymerization initiator (C) and the thermosetting compound (K) in the photosensitive composition from being oxidized and yellowed during the heat treatment step or ITO annealing.

[0242] Examples of the antioxidant (O) 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.

[0243] 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.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0251] The antioxidant (O) can be used alone or in combination of two or more kinds.

[0252] The content of the antioxidant (O) 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.

[0253] [Leveling agent (P)] The photosensitive composition of the present invention may contain a leveling agent (P), which further improves the wettability to the substrate during coating and the drying property.

[0254] Examples of the leveling agent (P) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0255] 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.

[0256] 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.

[0257] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0263] 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.

[0264] 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.

[0265] 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.

[0266] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0267] The leveling agent (P) can be used alone or in combination of two or more kinds.

[0268] The content of the leveling agent (P) 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.

[0269] [Storage stabilizer (Q)] The photosensitive composition of the present invention may contain a storage stabilizer (Q), which stabilizes the viscosity of the photosensitive composition over time.

[0270] Examples of the storage stabilizer (Q) 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.

[0271] The content of the storage stabilizer (Q) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the near-infrared absorbing pigment (A).

[0272] [Specific metal element content] From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains 300 mass ppm or less of the metals Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter simply referred to as specific metal elements) in total.

[0273] A photosensitive composition having a total amount of specific metal elements within the above range exhibits excellent stability and sensitivity even after storage. Furthermore, an optical filter produced using a photosensitive composition having a total amount of specific metal elements within the above range produces little foreign matter even when heated.

[0274] The total amount of the specific metal elements contained in the photosensitive composition is more preferably 200 mass ppm or less, particularly preferably 100 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more. Within the above range, costs can be reduced and storage stability is excellent.

[0275] The amount of each specific metal element contained in the photosensitive composition is preferably 40 ppm by mass or less, and more preferably 20 ppm by mass or less. Furthermore, among the specific metal elements, the content of Li, which has high reactivity with the photopolymerization initiator (C), is preferably 15 mass ppm or less, and more preferably 10 mass ppm or less.

[0276] The method for reducing the specific metal element contained in the photosensitive composition is not particularly limited, but since the specific metal element is contained in large amounts in the near-infrared absorbing pigment (A), it is preferable to remove the specific metal element from the near-infrared absorbing pigment (A). In addition, since the specific metal element is also mixed in from the equipment used to produce the photosensitive composition, it is also preferable to prevent mixing in from the equipment.

[0277] The method for reducing or removing the specific metal element contained in the near-infrared absorbing pigment (A) is not particularly limited, and known methods can be used. For example, methods for preventing contamination from equipment during the manufacturing process include those described in JP 2010-83997 A and JP 2018-36521 A. Furthermore, for example, methods for removing the specific metal element from the near-infrared absorbing pigment (A) include those described in JP 7-198928 A, JP 8-333521 A, JP 2009-7432 A, and JP 2010-83997 A. Among these, a method of washing the near-infrared absorbing pigment (A) with water containing a low content of the specific metal element, such as ion-exchanged water, is preferred.

[0278] The method for washing the near-infrared absorbing pigment (A) is not particularly limited, and known methods can be used. For example, the synthesized near-infrared absorbing pigment (A) is placed in a container containing ion-exchanged water and stirred. After stirring for a certain period of time, the mixture is filtered using a filter press to separate the near-infrared absorbing pigment (A) from the ion-exchanged water. This process is repeated until the amount of the specific metal element reaches the desired value. Washing is preferably performed while heating. The near-infrared absorbing pigment (A) is then dried with hot air and pulverized.

[0279] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0280] From the viewpoint of storage stability, the photosensitive composition of the present invention preferably also contains a reduced amount of metal elements other than the specific metal elements, such as Mn, Cs, Ti, Co, Si, and Pd.

[0281] [Water content] From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains water in an amount of 2.0% by mass or less.

[0282] When the water content of the photosensitive composition is within the above range, the composition is excellent in stability and sensitivity even after storage.

[0283] The water content in the photosensitive composition is more preferably 1.5% by mass or less, particularly preferably 1.0% by mass or less. The lower limit of the water content is preferably as low as possible, but there is no particular limit. Within the above range, the composition will have excellent stability and sensitivity even after storage.

[0284] The method for controlling the water content is not particularly limited, and known methods can be used. For example, a method for producing a photosensitive coloring composition while blowing dry air, an inert gas, or a mixed gas thereof, or a method for dehydrating the composition after production by adding a molecular sieve, etc. Among these, the method for producing the composition while blowing dry air, an inert gas, or a mixed gas thereof is preferred.

[0285] The water content can be measured by a known method such as the Karl Fischer method.

[0286] Although the mechanism is unclear, it is assumed that the reaction of the photopolymerization initiator (C) during storage was suppressed by reducing the amount of specific metal elements and water. It is particularly useful when the silane coupling agent (E) is included, and it is assumed that the reaction of the silane coupling agent (E) was suppressed.

[0287] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced by, for example, adding a near-infrared absorbing pigment (A), a dispersing resin (G), and an organic solvent (D) and dispersing them under dry air to produce a dispersion. Then, under dry air, the dispersion is blended with a polymerizable compound (B), a photopolymerization initiator (C), and the like, and mixed. The timing of blending each material is arbitrary. It is preferable to work in a humidity-controlled location to prevent water from entering the composition from the atmosphere.

[0288] 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.

[0289] The average dispersed particle size (secondary particle size) of the near-infrared absorbing pigment (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.

[0290] 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.

[0291] The photosensitive composition is preferably filtered using a sintered filter or a membrane filter to remove 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. 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.

[0292] <Cured film> The cured film of the present invention is a cured product of the photosensitive composition of the present invention, and the formed film is cured by exposure to light or the like.

[0293] [Method of manufacturing the cured film] The method for producing the cured film is not particularly limited, and the 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.

[0294] The method for producing the cured film will be described in detail below.

[0295] (Process (1)) In the step (1) of forming a layer of a photosensitive composition, the photosensitive composition is applied to a substrate by a method such as rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (prebaked) at a temperature of 50 to 100°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, a resin substrate, and a silicon substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light-emitting layer may be formed on these substrates. For example, an imaging element such as a CCD or a CMOS may be formed on the surface of the silicon substrate. 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 5.0 μm.

[0296] (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 active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pauses of light in short cycles (for example, milliseconds or less) (pulse exposure).

[0297] (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.

[0298] 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.

[0299] (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 80 to 300° C. The heating time is preferably about 2 minutes to 1 hour.

[0300] <Optical filters> The cured film of the present invention can be used for an optical filter. The optical filter is preferably used as, 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.

[0301] <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, but it can be used in combination with a color filter containing a colorant.

[0302] When the cured film of the present invention is used in combination with a color filter, it is preferable that the color filter is disposed on the optical path of the cured film of the present invention. For example, the cured film of the present invention and a color filter can be laminated to form a laminate. In the laminate, the cured film and the color filter may or may not be adjacent to each other in the thickness direction. When the cured film of the present invention and the color filter are not adjacent to each other, the cured film of the present invention may be formed on a substrate other than the substrate on which the color filter is formed. Furthermore, other members (for example, a microlens, a planarizing film, etc.) may be present between the cured film of the present invention and the color filter.

[0303] Examples of image display devices include liquid crystal displays and organic EL displays. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0304] <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 may be, for example, 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 transfer electrode made of polysilicon or the like, a light-shielding film made of tungsten or the like on the photodiodes and transfer electrodes with only the light-receiving portion of the photodiodes being opened, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portion of the photodiode, and the cured film of the present invention on the device protective film. Furthermore, a light-focusing means (such as a microlens) may be provided on the device protective film below the cured film of the present invention.

[0305] <Infrared sensor> The cured film of the present invention can be used in an infrared sensor. There are no particular limitations on the form in which it is used in an infrared sensor. Fig. 1 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 100 shown in Fig. 1 includes a solid-state imaging element 110.

[0306] The imaging area provided on the solid-state imaging device 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0307] The infrared cut filter 111 can be formed using the photosensitive composition of the present invention, and transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared range (for example, light with a wavelength of 800 to 1,300 nm).

[0308] The color filter 112 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range, and for example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

[0309] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 113 is disposed.

[0310] The infrared transmission filter 113 is a filter that has a visible light blocking property and transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0311] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0312] In the embodiment shown in FIG. 1, the resin film 114 is disposed, but instead of the resin film 114, an infrared transmission filter 113 may be formed.

[0313] 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.

[0314] 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, it is suitable for use in optical filters used in micro LEDs and micro OLEDs. Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

[0315] The cured film of the present invention can also be used in applications such as quantum dot displays, etc. Although not particularly limited, it is preferably used as an optical filter for use in quantum dot displays. [Example]

[0316] 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." Furthermore, in the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass residue after leaving the composition to stand in an oven at 230°C for 30 minutes.

[0317] Before describing the examples, each measurement method will be explained.

[0318] (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, and both columns were packed with "TSK-GEL SUPER HZM-N" packing. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0319] (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.

[0320] (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.

[0321] (Measurement of the content of compounds with aromatic rings) The content of the compound having an aromatic ring in the photosensitive composition was measured by gas chromatography.

[0322] (Measurement of specific metal element content) 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).

[0323] (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).

[0324] <Production of near-infrared absorbing pigment (A)> (Compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring) 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 Compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring, represented by the following chemical formula (14). 50 parts of the compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring, 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 for 12 hours at 60°C. Next, this kneaded mixture was added to 3,000 parts of ion-exchanged water, heated to 70°C, stirred for 1 hour, and then filtered (washing step). This washing step was repeated three times, and then dried overnight at 80°C and pulverized to obtain a finely divided compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring.

[0325] Chemical formula (14) [ka]

[0326] (Compound (A-2) having a π-conjugated plane containing a monocyclic or fused aromatic ring) 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, followed by stirring 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 compound (A-2) having a π-conjugated plane containing a monocyclic or fused aromatic ring, which is a mixture of compounds represented by the following chemical formula (15) (mixing ratio: n1:n2:n3:n4=7:19:59:15). The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was made into fine particles in the same manner as in the compound (A-1).

[0327] Chemical formula (15) [ka]

[0328] (Compound (A-3) having a π-conjugated plane containing a monocyclic or fused aromatic ring) In a reaction vessel, 178 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 40 parts of gallium trichloride were mixed and stirred, and after heating, the mixture was 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, to obtain 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 c. Next, in a reaction vessel, 159 parts of compound c were 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 120 parts of compound d. Four parts of diphenyl phosphate were added to 200 parts of N-methylpyrrolidone, thoroughly stirred and mixed, and then heated to 50°C. 10 parts of compound d 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 compound (A-3) having a π-conjugated plane containing a monocyclic or fused aromatic ring, which is a compound represented by the following chemical formula (16). The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was made into fine particles in the same manner as in the compound (A-1).

[0329] Chemical formula (16) [ka]

[0330] (Compound (A-4) having a π-conjugated plane containing a monocyclic or fused aromatic ring) Compound (A-4) having a π-conjugated plane containing a monocyclic or fused aromatic ring, represented by the following chemical formula (17), was obtained by performing the same operation as in Compound (A-3), except that 50 parts of indium trichloride was used instead of 40 parts of gallium trichloride. The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was made into fine particles in the same manner as in the compound (A-1).

[0331] Chemical formula (17) [ka]

[0332] (Compound (A-5) having a π-conjugated plane containing a monocyclic or fused aromatic ring) According to the description in National Publication No. 2017 / 002920, a compound (A-5) having a π-conjugated plane containing a monocyclic or fused aromatic ring represented by the following chemical formula (18) was obtained. The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was made into fine particles in the same manner as in the compound (A-1).

[0333] Chemical formula (18) [ka]

[0334] (Compound (A-6) having a π-conjugated plane containing a monocyclic or fused aromatic ring) According to the description of WO 2019 / 058882, a compound (A-6) having a π-conjugated plane containing a monocyclic or fused aromatic ring represented by the following chemical formula (19) was obtained. The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was made into fine particles in the same manner as in the compound (A-1).

[0335] Chemical formula (19) [ka]

[0336] (Compound (A-7) having a π-conjugated plane containing a monocyclic or fused aromatic ring) 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 e. In a reaction vessel, 13.5 parts of compound e, 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 ion-exchanged water, and dried to obtain compound (A-7) having a π-conjugated plane containing a monocyclic or fused aromatic ring, which is a mixture of compounds represented by the following chemical formula (20) (mixing ratio: dimer: trimer: tetramer = 81:17:2). The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was made into fine particles in the same manner as in the compound (A-1).

[0337] Chemical formula (20) [ka]

[0338] (Compound (A-8) having a π-conjugated plane containing a monocyclic or fused aromatic ring) The compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring was micronized by the following method. 50 parts of the compound (A-1) having a π-conjugated plane containing a monocyclic or fused aromatic ring, 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. Next, this kneaded mixture was added to 3,000 parts of tap water, stirred at room temperature for 1 hour, and then filtered. The mixture was then dried overnight at 80°C and pulverized to obtain a finely divided compound (A-8) having a π-conjugated plane containing a monocyclic or fused aromatic ring.

[0339] <Production of alkali-soluble resin (F)> (Alkali-soluble resin (F-1) solution) A separable four-neck flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer as a reaction vessel, and 160 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed in the reaction vessel. The vessel was heated to 120°C while nitrogen gas was injected into the vessel, and a mixture of 109.25 parts of benzyl methacrylate, 24.11 parts of methacrylic acid, 22.03 parts of dicyclopentanyl methacrylate, 3.6 parts of azobisisobutyronitrile as a polymerization initiator, and PGMAc was added dropwise from the dropping tube at the same temperature over 2.5 hours. After the dropwise addition, the mixture was stirred for another 2 hours at 120°C. PGMAc was then added to adjust the nonvolatile content to 20% by mass to prepare an alkali-soluble resin (F-1) solution. The alkali-soluble resin (F-1) had an acid value of 98 mgKOH / g and a weight-average molecular weight of 17,000.

[0340] <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.

[0341] <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 (D-1) was PGMAc. Compounds (A-1) Having a π-Conjugated Plane Containing a Monocyclic or Fused Aromatic Ring :15.0 copies Dispersion resin (G-1) solution: 20.0 parts Organic solvent (D-1): 65.0 parts

[0342] (Dispersion 2~8) Dispersions 2 to 8 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 1 were changed.

[0343] [Table 1]

[0344] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials and toluene, a compound having an aromatic ring, were added to a container while blowing dry air into it, and the mixture was stirred for 2 hours. After that, the mixture was filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. Dispersion 1: 35.0 parts Polymerizable compound (B-1): 7.0 parts Photopolymerization initiator (C-1): 0.8 parts Organic solvent (D-1): 19.9 parts Organic solvent (D-2): 5.0 parts Silane coupling agent (E-1): 0.1 parts Alkali-soluble resin (F-1) solution: 30.0 parts Sensitizer (J-1): 0.2 parts Thermosetting compound (K-1): 1.0 part Leveling agent (P): 1.0 part

[0345] The content of the specific metal element and the content of water in the obtained photosensitive composition 1 were measured.

[0346] [Examples 2 to 19, Comparative Examples 1 and 2] (Photosensitive Compositions 2 to 19, 21 and 22) Photosensitive compositions 2 to 19, 21, and 22 were prepared in the same manner as in Example 1, except that the types and amounts of raw materials used in photosensitive composition 1 in Example 1, and the amount of toluene relative to 100 parts by mass of a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring were changed as shown in Table 2, and the contents of specific metal elements and water were measured.

[0347] [Example 20] (Photosensitive composition 20) Photosensitive composition 20 of Example 20 was prepared in the same manner as photosensitive composition 1 of Example 1, except that the replacement with dry air was not carried out.

[0348] [Table 2-1]

[0349] [Table 2-2]

[0350] [Table 2-3]

[0351] The raw materials listed in the table are as follows:

[0352] [Polymerizable compound (B)] (B-1): Aronix M-402 (manufactured by Toagosei Co., Ltd.) (B-2): Aronix MT-3549 (manufactured by Toagosei Co., Ltd.)

[0353] [Photopolymerization initiator (C)] (C-1): The compound of the above chemical formula (10) (C-2): Irgacure OXE-02 (BASF)

[0354] [Organic solvent (D)] (D-1): Propylene glycol monomethyl ether acetate (D-2): Ethyl 3-ethoxypropionate

[0355] [Silane coupling agent (E)] (E-1): KBM-403 (Shin-Etsu Silicones Co., Ltd., functional group: epoxy group) (E-2): KBM-5103 (Shin-Etsu Silicones Co., Ltd., functional group: acryloyl group) (E-3): X-12-1048 (Shin-Etsu Silicones Co., Ltd., functional group: acryloyl group) (E-4): KBM-9659 (Shin-Etsu Silicones Co., Ltd., functional group: isocyanurate group) (E-5): KBM-803 (Shin-Etsu Silicones Co., Ltd., functional group: mercapto group) (E-6): KBM-603 (Shin-Etsu Silicones Co., Ltd., functional group: amino group)

[0356] [Sensitizer (J)] (J-1): 4,4'-bis(diethylamino)benzophenone

[0357] [Thermosetting compound (K)] (K-1): EHPE-3150 (manufactured by Daicel Corporation, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol with approximately 15 epoxy groups)

[0358] [Leveling agent (P)] (P-1): 2% PGMAc solution of BYK-330 (manufactured by BYK-Chemie)

[0359] <Evaluation of Photosensitive Composition> The following evaluations were carried out on the obtained photosensitive compositions 1 to 22. The evaluation results are shown in Table 3.

[0360] [Storage stability evaluation (1): Viscosity] The obtained photosensitive composition was placed in a sealed container and stored at 40°C for one week, and the rate of change in viscosity before and after storage was calculated and evaluated using the following formula. The viscosity was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. A value of 2 or higher is practical. [Viscosity change rate] = |([Initial viscosity] - [Viscosity after storage]) / [Initial viscosity]| x 100 3: Change rate is less than 5% 2: The rate of change is 5% or more but less than 10% 1: Change rate is 10% or more

[0361] [Storage stability evaluation (2): Foreign matter] 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 to room temperature, the coating was heated with a high-pressure mercury lamp at an illuminance of 30 mW / cm. 2 , 50mJ / cm 2 Then, it was exposed to ultraviolet light. The number of foreign particles on the cured film was counted and taken as the initial number of foreign particles. Measurements were performed using a metallurgical microscope "BX60" (manufactured by Olympus Systems Corporation) at a magnification of 500x, and the cumulative number of foreign particles observable in any five fields of view in transmitted light was counted. The photosensitive composition was placed in a sealed container and stored at 40°C for 1 week. The number of foreign matters after storage was counted under the same conditions as in the initial evaluation, and the result was evaluated according to the following criteria: 2 or more is usable. 3: The number of foreign particles after storage is less than 120% of the initial number of foreign particles. 2: The number of foreign particles after storage is between 120% and 150% of the initial number of foreign particles. 1: The number of foreign particles after storage is 150% or more of the initial number of foreign particles

[0362] [Storage stability evaluation (3): Sensitivity] The resulting photosensitive composition was applied by spin coating to a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) so that the dried film thickness was 2.0 μm, and then dried on a hot plate at 70 ° C for 1 minute. After cooling to room temperature, the composition was exposed to ultraviolet light through a photomask using a high-pressure mercury lamp. The composition was then spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C, washed with ion-exchanged water, air-dried, and heat-treated in a clean oven at 230 ° C for 30 minutes to form a striped pattern on the substrate. The width of the formed pattern was measured using a scanning electron microscope, and this was taken as the initial pattern width. The photosensitive composition was placed in a sealed container and stored at 40°C for one week. After storage, the photosensitive composition was measured for the pattern width under the same conditions as the initial evaluation and evaluated according to the following criteria: 2 or higher is usable. 3: The pattern width using the photosensitive composition after storage is in the range of 95 to 105% of the initial pattern width. 2: The pattern width using the photosensitive composition after storage is in the range of 90 to 110% of the initial pattern width. 1: The pattern width using the photosensitive composition after storage is less than 90% or more than 110% of the initial pattern width.

[0363] [High temperature and humidity resistance evaluation (1): Adhesion] 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 illuminance of 30 mW / cm. 2 , 50mJ / cm 2 After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was then heat-treated in a clean oven at 200°C for 30 minutes. The resulting cured film was cut with a utility knife to form a 1 mm square grid pattern (100 squares) and stored for 2 hours at a temperature of 120°C and humidity of 100%. After storage, a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was firmly pressed onto the film and peeled off in a direction of approximately 180°C. The state of the grid patterns was observed, and the number of peeled grid patterns was counted. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Less than 2 4: 2 or more, less than 5 3: 5 or more, less than 10 2: 10 or more, less than 15 1:15 pieces or more

[0364] [High temperature and humidity resistance evaluation (2): Spectral characteristics] 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. After cooling the substrate, the coating was heated with a high-pressure mercury lamp at an illuminance of 30 mW / cm. 2 , 50mJ / cm 2 It was exposed with. The absorbance of the obtained substrate was measured at the maximum absorption wavelength at an incident angle of 0°C using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and this was taken as the initial value. The substrate was then stored for 200 hours under conditions of a temperature of 120°C and a humidity of 85%. After cooling, the absorbance was measured again, and this was used as the value after storage. The residual rate was calculated using the following formula. The evaluation criteria are as follows, with 3 or higher being practical. Residual rate = (absorbance after storage) ÷ (initial absorbance) × 100 5: Survival rate is 97% or more 4: Residual rate is 95% or more but less than 97% 3: Residual rate is 93% or more but less than 95% 2: Residual rate is 90% or more but less than 93% 1: Residual rate is less than 90%

[0365] [Table 3] [Explanation of symbols]

[0366] 100 Infrared Sensor 110 Solid-state imaging device 111 Infrared cut filter 112 Color Filter 113 Infrared transmission filter 114 Resin Film 115 Micro Lens 116 Flat membrane

Claims

1. A photosensitive composition comprising a near-infrared absorbing pigment (A), a polymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D), the near-infrared absorbing pigment (A) contains a compound having a π-conjugated plane containing a monocyclic or fused aromatic ring, The photopolymerization initiator (C) contains a compound represented by the following general formula (9): The photosensitive composition, wherein the organic solvent (D) contains a compound having an aromatic ring, and the content of the compound having an aromatic ring is 0.005 to 0.5 parts by mass relative to 100 parts by mass of the compound having a π-conjugated plane containing a monocyclic or fused aromatic ring. General formula (9) 【Chemistry 1】 (In general formula (9), 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.)

2. 2. The photosensitive composition according to claim 1, further comprising: a total content of metals Li, Na, K, Mg, Ca, Fe, and Cr of 300 ppm by mass or less; and a water content of 2.0% by mass or less.

3. 3. The photosensitive composition according to claim 1, wherein the compound having a π-conjugated plane containing a monocyclic or fused aromatic ring is at least one compound selected from the group consisting of squarylium compounds, pyrrolopyrrole compounds, naphthalocyanine compounds, and indigo compounds.

4. 4. The photosensitive composition according to claim 3, wherein the central element of the naphthalocyanine compound is at least one element selected from the group consisting of Al, Ga and In.

5. 5. The photosensitive composition according to claim 3, wherein the naphthalocyanine compound has a ligand containing a phosphorus atom.

6. 6. The photosensitive composition according to claim 5, wherein the phosphorus atom-containing ligand is a ligand having a hydrophobic group.

7. The photosensitive composition according to any one of claims 1 to 6, further comprising a silane coupling agent (E).

8. A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 7.

9. An optical filter comprising the cured film according to claim 8 .

10. An image display device comprising the cured film according to claim 8.

11. A solid-state imaging device comprising the cured film according to claim 8 .

12. An infrared sensor comprising the cured film according to claim 8.

Images