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 excellent in developability and pattern formability and capable of forming a cured film excellent in resistance (solvent resistance and heat cycle resistance) by curing at a low temperature (130°C or lower).SOLUTION: A photosensitive composition contains a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The polymerizable compound (C) contains a polymerizable compound (C1) having a structure selected from dendrimer structures and hyperbranched structures.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive composition containing a near-infrared absorbing dye and its use.

Background Art

[0002] In video cameras, digital cameras, mobile devices with camera functions, etc., CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), which are solid-state imaging devices for color images, are used. Since silicon photodiodes sensitive to infrared rays are used in the light-receiving parts of these solid-state imaging devices, it is necessary to perform visual sensitivity correction, and an infrared cut filter or the like is arranged. The infrared cut filter is manufactured, for example, using a composition containing a near-infrared absorbing dye.

[0003] Conventionally, infrared cut filters have been used as flat films, but in recent years, it has been studied to form patterns on infrared cut filters by photolithography. However, since the composition containing a near-infrared absorbing dye used for an infrared cut filter easily transmits light of actinic energy rays (such as i-rays), when exposed through a photomask, the unexposed portion at the mask periphery is also easily exposed by reflected light or scattered light from the substrate or the like, and the reaction of the portion covered with the mask easily proceeds. Therefore, there have been problems such as a decrease in solubility in the developer, a thickening of the line width of the obtained pattern, and an inability to obtain a desired line width, and the occurrence of development residues. So far, methods for solving the above problems have been studied, such as adjusting the amount of active radical generation, that is, adjusting the type and amount of a photopolymerization initiator, or adjusting the exposure amount. For example, in the case of a thick line width, a method of reducing the amount of active radicals to an appropriate line width by using a photopolymerization initiator with low sensitivity or reducing the amount used, or a method of reducing the exposure amount to reduce reflected light and scattered light from the substrate or the like to an appropriate line width. However, this method has a problem that the resistance of the cured film decreases and the pattern shape and the resistance of the cured film deteriorate. When forming a pattern by photolithography, heat treatment (hereinafter referred to as post-baking) is performed at 200 °C or higher to sufficiently cure the cured film. However, since the near-infrared absorbing dye has low heat resistance and its near-infrared absorption ability is likely to decrease during post-baking, heat treatment at a low temperature is performed. Therefore, the solvent resistance of the cured film is more likely to deteriorate.

[0004] Therefore, Patent Document 1 discloses a photosensitive composition containing a phthalocyanine compound having an absorption maximum wavelength in the near-infrared region, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Further, Patent Document 2 discloses a near-infrared absorbing composition containing an infrared absorbing dye and a resin having a glass transition temperature of 0 to 100 °C, wherein the resin has a crosslinking group or contains a compound having a crosslinking group other than the resin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the compositions described in Patent Documents 1 and 2 could not satisfy all of developability, pattern formability, and cured film resistance at a certain level or higher. There was also a problem of heat cycle resistance in which the cured film peeled or cracked due to changes in the temperature range used.

[0007] An object of the present invention is to provide a photosensitive composition capable of forming a cured film excellent in developability and pattern formability and having excellent resistance (solvent resistance, heat cycle resistance) at low temperature (130 °C or lower) curing.

Means for Solving the Problems

[0008] The present invention relates to a photosensitive composition containing a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) includes a polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure.

Advantages of the Invention

[0009] According to the present invention described above, it is possible to provide a photosensitive composition capable of forming a cured film that is excellent in developability and pattern formability and has excellent resistance (solvent resistance, heat cycle resistance) in curing at a low temperature (130°C or lower). Further, the present invention can provide a cured film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0012] In this specification, unless otherwise specified, “(meth)acryloyl”, “(meth)acryl”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” means “acryloyl and / or methacryloyl”, “acryl and / or methacryl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. Also, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compound in the present invention, for a low molecular weight compound whose molecular weight can be specified, it is the value calculated by calculation (formula weight) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). For a compound having a molecular weight distribution, it is the polystyrene-reduced weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that forms a resin by polymerization. The monomer is in an unreacted state, and the monomer unit is the state in which the monomer forms a resin after polymerization.

[0013] <Photosensitive Composition> The photosensitive composition of the present invention is a photosensitive composition containing a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), characterized in that the polymerizable compound (C) contains a polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure.

[0014] Although the mechanism by which the photosensitive composition having the above configuration can solve the problems of the present invention is not clear, it is speculated as follows.

[0015] The polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure has a shorter distance between polymerizable groups in the molecule and a higher density compared to a general linear polymerizable compound. Therefore, it is less affected by oxygen inhibition and chain transfer of the solvent, and can sufficiently react even when the amount of the photoinitiator or the exposure amount is small or in the case of low-temperature curing, and it is presumed that a cured film with high resistance can be obtained. Also, due to its unique radial structure, it is presumed that external stress or internal stress can be effectively relaxed and it is less affected by temperature differences.

[0016] [Near-infrared absorbing dye (A)] The photosensitive composition of the present invention contains a near-infrared absorbing dye (A).

[0017] The near-infrared absorbing dye (A) is a compound having a maximum absorption at a wavelength of 700 to 2,000 nm, and may be a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye). Also, a near-infrared absorbing pigment and a near-infrared absorbing dye may be used in combination. From the viewpoint of heat resistance, a near-infrared absorbing pigment is preferred. In the present invention, the near-infrared absorbing pigment preferably has a solubility of less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less, with respect to 100 g of propylene glycol monomethyl ether acetate at 25°C.

[0018] From the viewpoint of solvent resistance, the near-infrared absorbing dye (A) preferably has a π-conjugated plane containing a monocyclic or condensed aromatic ring. Due to the π-π interaction between the aromatic rings, the near-infrared absorbing dyes (A) associate with each other, suppressing elution into the solvent. Also, due to the π-π interaction with the aromatic ring-containing monomer unit (b1) of the resin (B1) described later, the solvent resistance is further improved.

[0019] The π-conjugated plane of the near-infrared absorbing dye (A) preferably contains 2 to 100 aromatic rings, more preferably 3 to 50 aromatic rings, still more preferably 4 to 40 aromatic rings, and particularly preferably 5 to 30 aromatic rings. The aromatic rings include, for example, benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, pentalene ring, indacene ring, perylene ring, pentacene ring, quaterrylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, indole ring, isoindole ring, carbazole ring, and condensed rings having these rings.

[0020] Examples of the near-infrared absorbing dye (A) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, oxonol compounds, pyromethene compounds, azomethine compounds, triarylmethane compounds, dibenzofuranone compounds, and the like. Among these, from the viewpoint of heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferred, and indigo compounds and naphthalocyanine compounds are more preferred.

[0021] Cyanine compounds include those described in International Publication No. 2006 / 006573, International Publication No. 2010 / 073857, Japanese Patent Application Laid-Open No. 2013-241598, Japanese Patent Application Laid-Open No. 2016-113501, Japanese Patent Application Laid-Open No. 2016-113504, etc.; phthalocyanine compounds include those described in Japanese Patent Application Laid-Open No. 4-23868, Japanese Patent Application Laid-Open No. 06-192584, Japanese Patent Application Laid-Open No. 2000-63691, International Publication No. 2014 / 208514, etc.; naphthalocyanine compounds include those described in Japanese Patent Application Laid-Open No. 11-152414, Japanese Patent Application Laid-Open No. 2000-86919, Japanese Patent Application Laid-Open No. 2009-29955, International Publication No. 2017 / 002920, International Publication No. 2018 / 186490, etc.; indigo compounds include those described in Japanese Patent Application Laid-Open No. 2012-224593, Japanese Patent Application Laid-Open No. 2013-87233, Japanese Patent Application Laid-Open No. 2013-230412, etc.; immonium compounds include those described in Japanese Patent Application Laid-Open No. 2005-336150, Japanese Patent Application Laid-Open No. 2007-197492, Japanese Patent Application Laid-Open No. 2008-88426, etc.; anthraquinone compounds include those described in Japanese Patent Application Laid-Open No. 62-903, Japanese Patent Application Laid-Open No. 1-172458, etc.; pyrrolopyrrole compounds include those described in Japanese Patent Application Laid-Open No. 2009-263614, Japanese Patent Application Laid-Open No. 2010-90313, Japanese Patent Application Laid-Open No. 2011-068731; squarylium compounds include those described in Japanese Patent Application Laid-Open No. 2011-132361, Japanese Patent Application Laid-Open No. 2016-142891, International Publication No. 2017 / 135359, International Publication No. 2018 / 225837, Japanese Patent Application Laid-Open No. 2019-001987, International Publication No. 2020 / 054718, etc.; croconium compounds include the compounds described in International Publication No. 2019 / 021767, etc.

[0022] (Squarylium compound) As the squarylium compound, a compound represented by the following general formula (1) is preferable. General formula (1) [Chemical formula]

[0023] In general formula (1), R 1 ~R 4 are each independently 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, -OR10 、 -COR 11 、 -COOR 12 、 -OCOR 13 、 -NR 14 R 15 、 -NHCOR 16 、 -CONR 17 R 18 、 -NHCONR 19 R 20 、 -NHCOOR 21 、 -SR 22 、 -SO2R 23 、 -SO2OR 24 、 -NHSO2R 25 、 -SO2NR 26 R 27 、 -B(OR 28 )2, and -NHBR 29 R 30 represents. R 10 ~R 30 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. Note that when R 12 of -COOR 12 is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in a salt state. Also, when R 24 of -SO2OR 24 is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group) or may be in a salt state. Also, R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.)

[0024] Examples of the "substituent" include 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 、 -CONR107 R 108 、 -NHCONR 109 R 110 、 -NHCOOR 111 、 -SR 112 、 -SO2R 113 、 -SO2OR 114 、 -NHSO2R 115 or -SO2NR 116 R 117 may be mentioned. 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. In addition, when R 102 of -COOR 102 is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in a salt state. Also, when R 114 of -SO2OR 114 is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group) or may be in a salt state.

[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 of 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 of 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 of 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 number of carbon atoms of the aryl group is preferably 6 to 25, more preferably 6 to 15, and particularly preferably 6 to 10. The alkyl portion of the aralkyl group is the same as the above alkyl group. The aryl portion of the aralkyl group is the same as the above aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and particularly preferably 7 to 25. The heteroaryl group is preferably a monocyclic or condensed ring, more preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and particularly preferably a monocyclic or condensed ring having 2 to 4 condensed 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 ring or a 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 or may not have a substituent, and may be unsubstituted. Examples of the substituent include the above-mentioned "substituent".

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

Chemical formula

[0027] (In general formula (2), R 5 ~R 8 are each independently 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 , -SR62 、 -SO2R 63 、 -SO2OR 64 、 -NHSO2R 65 or -SO2NR 66 R 67 、 -B(OR 68 )2, and -NHBR 69 R 70 represents. R 50 ~R 70 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. Note that for -COOR 52 when R 52 is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in a salt state. Also, for -SO2OR 64 when R 64 is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group) or may be in a salt state. Also, R 5 and R 6 , R 7 and R 8 may be bonded to each other to form a ring.)

[0028] "Substituent" has the same meaning as the "substituent" described above.

[0029] Hereinafter, specific examples of squarylium compounds are shown. Note that the present invention is not limited thereto.

[0030]

Chemical formula

[0031]

Chemical formula

[0032] (Pyrrolopyrrole compound) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (3).

[0033] General formula (3) [Chemical formula]

[0034] (In general formula (3), R 1x and R 1y each independently represent an alkyl group, an aryl group or a heteroaryl group, and R 2 and R 3 each independently represent a hydrogen atom or a substituent, and R 2 and R 3 may be bonded to each other to form a ring, and R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4x R 4y or a metal atom, and 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, and R 4x R 4y each independently represent a substituent. General formula (3) is described in JP-A-2009-263614, JP-A-2011-68731, and WO 2015 / 166873.

[0035] R 1x and R 1y each independently preferably represent an aryl group or a heteroaryl group, more preferably an aryl group. Further, the alkyl group, aryl group and heteroaryl group represented by R 1x and R 1y 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 and the like. R 11 ~R 13Each independently represents a hydrocarbon group or a heteroaryl group. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among them, preferred substituents include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 . R 1x and R 1y are preferably an alkoxy group having a branched alkyl group or an aryl group having a group represented by -OCOR 11 as a substituent. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

[0036] R 2 and R 3 are preferably at least one of an electron-withdrawing group, more preferably R 2 represents an electron-withdrawing group, and R 3 represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a monocyclic or condensed ring, more preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and even more preferably a monocyclic or condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has at least one nitrogen atom. The two R 2 in the general formula (3) may be the same or different. Also, the two R 3 in the general formula (3) may be the same or different.

[0037] R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR 4x R 4y , more preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by -BR 4x R 4y , and even more preferably -BR 4x R 4yThe group represented by is particularly preferred. R 4x R 4y As the substituent represented by , a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferred, an alkyl group, an aryl group, or a heteroaryl group is more preferred, and an aryl group is particularly preferred. These groups may further have a substituent. The two R's in general formula (3) 4 may be the same or different from each other.

[0038] Hereinafter, specific examples of the pyrrolopyrrole compound will be shown. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, paragraphs 0037 to 0052 of JP-A-2011-68731, paragraphs 0014 to 0027 of JP-A-2014-130343, and paragraphs 0010 to 0033 of WO 2015 / 166873. Note that the present invention is not limited thereto.

[0039]

Chemical formula

[0040] (Naphthalocyanine compound) As the naphthalocyanine compound, a compound represented by the following general formula (4) is preferred.

[0041] General formula (4)

Chemical formula

[0042] The "alkyl group" of the alkyl group which may have a substituent includes, for example, linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group and the like. Examples of the "alkyl group having a substituent" include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

[0043] Examples of the "aryl group" of the aryl group which may have a substituent include phenyl group, naphthyl group, anthryl group and the like. "Aryl group having a substituent" includes, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group, and the like.

[0044] The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes, for example, cyclopentyl group, cyclohexyl group, adamantyl group, and the like. "Cycloalkyl group having a substituent" includes, for example, 2,5-dimethylcyclopentyl group, 4-tert-butylcyclohexyl group, and the like.

[0045] Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, and the like. Examples of the "heterocyclic group having a substituent" include 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group, and the like.

[0046] The "alkoxyl group" of the alkoxyl group which may have a substituent includes, for example, linear or branched alkoxyl groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyl oxy group, 2,3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, and the like. "Alkoxyl group having a substituent" includes, for example, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, and the like.

[0047] The "aryloxy group" of the aryloxy group which may have a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, etc., Examples of the "aryloxy group which may have 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.

[0048] The "alkylthio group" of the alkylthio group which may have a substituent includes, for example, 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, an octadecylthio group, etc. Examples of the "alkylthio group which may have a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, etc.

[0049] The "arylthio group" of the arylthio group which may have a substituent includes, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, etc. Examples of the "arylthio group which may have a substituent" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, etc.

[0050] Examples of the substituent of 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.

[0051] General formula (5)

Chemical formula

[0052] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, a terphenylene group, and an anthrylene group.

[0053] The monomer unit represented by general formula (5) can be obtained, for example, by copolymerizing monomers such as (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, and (2-(meth)acryloyloxyisopropyl) acid phosphate. It can also be obtained by copolymerizing in combination with monomers other than these monomers (hereinafter also referred to as other monomers).

[0054] Examples of other monomers include (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth)acrylonitrile, acid group-containing monomers, heat crosslinkable group-containing monomers, and the like.

[0055] The weight average molecular weight of the polymer part is preferably 5,000 to 20,000, more preferably 8,000 to 15,000. Having an appropriate molecular weight improves the optical properties and heat resistance.

[0056] The glass transition temperature (Tg) of the polymer part is preferably -50 to 150 °C, more preferably 20 to 80 °C. Appropriate Tg improves the optical properties.

[0057] General formula (6)

Chemical formula

[0058] Examples of the "alkyl group" of the alkyl group which may have a substituent, the "aryl group" of the aryl group which may have a substituent, the "alkoxyl group" of the alkoxyl group which may have a substituent, and the "aryloxy group" of the aryloxy group which may have a substituent are the same as those exemplified in the description of the above general formula (4).

[0059] From the viewpoints of dispersibility and color characteristics, in general formula (6), it is preferable that at least one of R 29 and R 30 is an aryl group which may have a substituent or an aryloxy group which may have a substituent, and it is more preferable that both R 29 and R 30 are an aryl group or an aryloxy group, and it is even more preferable that both R 29 and R 30 are a phenyl group or a phenoxy group.

[0060] As the naphthalocyanine compound, a compound represented by the following general formula (7) is more preferable.

[0061] General formula (7)

Chemical formula

[0062] The alkyl group which may have a substituent, the aryl group which may have a substituent, the cycloalkyl group which may have a substituent, the heterocyclic group which may have a substituent, the alkoxyl group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, the arylthio group which may have a substituent, the phthalimidomethyl group which may have a substituent, or the sulfamoyl group which may have a substituent is as described in the above explanation of general formula (4).

[0063] In general formula (7), Y9 to Y 16 , R8 to R 21 are preferably a hydrogen atom, a halogen atom, or an alkoxyl group which may have a substituent from the viewpoints of dispersibility and color characteristics.)

[0064] Specific examples of the naphthalocyanine compound are shown below. Note that the present invention is not limited thereto.)

Chemical formula

Chemical formula

[0065] (Indigo compound) As the indigo compound, compounds represented by the following general formula (8) and general formula (9) are preferable.

[0066] [Chemical formula] (In general formula (8) and general formula (9), X1 to X 40 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an amino group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO3H; -COOH; and monovalent to trivalent metal salts of these acidic groups; an alkylammonium salt. M represents a metal atom.)

[0067]

[0068] 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. The "aryl group having a substituent" includes, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group, and the like.

[0069] The "alkoxyl group" of the alkoxyl group which may have a substituent includes, for example, linear or branched alkoxyl groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, and the like. The "alkoxyl group having a substituent" includes, for example, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group, and the like.

[0070] The "aryloxy group" of the aryloxy group which may have a substituent includes, for example, phenoxy group, naphthoxy group, anthryloxy group, etc., and the "aryloxy group having a substituent" includes, for example, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, and the like.

[0071] The "arylalkyl group which may have a substituent" includes, for example, benzyl group, 2-phenylpropan-yl group, styryl group, diphenylmethyl group, triphenylmethyl group, and the like.

[0072] The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group and the like.

[0073] The "alkylthio group" of the alkylthio group which may have a substituent includes, for example, 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, an octadecylthio group and the like. Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

[0074] The "arylthio group" of the arylthio group which may have a substituent includes, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like. Examples of the "arylthio group having a substituent" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group and the like.

[0075] The "alkylamino group" of the alkylamino group which may have a substituent includes, for example, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group and the like.

[0076] The "arylamino group" of the arylamino group which may have a substituent includes, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluorenamino group, 2-fluorenamino group, 2-thiazolamino group, p-terphenylamino group and the like.

[0077] Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0078] Examples of the acidic group include -SO3H and -COOH. Examples of the monovalent to trivalent metal salts of these acidic groups include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt and the like. Examples of the alkylammonium salts of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkylammonium salts such as palmityltrimethylammonium, lauryltrimethylammonium, dilauryl dimethylammonium and distearyl dimethylammonium salts.

[0079] Among the above substituents, X1 to X40 Preferred substituents include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and -SO3H.

[0080] M represents a metal atom. Examples of the metal atom include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, Ba, etc. Among them, a divalent metal atom is preferred, and Zn, Co, and Ni are more preferred.

[0081] Specific examples of the indigo compound are shown below. Note that the present invention is not limited thereto.

[0082]

Chemical formula

[0083]

Chemical formula

[0084]

Chemical formula

[0085]

Chemical formula

[0086] The near-infrared absorbing dye (A) can be used alone or in combination of two or more. When used in combination of two or more, it is preferable to use at least two compounds having different maximum absorption wavelengths. Thereby, compared with the case where one kind of near-infrared absorbing dye (A) is used, the waveform of the absorption spectrum spreads, and near-infrared rays in a wide wavelength range can be absorbed.

[0087] From the viewpoint of near-infrared absorption, the content of the near-infrared absorbing dye (A) is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[0088] [Other near-infrared absorbing compounds] The photosensitive composition of the present invention can contain a compound having a near-infrared absorbing ability other than the near-infrared absorbing dye (A) (hereinafter also referred to as other near-infrared absorbing compounds). Examples of other near-infrared absorbing compounds include metal oxide particles or metal particles such as 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, and gold.

[0089] [Resin (B)] The photosensitive composition of the present invention contains a resin (B).

[0090] The resin (B) is used, for example, for the purpose of dispersing particles such as the near-infrared absorbing dye (A) in the photosensitive composition and for the purpose of imparting resistance to the cured film. Note that the resin (B) mainly used for dispersing particles such as the near-infrared absorbing dye (A) is also referred to as a dispersion resin, and the resin (B) used for imparting resistance to the cured film is also referred to as a binder resin. However, such uses of the resin (B) are merely examples, and it can also be used for other purposes.

[0091] The resin (B) is not particularly limited, and known resins can be used. For example, (meth)acrylic resins, styrene resins, styrene-acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, cyclic olefin resins, etc. can be mentioned. These can be used alone or in combination of two or more.

[0092] The weight average molecular weight (Mw) of the resin (B) is preferably 4,000 to 40,000, more preferably 4,000 to 30,000.

[0093] The content of the resin (B) is preferably 3 to 400 parts by mass, more preferably 5 to 250 parts by mass, based on 100 parts by mass of the near-infrared absorbing dye (A).

[0094] (Resin (B1)) From the viewpoints of developability, pattern formability, and resistance of the cured film, it is preferable that the resin (B) contains, as a binder resin, a resin (B1) having an aromatic ring-containing monomer unit (b1) and a polymerizable group-containing monomer unit (b2), and the glass transition temperature of the homopolymer of the aromatic ring-containing monomer unit (b1) is 80°C or higher. The resin (B1) is not particularly limited, and known resins can be used. For example, a copolymer of a monomer forming an aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80°C or higher and a monomer forming a polymerizable group-containing monomer unit (b2), or a copolymer of a monomer forming an aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80°C or higher and another monomer copolymerizable therewith, to which a compound having a polymerizable group is reacted to introduce a polymerizable group-containing monomer unit (b2), or a copolymer obtained by the method described in JP-A-2008-165059, etc. can be mentioned. In addition, it is preferable that the polymerizable group-containing monomer unit (b2) is obtained by modifying a polymerizable group-containing monomer unit (b2) precursor of copolymerization to impart a polymerizable group.

[0095] [Aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80°C or higher] Examples of the aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80°C or higher include the following units (b1-1) to (b1-5). The glass transition temperatures of the units (b1-1) to (b1-5) are 100°C, 102°C, 159°C, 227°C, and 276°C, respectively. Note that the present invention is not limited thereto. Among these, from the viewpoint of the resistance of the cured film, (b1-1) and (b1-2) are preferable. The upper limit of the glass transition temperature is not particularly limited, but is preferably 300°C or lower.

[0096]

Chemical formula

[0097] The content of the aromatic ring-containing monomer unit (b1) with a glass transition temperature of the homopolymer of 80°C or higher is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, in all the constituent units of the resin (B1) from the viewpoints of pattern formability and resistance of the cured film.

[0098] [Polymerizable group-containing monomer unit (b2)] Examples of the polymerizable group of the polymerizable group-containing monomer (b2) include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. Examples of the method for incorporating the polymerizable group-containing monomer unit (b2) include the following methods (i) to (iii).

[0099] [Method (i)] There is a method (i) of adding the carboxyl group of the carboxyl group-containing monomer to the epoxy group of the resin containing the aromatic ring-containing monomer unit (b1) with a glass transition temperature of the homopolymer of 80°C or higher and the epoxy group-containing monomer unit.

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

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

[0102] From the viewpoint of developability, a reaction product of an acid anhydride with the site where the carboxyl group of the carboxyl group-containing monomer is added to the epoxy group of the epoxy group-containing monomer unit is also useful as the polymerizable group-containing monomer unit (b2).

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

[0104] <Method (ii)> There is a method (ii) of adding an epoxy group of an epoxy group-containing monomer to a carboxyl group of a resin containing an aromatic ring-containing monomer unit (b1) having a glass transition temperature of 80°C or higher and a carboxyl group-containing monomer unit.

[0105] <Method (iii)> There is a method (iii) of reacting an isocyanate group of an isocyanate group-containing monomer with a hydroxyl group of a resin containing an aromatic ring-containing monomer unit (b1) having a glass transition temperature of 80°C or higher and a hydroxyl group-containing monomer unit.

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

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

[0108] Examples of the polymerizable group-containing monomer unit (b2) include the following units (b2-1) to (b2-8). However, the present invention is not limited thereto.

[0109]

Chemical formula

[0110] From the viewpoint of the resistance of the cured film, the content of the monomer unit (b2) containing a coincidence group is preferably 5 to 95 mol%, more preferably 15 to 90 mol%, based on all the constituent units of the resin (B1).

[0111] 〔Alicyclic hydrocarbon-containing monomer unit (b3)〕 From the viewpoint of pattern formability, the resin (B1) preferably further contains an alicyclic hydrocarbon-containing monomer unit (b3). Examples of the alicyclic hydrocarbon-containing monomer unit (b3) include the following units (b3-1) to (b3-6). However, the present invention is not limited thereto.

[0112]

Chemical formula

[0113] From the viewpoint of pattern formability, the content of the alicyclic hydrocarbon-containing monomer unit (b3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on all the constituent units of the resin (B1).

[0114] 〔Other monomer unit (b4)〕 The resin (B1) can contain monomer units other than the monomer units (b1) to (b3) (hereinafter also referred to as other monomer units (b4)).

[0115] Examples of the monomer forming the other monomer unit (b4) include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate; Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl fatty acids such as vinyl acetate or vinyl propionate, etc. may be mentioned.

[0116] Other monomer units (b4) include, for example, the units of the following (b4-1) to (b4-9). Note that the present invention is not limited thereto.

[0117]

Chemical formula

[0118] The weight average molecular weight (Mw) of the resin (B1) is preferably 4,000 to 40,000, and more preferably 3,000 to 30,000.

[0119] From the perspective of developability, the acid value of the resin (B1) is preferably 30 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g.

[0120] The resin (B1) can be used alone or in combination of two or more.

[0121] The content of the resin (B1) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0122] (Resin (B2)) From the perspective of low-temperature curing, the resin (B) preferably contains, as a binder resin, a resin (B2) having a blocked isocyanate group-containing monomer unit (b5). The resin (B2) is not particularly limited, and known resins can be used. For example, a copolymer of a monomer forming a blocked isocyanate group-containing monomer unit (b5) and another monomer copolymerizable therewith can be mentioned.

[0123] [Blocked Isocyanate Group-Containing Monomer Unit (b5)] The blocked isocyanate group-containing monomer unit (b5) is a structural unit derived from a blocked isocyanate group-containing monomer. Examples of the blocked isocyanate group-containing monomer include compounds in which the isocyanate group in an isocyanate compound having a polymerizable group is blocked with a blocking agent.

[0124] Isocyanate compounds having a coincidence group include, for example, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, and the like. Further, an equimolar reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0125] The blocking agents include lactam-based compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; alcohol-based compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol; phenol-based compounds such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol; active methylene-based compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone; mercaptan-based compounds such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; amine-based compounds such as diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amide-based compounds such as acetanilide, acetanisidide, acetic acid amide, benzamide; acid imide-based compounds such as succinimide, maleimide; imidazole-based compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole; Pyrazole-based compounds such as pyrazole and 3,5-dimethylpyrazole; Oxime-based compounds such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime can be mentioned. These blocking agents can be used alone or in combination of two or more. From the viewpoint of low-temperature curing, diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, and 3,5-xylenol are preferred as the blocking agent.

[0126] Commercially available products of the blocked isocyanate group-containing monomer include Karens MOI-DEM, MOI-BP, MOI-BM, etc. manufactured by Showa Denko KK.

[0127] From the viewpoint of low-temperature curing, the content of the blocked isocyanate group-containing monomer unit (b5) is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all the constituent units of the resin (B2).

[0128] The monomer units other than the blocked isocyanate group-containing monomer unit (b5) are not particularly limited as long as they are units formed from monomers copolymerizable with the blocked isocyanate group-containing monomer, and known monomers can be used. For example, the monomer units (b1) to (b4) described in the resin (B1) can be mentioned.

[0129] The production method of the resin (B2) is not particularly limited, and known methods can be used. For example, the methods described in JP-A-2010-197567 and WO 2014 / 141731 can be mentioned.

[0130] The weight average molecular weight (Mw) of the resin (B2) is preferably 4,000 to 40,000, more preferably 4,000 to 30,000.

[0131] From the viewpoint of developability, the acid value of the resin (B2) is preferably 30 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g.

[0132] The resin (B2) can be used alone or in combination of two or more.

[0133] From the viewpoint of the content of the resin (B2), relative to 100 parts by mass of the near-infrared absorbing dye (A), 20 to 400 parts by mass is preferable, and 50 to 250 parts by mass is more preferable.

[0134] (Resin (B3)) From the viewpoint of dispersion stability, in addition to the resin (B1) and the resin (B2), the resin (B) preferably contains the resin (B3) as a dispersion resin.

[0135] The resin (B3) is preferably a resin having an adsorption group with high affinity for the near-infrared absorbing dye (A). The adsorption group preferably has at least one of a basic group and an acidic group.

[0136] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0137] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0138] The resin species of the resin (B3) include, for example, urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyamino amidine salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with a polyester having a free carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinyl pyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based, and the like.

[0139] Examples of the structure of the resin (B3) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, a block structure or a comb structure is preferable.

[0140] Resin (B3) specifically includes 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, 2164 manufactured by BYK-Chemie Japan; Anti-Terra-U203, 204; BYK-P104, P104S, 220S; Lactimon, Lactimon-WS; Bykumen; 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, 76500 manufactured by Lubrizol Japan; 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 manufactured by BASF Japan; Ajisuper PA111, PB711, PB821, PB822 manufactured by Ajinomoto Fine-Techno Co., Ltd.Examples of the resin include those described in PB824, JP-A No. 2008-029901, JP-A No. 2009-155406, JP-A No. 2010-185934, JP-A No. 2011-157416, WO2008 / 007776, JP-A No. 2008-029901, JP-A No. 2009-155406, JP-A No. 2010-185934, JP-A No. 2011-157416, JP-A No. 2012-255128, JP-A No. 2009-251481, JP-A No. 2007-23195, JP-A No. 1996-143651, etc.

[0141] The resin (B3) can be used alone or in combination of two or more.

[0142] From the viewpoint of dispersion stability, the content of the resin (B3) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the near-infrared absorbing dye (A).

[0143] [Polymerizable compound (C)] (Polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure) The photosensitive composition of the present invention contains, as the polymerizable compound (C), a polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure.

[0144] From the viewpoints of pattern formability and the resistance of the cured film, the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure preferably has a weight average molecular weight (Mw) of 1,000 to 30,000, more preferably 1,000 to 25,000.

[0145] From the viewpoints of developability, pattern formability, and the resistance of the cured film, the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure preferably has an average of 6 to 18 polymerizable groups.

[0146] The polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure preferably has at least one polymerizable group selected from the group consisting of an epoxy group, a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, more preferably a (meth)acryloyl group, from the viewpoints of pattern formability and resistance of the cured film.

[0147] From the viewpoint of the resistance of the cured film, the content of the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more in 100% by mass of the polymerizable compound (C).

[0148] The polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more.

[0149] As the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure, those synthesized as appropriate may be used, or commercially available products may be used.

[0150] As methods for synthesizing a dendrimer structure, a divergent method in which synthesis proceeds from the core to the outside, a convergent method in which synthesis proceeds from the terminal polymerizability to the inside, and a combination of these two are known. For example, using the convergent method, as the first step, 2-(4-hydroxyphenoxyethyl)-acrylate and 5-hydroxyisophthalic acid are coupled, and in the second step, trimesic acid is coupled to obtain a polymerizable compound having a dendrimer structure. As a method for synthesizing a hyperbranched structure, it can be obtained by self-condensation of an ABx-type molecule having a total of three or more of two types of substituents in one molecule. For example, using 3,5-dihydroxybenzoic acid as a raw material, a hyperbranched polyester can be obtained by polycondensation. In this case, a hydroxyl group is present at the terminal, and by reacting (meth)acrylic acid therewith, a polymerizable compound having a hyperbranched structure can be obtained.

[0151] The polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure includes, for example, "Biscoat #1000" (dendrimer structure, weight average molecular weight 2,000, average number of acryloyl groups 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., "Miramer SP-1106" (dendrimer structure, weight average molecular weight 1,630, average number of acryloyl groups 18), "Miramer SP-1108" (dendrimer structure, weight average molecular weight 3,000, average number of acryloyl groups 13) manufactured by Miwon Specialty Chemical Co., Ltd., "CN2301" (hyperbranched structure, weight average molecular weight 7,500, average number of acryloyl groups 9), "CN2302" (hyperbranched structure, weight average molecular weight 1,500, average number of acryloyl groups 16), "CN2303" (hyperbranched structure, weight average molecular weight 1,400, average number of acryloyl groups 6), "CN2304" (hyperbranched structure, weight average molecular weight 2,900, average number of acryloyl groups 18) manufactured by Sartomer Co., etc.

[0152] (Other polymerizable compound (C2)) The polymerizable compound (C) can contain a polymerizable compound (C2) other than the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure (hereinafter also referred to as other polymerizable compound (C2)).

[0153] The other polymerizable compound (C2) is not particularly limited, and known compounds polymerizable by radicals, acids, or heat can be used. For example, compounds having a polymerizable group can be mentioned. Examples of the polymerizable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc.

[0154] Specifically, various acrylic esters and methacrylic esters such as polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy (meth)acrylate, EO-modified bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyester (meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, tris(methacryloxyethyl)isocyanurate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra(meth)acrylate, epoxy acrylate, pentaerythritol tetra(meth)acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc. can be mentioned.

[0155] In addition, the other polymerizable compound (C2) may contain an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc.

[0156] Examples of the polymerizable compound containing an acid group include esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, etc. Specifically, monohydroxy oligoacrylates or monohydroxy oligo(meth)acrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc., and free carboxyl group-containing monoesterified products of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid, etc.; free carboxyl group-containing oligoesterified products of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, etc., and monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.

[0157] In addition, the other polymerizable compound (C2) may contain a urethane bond. For example, polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with an alcohol and then reacting with a (meth)acrylate having a hydroxyl group, etc. can be mentioned.

[0158] Examples of the (meth)acrylate having a salicylic acid group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0159] Commercially available products of other polymerizable compounds (C2) 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, D-330, DPCA-20, DCPA-30, DCPA-60 manufactured by Nippon Kayaku Co., Ltd.; Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, M-510, M-520, M-521 manufactured by Toagosei Co., Ltd.; Biscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Industry Co., Ltd.; OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.; Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd.; NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.; EBECRYL 40, 130, 140, 145 manufactured by Daicel Ornex Co., Ltd., and the like.

[0160] Other polymerizable compounds (C2) can be used alone or in combination of two or more.

[0161] From the viewpoints of pattern formability and resistance of the cured film, the content of the polymerizable compound (C) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0162] [Photoinitiator (D)] The photosensitive composition of the present invention contains a photoinitiator (D). Thereby, the photosensitive composition can be cured by irradiation with active energy rays to form a cured film.

[0163] The photoinitiator (D) is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 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, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; a triazine-based compound 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; an oxime ester-based compound such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime); an acylphosphine-based compound such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the quinone compounds include 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc.; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

[0164] In commercially available products, as acetophenone compounds, Omnirad 907, 369E, 379EG manufactured by IGM Resins; as acylphosphine compounds, Omnirad 819, TPO manufactured by IGM Resins; as oxime compounds, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF, N-1919, NCI-730, 831, 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306, EOX-01 manufactured by Daito Chemicals, etc. can be mentioned. In addition, oxime compounds described in JP-A No. 2007-210991, JP-A No. 2009-179619, JP-A No. 2010-037223, JP-A No. 2010-215575, JP-A No. 2011-020998, WO 2015 / 036910, etc. can also be mentioned.

[0165] When the photosensitive composition of the present invention contains a colorant (F) described later, it is preferable to contain an oxime compound as the photopolymerization initiator (D).

[0166] Specific examples of the oxime compounds include, for example, the following. Note that the present invention is not limited thereto.

[0167]

Chemical formula

[0168] Chemical formula (14)

Chemical formula

[0169] The method for producing the compounds of chemical formulas (10) to (16) is not particularly limited, and known methods can be used. For example, the methods described in JP-T-2004-534797, JP-A-2008-80068, JP-T-2012-526185, WO2015 / 036910, WO2015 / 152153, JP-T-2016-504270, JP-T-2017-512886, JP-T-2017-523465, JP-A-2021-011486, etc. can be mentioned.

[0170] From the viewpoints of pattern formability and resistance of the cured film, the content of the photopolymerization initiator (D) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0171] [Sensitizer (E)] The photosensitive composition of the present invention can contain a sensitizer (E).

[0172] The sensitizer (E) includes, for example, chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyllin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, or benzophenone compounds, etc. Among these, from the viewpoints of developability and pattern formability, thioxanthone compounds (E1) or benzophenone compounds (E2) are preferred, and benzophenone compounds (E2) are more preferred.

[0173] (Thioxanthone compounds (E1)) Examples of the thioxanthone compounds (E1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

[0174] (Benzophenone compounds (E2)) Benzophenone compounds (E2) include, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0175] The sensitizer (E) can be used alone or in combination of two or more.

[0176] From the viewpoints of developability and pattern formability, the content of the sensitizer (E) is preferably 50 to 400 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D).

[0177] [Colorant (F)] The photosensitive composition of the present invention can contain a colorant (F). Thereby, the transmittance of each wavelength region of the optical filter can be controlled, and the color separation property and the shielding property are improved.

[0178] The colorant (F) may be either a pigment or a dye, and they can be used in combination.

[0179] (Pigment) Compounds classified as pigments in the Color Index are preferred as the pigment. Red pigments include, for example, C.I. 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, the pigments described in JP-A-2014-134712, the pigments described in Patent No. 6368844, and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. 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 Patent No. 6368844 are preferable, and C.I. Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Patent No. 6368844 are more preferable.

[0180] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, and the like.

[0181] Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, pigments described in JP-A No. 2012-226110, JP-A No. 2017-171912, JP-A No. 2017-171913, JP-A No. 2017-171914, JP-A No. 2017-171915, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A No. 2012-226110 are preferred.

[0182] Green pigments include, for example, C.I. 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, 63, etc. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

[0183] Examples of the cyan pigment include C.I. 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, 79, etc. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

[0184] Examples of the magenta pigment include C.I. 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, 50, etc. Among these, C.I. Pigment Violet 19, 23 are preferred.

[0185] Examples of the black pigment include C.I. Pigment Black 1, 6, 7, 12, 20, 31, 32, etc. In addition, compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, JP-A-1-170601, JP-A-2-34664, etc. are also included.

[0186] When the photosensitive composition of the present invention is used for an infrared transmission filter, as the colorant (F), it preferably contains two or more pigments selected from the group consisting of a red pigment, a yellow pigment, a cyan pigment, a green pigment, and a magenta pigment and exhibits black.

[0187] Examples of the combination that exhibits black include the following embodiments. (1) Containing a yellow pigment and a magenta pigment. (2) Containing a red pigment, a yellow pigment, and a magenta pigment. (3) Containing a red pigment, a yellow pigment, and a cyan pigment. (4) Containing a red pigment, a yellow pigment, and a green pigment. (5) Containing a yellow pigment, a cyan pigment, and a magenta pigment. It contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment.

[0188] The aspect of (1) above includes an aspect that contains at least one selected from C.I. Pigment Yellow 139, 185, 231, 233 as the yellow pigment and C.I. Pigment Violet 23 as the purple pigment. The aspect of (2) above includes an aspect that contains at least one selected from C.I. Pigment Red 177, 254, 291, 295, 296 in the red pigment, one or more selected from C.I. Pigment Yellow 139, 185, 231, 233 in the yellow pigment, and C.I. Pigment Violet 23 in the purple pigment. The aspect of (3) above includes an aspect that contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296 in the red pigment, one or more selected from C.I. Pigment Yellow 139, 185, 231, 233 in the yellow pigment, and one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6 in the blue pigment. The aspect of (4) above includes an aspect that contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296 in the red pigment, one or more selected from C.I. Pigment Yellow 139, 185, 231, 233 in the yellow pigment, and one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63 in the green pigment. The aspect of (5) above includes an aspect that contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233 in the yellow pigment, one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6 in the blue pigment, and C.I. Pigment Violet 23 in the purple pigment. The embodiment of (6) above includes an embodiment containing at least one selected from C.I. Pigment Red 177, 254, 291, 295, 296 as the red pigment, at least one selected from C.I. Pigment Yellow 139, 185, 231, 233 as the yellow pigment, at least one selected from C.I. Pigment Blue 15:3, 15:4, 15:6 as the blue pigment, and C.I. Pigment Violet 23 as the purple pigment.

[0189] Among the embodiments of (1) to (6) above, from the viewpoint of light shielding property, the embodiment of (5) above is preferable.

[0190] Among the embodiments of (5) above, it is more preferable to contain C.I. Pigment Yellow 139 as the yellow pigment, C.I. Pigment Blue 15:6 as the blue pigment, and C.I. Pigment Violet 23 as the purple pigment.

[0191] Table 1 shows the preferable mass ratios (mass %) of each organic pigment in each embodiment.

[0192]

Table 1

[0193] Among pigments, inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc.

[0194] (Dye) Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Also included are derivatives thereof and lake pigments obtained by lake-forming dyes.

[0195] Acidic dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. Further, a salt-forming compound which is a salt of an acidic dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Further, a salt-forming compound which is a salt of a resin component having these functional groups and an acidic dye is also preferable. Further, the salt-forming compound is easily obtained as a photosensitive composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification into a sulfonic acid amide compound. Further, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because of its excellent resistance (light resistance, solvent resistance). Note that as the compound having an onium base, a resin having a cationic group is preferable.

[0196] Basic dyes can be used as they are, but salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof are preferable. The salt-forming compounds of basic dyes are preferable because of their excellent resistance (light resistance, solvent resistance) and affinity with pigments. Further, as the anionic component acting as a counterion in the salt-forming compound of a basic dye, an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, and a salt-forming compound formed by salting with an acidic dye are preferable. Note that the resistance of the salt-forming compound is further improved when it contains a polymerizable group in the molecule.

[0197] The chemical structure of the dye is derived from a dye selected from, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof, etc.

[0198] Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferable.

[0199] The colorant (F) can be used alone or in combination of two or more.

[0200] The content of the colorant (F) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0201] (Micronization of Pigment) The pigment is preferably used after being refined. The refining method is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment by the kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the refined pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0202] Salt milling treatment is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by water washing. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling treatment of the pigment, a pigment with a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0203] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, and sodium sulfate, and sodium chloride (table salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, from both the viewpoints of treatment efficiency and production efficiency.

[0204] The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, from the viewpoint of safety, a high-boiling solvent with a boiling point of 120 °C or higher is preferred. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

[0205] For the salt milling treatment, a resin may be added as necessary. The type of the resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in the above organic solvent. The addition amount of the resin is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0206] [Dye Derivative (H)] The photosensitive composition of the present invention can contain a dye derivative (H).

[0207] Examples of the dye derivative (H) include compounds having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (H) includes, for example, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphate group, etc., and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of the organic pigment include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, phthalocyanine-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, and polyazo, squarylium compounds, naphthalocyanine compounds, and the like.

[0208] Specifically, as diketopyrrolopyrrole-based pigment derivatives, there are those described in JP-A No. 2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A No. 2017-156397; as phthalocyanine-based pigment derivatives, there are those described in JP-A No. 2007-226161, WO 2016 / 163351, JP-A No. 2017-165820, Patent No. 5753266; as anthraquinone-based pigment derivatives, there are those described in JP-A No. 63-264674, JP-A No. 09-272812, JP-A No. 10-245501, JP-A No. 10-265697, JP-A No. 2007-079094, WO 2009 / 025325; as quinacridone-based pigment derivatives, there are those described in JP-A No. 48-54128, JP-A No. 03-9961, JP-A No. 2000-273383; as dioxazine-based pigment derivatives, there are those described in JP-A No. 2011-162662; as thiazine indigo-based pigment derivatives, there are those described in JP-A No. 2007-314785; as triazine-based pigment derivatives, there are those described in JP-A No. 61-246261, JP-A No. 11-199796, JP-A No. 2003-165922, JP-A No. 2003-168208, JP-A No. 2004-217842, JP-A No. 2007-314681; as benzisoindole-based pigment derivatives, there are those described in JP-A No. 2009-57478; as quinophthalone-based pigment derivatives, there are those described in JP-A No. 2003-167112, JP-A No. 2006-291194, JP-A No. 2008-31281, JP-A No. 2012-226110; as naphthol-based pigment derivatives, there are those described in JP-A No. 2012-208329, JP-A No. 2014-5439; as azo-based pigment derivatives, there are those described in JP-A No. 2001-172520, JP-A No. 2012-172092; as acidic substituents, there are those described in JP-A No. 2004-307854; as basic substituents, there are those described in JP-A No. 2002-201377, JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, etc. Known pigment derivatives described therein can be mentioned.In these documents, the dye derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds. However, a compound having a substituent such as an acidic group, a basic group, or a neutral group in the above-described organic dye residue is synonymous with a dye derivative.

[0209] The dye derivative (H) can be used alone or in combination of two or more.

[0210] [Thermosetting compound (I)] The photosensitive composition of the present invention can contain a thermosetting compound (I). Thereby, the thermosetting compound (I) reacts in the heating step, and the crosslinking density increases, so that the heat resistance is improved.

[0211] The thermosetting compound (I) may be a low molecular compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (I) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0212] The thermosetting compound (I) can be used alone or in combination of two or more.

[0213] [Curing agent (curing accelerator)] The photosensitive composition of the present invention can be used in combination with a curing agent (curing accelerator) in order to assist the curing of the thermosetting compound (I). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like.

[0214] The curing agent can be used alone or in combination of two or more.

[0215] The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (I).

[0216] [Thiol-based chain transfer agent (J)] The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (J). When the thiol-based chain transfer agent (J) is used in combination with a photoinitiator (D), during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, and the photosensitivity of the photosensitive composition is improved.

[0217] As the thiol-based chain transfer agent (J), a polyfunctional thiol having two or more thiol groups (SH groups) is preferable, and a polyfunctional thiol having four or more is more preferable. As the number of functional groups increases, it becomes easier for the film to be photocured from the surface to the deepest part.

[0218] Examples of the polyfunctional thiol 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 tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. are mentioned.

[0219] The thiol-based chain transfer agent (J) can be used alone or in combination of two or more.

[0220] The content of the thiol-based chain transfer agent (J) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0221] [Polymerization inhibitor (K)] The photosensitive composition of the present invention can contain a polymerization inhibitor (K).

[0222] Examples of the polymerization inhibitor (K) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol; alkyl resorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol; alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide; phosphite compounds such as triphenyl phosphite, trisnonylphenyl phosphite; pyrogallol, phloroglucin, and the like.

[0223] The content of the polymerization inhibitor (K) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0224] [Ultraviolet absorber (L)] The photosensitive composition of the present invention can contain an ultraviolet absorber (L).

[0225] The ultraviolet absorber (L) is an organic compound having an ultraviolet absorption 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.

[0226] The content of the ultraviolet absorber (L) is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[0227] [Antioxidant (M)] The photosensitive composition of the present invention can contain an antioxidant (M). The antioxidant (M) prevents yellowing caused by oxidation of the photopolymerization initiator (D) and the thermosetting compound (I) in the photosensitive coloring composition during thermosetting or the heat treatment during ITO annealing. In particular, when the concentration of the near-infrared absorbing dye (A) in the photosensitive composition is high, the content of the polymerizable compound (C) relatively decreases. Therefore, when dealing with this by increasing the amount of the photopolymerization initiator (D) or blending the thermosetting compound, the cured film is likely to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

[0228] Examples of the antioxidant (M) include compounds such as hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0229] The antioxidant (M) can be used alone or in combination of two or more.

[0230] The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0231] [Leveling agent (N)] The photosensitive composition of the present invention can contain a leveling agent (N). Thereby, the wettability and drying property with respect to the substrate during coating are further improved. Examples of the leveling agent (N) include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and the like.

[0232] Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or terminals.

[0233] Examples of commercially available products include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning; 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, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0234] Examples of the fluorosurfactant include surfactants or leveling agents having a fluorocarbon chain.

[0235] Examples of commercially available products include Surfron S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Ftergent 602A manufactured by Neos Corporation.

[0236] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrylated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, 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 sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, and the like.

[0237] Commercially available products include, for example, Kao's 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, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodol 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), Amite 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapulronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid-based (co)polymers Polyflow - No. 75, No. 90, No. 95, etc.

[0238] Examples of cationic surfactants include alkylamine salts and alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0239] Commercially available products include, for example, Kao's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0240] Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, and the like.

[0241] Commercially available products include, for example, Ftergent 100, 150 manufactured by Neos Co., Ltd., ADEKA Hope YES-25 manufactured by ADEKA Corporation, ADEKA Cole TS-230E, PS-440E, EC-8600, and the like.

[0242] Amphoteric surfactants include, for example, alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0243] Commercially available products include Anhtol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0244] The leveling agent (N) can be used alone or in combination of two or more.

[0245] The content of the leveling agent (N) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[0246] [Storage stabilizer (O)] The photosensitive composition of the present invention can contain a storage stabilizer (O). Thereby, the viscosity of the photosensitive composition over time is stabilized. Examples of the storage stabilizer (O) include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites, etc.

[0247] The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0248] [Adhesion improver (P)] The photosensitive composition of the present invention can contain an adhesion improver (P). Thereby, the adhesion between the cured film and the substrate is improved. Also, it becomes easier to form a pattern with a narrow width by the photolithography method.

[0249] Examples of the adhesion improver (P) include silane coupling agents, etc.

[0250] The adhesion improver (P) can be used alone or in combination of two or more.

[0251] The content of the adhesion improver (P) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0252] [Organic solvent (Q)] The photosensitive composition of the present invention can contain an organic solvent (Q).

[0253] The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc. may be mentioned. Among these, from the viewpoints of the dispersibility of the pigment and the solubility of the alkali-soluble resin, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferable.,

[0254] The organic solvent (Q) can be used alone or in combination of two or more kinds.

[0255] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced, for example, by adding a near-infrared absorbing dye (A), a dispersion resin, an organic solvent (Q), etc. and performing a dispersion treatment to produce a dispersion. Then, a binder resin (preferably an alkali-soluble resin), a polymerizable compound (C), a photopolymerization initiator (D), etc. are blended and mixed with the dispersion. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0256] Examples of the disperser for performing 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, or an attritor.

[0257] The average dispersed particle diameter (secondary particle diameter) of the near-infrared absorbing dye (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A photosensitive composition having high dispersion stability is easily obtained when it has an appropriate particle diameter.

[0258] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power spectrum method), the particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. As the dilution solvent for measurement, the organic solvents used for dispersion are respectively used, and when measuring the sample immediately after sample preparation for the sample treated with ultrasonic waves, results with less variation are easily obtained and are preferable.

[0259] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means such as centrifugation, filtration through a sintered filter or a membrane filter. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0260] [Cured film] The cured film of the present invention is obtained by curing a film formed using the photosensitive composition of the present invention by treatment such as exposure. Note that the cured film may be a flat film.

[0261] [Method for producing cured film] The method for manufacturing the cured film is not particularly limited. For example, it can be produced by performing the following steps: (1) a step of applying a photosensitive composition onto a substrate to form a layer of the composition; (2) a step of exposing the layer in a pattern through a mask; (3) a step of developing the unexposed portion with an alkali to form a patterned cured film; and (4) a step of heat-treating (post-baking) the pattern.

[0262] Hereinafter, the method for manufacturing the cured film will be described in detail. (Step (1)) In step (1) of forming a layer of the composition, the photosensitive composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and dried (pre-baked) at a temperature of 50 to 100°C for 10 to 120 seconds using an oven, hot plate, etc., as necessary. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an imaging element such as a CCD or CMOS formed on its surface, for example. Further, a undercoat layer may be provided on the substrate as necessary to improve adhesion to an upper layer, prevent diffusion of substances, and planarize the substrate surface. The film thickness of the layer is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm, after drying.

[0263] (Step (2)) In the exposure step, the layer obtained in step (1) is exposed through a mask to a specific pattern using an exposure apparatus such as a stepper, etc. Thereby, a cured film is obtained. Examples of the radiation used for exposure include ultraviolet rays such as g-line, h-line, and i-line.

[0264] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the layer of the composition in the unexposed portion is eluted in an aqueous alkali solution, and only the cured portion remains to obtain a patterned cured film. The developing solution includes, for example, alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. The concentration of the alkaline developing solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developing solution is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved.

[0265] Examples of the developing method include dip method, spray method, paddle method, etc. The developing temperature is preferably 15 to 40°C. After alkaline development, it is preferably washed with pure water.

[0266] (Step (4)) The heat treatment (post-bake) sufficiently cures the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 130°C or lower, more preferably 100°C or lower. Also, the heating time is preferably about 5 minutes to 1 hour, more preferably about 5 minutes to 30 minutes.

[0267] <Optical filter> The optical filter of the present invention has a cured film. The uses of the optical filter are preferably an infrared cut filter and an infrared transmission filter, more preferably an infrared cut filter. The optical filter of the present invention can be manufactured by the same method as the above-mentioned cured film.

[0268] <Image display device> The image display device of the present invention has a cured film. When used in an image display device, it is not particularly limited, but it can be used as a color filter or a black matrix. The black matrix includes black edges provided at the peripheral portions of image display devices such as solid-state imaging devices and liquid crystal display devices, lattice-shaped and / or striped black portions between red, blue, and green pixels, black patterns on dots and / or linear shapes for TFT light shielding, and the like.

[0269] An example of the image display device of the present invention will be described. The image display device includes the cured film of the present invention and a light source. Examples of the light source include a cold cathode tube (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of the expansion of the red reproduction region. FIG. 1 is a schematic cross-sectional view showing a configuration example of an image display device including the cured film of the present invention. The image display device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a gap therebetween, and a liquid crystal LC is encapsulated between them.

[0270] On the inner surface of the first transparent substrate 11, a TFT (thin film transistor) array 12 is formed, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Further, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0271] On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0272] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is further formed thereon, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0273] Further, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0274] The liquid crystal LC is aligned according to driving modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). On the inner surface of the first transparent substrate 11, a TFT (Thin Film Transistor) array 12 is formed, and on top of it, a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Also, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0275] On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

[0276] Covering the color filter 22, a transparent protective film (not shown) is formed as needed, and on top of it, a transparent electrode layer 23 made of, for example, ITO is formed, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0277] Also, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0278] As white LED light sources, there are those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in the resin package of a blue LED. They have a wavelength (λ3) at which the emission intensity is maximized within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity is maximized within the range of 530 nm to 580 nm, a wavelength (λ5) at which the emission intensity is maximized within the range of 600 nm to 650 nm, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less. A white LED light source (LED1) having such spectral characteristics, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferable.

[0279] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.), NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.), and the like.

[0280] Examples of LED2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.), NSSW304D (manufactured by Nichia Chemical Industries, Ltd.), and the like.

[0281] <Solid-state imaging device> The solid-state imaging device of the present invention has a cured film. When used in a solid-state imaging device, it is not particularly limited. For example, on a substrate, it has a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, or organic CMOS image sensor, etc.) and a light-receiving element made of polysilicon or the like, and has the cured film of the present invention on the light-receiving element formation surface side or the opposite side of the formation surface. FIG. 2 is a schematic cross-sectional view showing a configuration example of the solid-state imaging device provided with the cured film of the present invention.

[0282] As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging element 201 and a transparent cover glass 203 that is held above the solid-state imaging element 201 and seals the solid-state imaging element 201. Further, a lens layer 211 is provided on the cover glass 203 with a spacer 104 interposed therebetween. The lens layer 211 is composed of a support 213 and a lens material 212. When stray light enters the peripheral region of the lens layer 211, the light collection effect by the lens material 212 is weakened due to light diffusion, and the light reaching the imaging unit 202 is reduced. Also, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 211 is provided with the cured film 214 of the present invention to block light.

[0283] The solid-state imaging element 201 photoelectrically converts an optical image formed at the imaging unit 202 serving as its light-receiving surface and outputs it as an image signal. The solid-state imaging element 201 includes a laminated substrate 205 formed by laminating two substrates. The laminated substrate 205 is composed of a rectangular chip substrate 206 and a circuit substrate 207 of the same size, and the circuit substrate 207 is laminated on the back surface of the chip substrate 206.

[0284] An imaging unit 202 is provided at the center of the surface of the chip substrate 206. Also, when stray light enters the peripheral region of the imaging unit 202, dark current (noise) is generated from the circuits within this peripheral region. Therefore, this peripheral region is provided with the cured film (light-blocking) 215 of the present invention to block light.

[0285] A plurality of electrode pads 208 are provided at the edge of the surface of the chip substrate 206. The electrode pads 208 are electrically connected to the imaging unit 202 via signal lines (not shown) provided on the surface of the chip substrate 206.

[0286] On the back surface of the circuit board 207, external connection terminals 209 are provided at positions substantially below each electrode pad 208. Each external connection terminal 209 is connected to an electrode pad 208 via a through electrode 210 that vertically penetrates the multilayer substrate 205. Further, each external connection terminal 209 is connected to a control circuit that controls the driving of the solid-state imaging device 201 and an image processing circuit that performs image processing on the imaging signal output from the solid-state imaging device 201 via wiring (not shown).

[0287] <Infrared sensor> The infrared sensor of the present invention has a cured film. FIG. 3 is a schematic cross-sectional view showing a configuration example of the infrared sensor provided with the cured film of the present invention. The infrared sensor shown in FIG. 3 includes 300 and a solid-state imaging device 310.

[0288] The imaging region provided on the solid-state imaging device 310 is configured by combining an infrared cut filter 311 and a color filter 312. The infrared cut filter 311 is a filter that transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm) and shields light in the infrared region (for example, light having a wavelength of 800 to 1300 nm). The cured film of the present invention containing the above-described near-infrared absorbing dye (A) can be used. The color filter 312 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed is used.

[0289] A resin film 314 that can transmit light having a wavelength transmitted through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging device 310. The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength. A cured film containing two or more types of colored colorants in the photosensitive composition of the present invention can be used. The infrared transmission filter 313 preferably shields light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm.

[0290] On the incident light side of the color filter 312 and the infrared transmission filter 313, a microlens 315 is disposed. A planarization film 316 is formed so as to cover the microlens 315.

[0291] In the form shown in FIG. 3, a resin film 314 is disposed, but an infrared transmission filter 313 may be formed in place of the resin film 314.

[0292] According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like for recognizing a target to be detected for motion is possible. Further, according to this infrared sensor, since distance information can be obtained, photographing an image including 3D information or the like is also possible. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

[0293] In addition, the cured film of the present invention can also be used as a colored spacer. For example, when a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and the colored spacer is used to prevent this. The colored spacer can be formed in the same manner as the above-described black matrix except that a mask for the colored spacer is used.

[0294] In addition, the cured film of the present invention can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is preferably used for members that impart light shielding properties and antireflection properties in addition to optical filters used for micro LEDs and micro OLEDs. Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.

[0295] In addition, the cured film of the present invention can also be used in applications such as quantum dot displays. Although not particularly limited, it is preferably used for members that impart light-shielding properties and antireflection properties, in addition to optical filters used in quantum dot displays.

Examples

[0296] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. In addition, "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the nonvolatile content or nonvolatile concentration refers to the mass residue after oven standing at 280°C for 30 minutes.

[0297] Each measurement method will be described. The measurement of the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin is as follows.

[0298] (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. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus. Two separation columns were connected in series, and for both fillers, "TSK-GEL SUPER HZM-N" was connected in pairs and used. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at 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 were injected. The molecular weight is in terms of polystyrene conversion.

[0299] (Acid value of resin) To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to dissolve uniformly. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was performed using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g). Then, from the acid value of the resin solution and the nonvolatile content concentration of the resin solution, the acid value per nonvolatile content of the resin was calculated.

[0300] (Amine value of the resin) The amine value of the resin is the value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 to a non-volatile content basis.

[0301] (Production of near-infrared absorbing dye (A)) (Near-infrared absorbing dye (A-1)) 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 part of p-toluenesulfonic acid monohydrate were mixed, heated and stirred in an atmosphere of nitrogen gas, and refluxed for 3 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the toluene was distilled off, and the dark brown solid obtained was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in an atmosphere of nitrogen gas and refluxed for 8 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and while stirring the obtained reaction mixture, 200 parts of hexane was added. After the obtained blackish brown precipitate was filtered off, it was washed successively with hexane, ethanol and acetone, dried under reduced pressure, and a near-infrared absorbing dye (A-1) represented by the following chemical formula (17) was obtained. 50 parts of the obtained near-infrared absorbing dye (A-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 °C for 12 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80 °C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 °C for a whole day and night and pulverized to obtain a micronized near-infrared absorbing dye (A-1).

[0302] Chemical formula (17) [Chemical formula]

[0303] (Near-infrared absorbing dye (A-2)) 400 parts of toluene was mixed with 40.0 parts of 1,8-diaminonaphthalene, 50.1 parts of 2-hydroxy-9-fluorenone, and 0.087 part of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in an atmosphere of nitrogen gas and refluxed for 3 hours. The water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the toluene was distilled off, and the dark brown solid obtained was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in an atmosphere of nitrogen gas and refluxed for 8 hours. The water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and while stirring the obtained reaction mixture, 200 parts of hexane was added. The obtained blackish brown precipitate was separated by filtration and then washed successively with hexane, ethanol, and acetone and dried under reduced pressure to obtain a near-infrared absorbing dye (A-2) represented by the following chemical formula (18). A micronized near-infrared absorbing dye (A-2) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0304] Chemical formula (18) [Chemical formula]

[0305] (Near-infrared absorbing dye (A-3)) In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts of aluminum trichloride were mixed and stirred, and after heating, the mixture was refluxed at 136 °C for 5 hours. The reaction solution cooled to 30 °C while stirring was 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 a. Next, in a reaction vessel, 140 parts of Compound a was added to 1,500 parts of concentrated sulfuric acid under an ice bath, and stirring was carried out 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 treated in the order of filtration, washing with water, washing with a 2.5% aqueous sodium hydroxide solution, and washing with water, and then dried to obtain Compound b. 5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and after sufficient stirring and mixing, it was heated to 50°C. To this solution, 10 parts of Compound b was added little by little, and then stirring was carried out at 90°C for 120 minutes. The end point of the reaction was confirmed by, for example, dropping the reaction solution onto filter paper and taking the point where there was no bleeding as the end point. Subsequently, this reaction solution was poured into 2,000 parts of ion-exchanged water, and the resulting precipitate was treated in the order of filtration and washing with water, and then dried to obtain a mixture of compounds represented by the following Chemical Formula (19) (mixing ratio: n1:n2:n3:n4 = 7:19:59:15), a near-infrared absorbing dye (A-3). A micronized near-infrared absorbing dye (A-3) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0306] Chemical Formula (19)

Chemical Formula

[0307] (Near-infrared absorbing dye (A-4)) According to the description in International Publication No. 2019 / 058882, a near-infrared absorbing dye (A-4) represented by the following Chemical Formula (20) was obtained. A micronized near-infrared absorbing dye (A-4) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0308] Chemical Formula (20)

Chemical Formula

[0309] (Near-infrared absorbing dye (A-5)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / l toluene solution of titanium tetrachloride were added dropwise. After the addition, 10.0 parts of indigo were added and refluxed for 10 hours. After completion of the reaction, methanol was added, and filtration was performed to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred. After heating, the mixture was stirred at 40 °C for 5 hours. The reaction solution, which was cooled to 30 °C while stirring, was poured into 500 parts of methanol while stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, then washed with 500 parts of water, and dried to obtain a near-infrared absorbing dye (A-5) which is a mixture of compounds represented by the following chemical formula (21) (mixing ratio: dimer: trimer: tetramer = 81:17:2). Subsequently, a micronized near-infrared absorbing dye (A-5) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0310] Chemical formula (21) [Chemical formula]

[0311] [Production of resin (B)] (Solution of resin (B1-1)) A separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer was charged with 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc), and heated to 120 °C while injecting nitrogen gas into the flask. Then, 0.1 mol of styrene, which is a monomer forming an aromatic-containing monomer unit (b1), 0.3 mol of dicyclopentanyl methacrylate, which is a monomer forming an alicyclic hydrocarbon-containing monomer unit (b3), 0.6 mol of glycidyl methacrylate, which is a monomer forming another monomer unit (b4), and a mixture of t-butyl peroxy-2-ethylhexanoate, which is a polymerization initiator, and PGMAc were added dropwise from a dropping funnel over 2.5 hours. After completion of the dropping, the mixture was further stirred at 120 °C for 2 hours. Then, the inside of the flask was replaced with air, 0.6 mol of acrylic acid, triphenylphosphine and methylhydroquinone, which are catalysts, were added, and the mixture was stirred at 110 °C for 10 hours to react the epoxy group of glycidyl methacrylate with the carboxyl group of acrylic acid. Then, 0.38 mol of tetrahydrophthalic anhydride was added, and the mixture was stirred at 110 °C for 4 hours. Thereby, a polymerizable group-containing monomer unit (b2) was formed. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass to prepare a resin (B1-1) solution. The resin (B1-1) had an acid value of 80 mgKOH / g and a weight average molecular weight of 9,000.

[0312] (Resin (B1-2) to (B1-13) solutions) Resins (B1-2) to (B1-13) were synthesized so as to have the molar ratios of the respective components described in Table 1, and PGMAc was added to make the nonvolatile content 40% by mass.

[0313]

Table 2

[0314] Each monomer unit (b1) to (b4) of the components described in Table 2 is the above-described unit, and corresponding monomers or their precursors were used for the synthesis.

[0315] (Resin (B2-1) solution) After putting 257.3 g of PGMAc into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, the mixture was stirred while purging with nitrogen and heated to 78°C. Next, 30 mol of dicyclopentanyl methacrylate, which is a monomer forming the alicyclic hydrocarbon-containing monomer unit (b3), 32 mol of glycidyl methacrylate, which is a monomer forming the other monomer unit (b4), 33 mol of methacrylic acid, which is a monomer forming the other monomer unit (b4), and 5.0 mol of malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, which is a monomer forming the block isocyanate group-containing monomer unit (b5), were added to 78.7 g of PGMAc, and 13.4 g of 2,2’-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was dissolved therein. The resulting solutions were each dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 78°C for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass to prepare a resin (B2-1) solution. The resin (B2-1) had an acid value of 111 mgKOH / g and a weight average molecular weight of 7,500.

[0316] (Resin (B3-1) solution) Into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the system was 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. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the mixture was stirred while maintaining the temperature at 110 °C under a nitrogen atmosphere to continue the reaction. Two hours after the addition, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the polymer had a mass average molecular weight of 20,000 and a molecular weight distribution Mw / Mn of 1.4, and the reaction conversion rate was 98.5%. In this way, a resin (B3-1) with an amine value of 169.8 mgKOH / g per non-volatile content was obtained. After cooling to room temperature, about 2 g was sampled and dried by heating at 180 °C for 20 minutes to measure the non-volatile content, and PGMAc was added so that the non-volatile content became 30 mass% to prepare a resin (B3-1) solution.

[0317] (Resin (B3-2) solution) Into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funacryl FA-711MM) as the second block (A block) monomer were added to this reactor, and the mixture was stirred while maintaining the temperature at 110 °C in a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added for dilution so that the non-volatile content became 30% in the non-volatile content measurement, and a resin (B3-2) solution with an amine value of 57 mg KOH / g and a number average molecular weight of 4,500 (Mn) per non-volatile content was obtained.

[0318] (Resin (B3-3) solution) Into a reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc was added while reacting for 7 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added for dilution so that the non-volatile content became 30% by non-volatile content measurement, and a resin (B3-3) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

[0319] <Production of polymerizable compound (C)> (Other polymerizable compound (C2-3) solution) Into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged, the temperature was raised to 70 °C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm -1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were charged, and the reaction was carried out at a temperature of 50 to 60 °C for 6 hours. It was adjusted so that the non-volatile content became 50% by mass, and an other polymerizable compound (C2-3) solution was obtained.

[0320] <Production of colorant (F)> (Fine green pigment (F-1)) 100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 °C for 6 hours. This kneaded product was poured into 3,000 parts of warm water and stirred with a high-speed mixer for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night and pulverized to obtain a micronized green pigment (F-1).

[0321] (Micronized red pigment (F-2)) 100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 °C for 6 hours. Next, the kneaded mixture was poured into warm water and stirred with a high-speed mixer for 1 hour while heating to about 80 °C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night and pulverized to obtain a micronized red pigment (F-2).

[0322] (Micronized blue pigment (F-3)) 100 parts of C.I. Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50 °C for 12 hours. This mixture was poured into 3,000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for 24 hours and pulverized to obtain a micronized blue pigment (F-3).

[0323] (Micronized yellow pigment (F-4)) 100 parts of C.I. Pigment Yellow 138, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 °C for 12 hours. This mixture was poured into 3000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70 °C to form a slurry, and then filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. After that, it was dried at 80 °C for a whole day and night and pulverized to obtain a finely divided yellow pigment (F-4).

[0324] (Finely divided purple pigment (F-5)) 100 parts of C.I. Pigment Violet 23, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 °C for 12 hours. This mixture was poured into 3000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70 °C to form a slurry, and then filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. After that, it was dried at 80 °C for a whole day and night and pulverized to obtain a finely divided purple pigment (F-5).

[0325] <Production of Dispersion> (Dispersion 1) After stirring and mixing the following raw materials uniformly, using zirconia beads with a diameter of 0.5 mm, it was dispersed with an Eiger mill (manufactured by Eiger Japan Co., Ltd., "Mini Model M-250 MKII") for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (P-1) is PGMAc. Near-infrared absorbing dye (A-1): 15.0 parts Resin (B3-1) solution: 20.0 parts Organic solvent (P-1): 65.0 parts

[0326] (Dispersions 2 to 10) Dispersions 2 to 10 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 3 were changed.

[0327]

Table 3

[0328] <Manufacture of photosensitive composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive composition 1. Dispersion 1: 15.0 parts Dispersion 3: 20.0 parts Resin (B1-1) solution: 15.0 parts Polymerizable compound (C1-1): 10.0 parts Photoinitiator (D-2): 0.25 part Photoinitiator (D-4): 0.25 part Sensitizer (E2-1): 0.75 part Leveling agent (N): 1.0 part Organic solvent (P): 37.75 parts

[0329] [Examples 2 to 39, Comparative Examples 1 and 2] (Photosensitive compositions 2 to 41) Photosensitive compositions 2 to 41 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 4-1 to 4-4 were changed.

[0330] [Table 4-1]

[0331] [Table 4-2]

[0332] [Table 4-3]

[0333] [Table 4-4]

[0334] Regarding each of the raw materials described in Tables 4-1 to 4-4, it is as follows.

[0335] [Polymerizable Compound (C)] (Polymerizable Compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure) C1-1: Miramer SP-1108 (manufactured by Miwon Specialty Chemical, a polymerizable compound having a dendrimer structure with a weight average molecular weight of 3,000 and an average number of acryloyl groups of 13) C1-2: Biscoat #1000 (manufactured by Osaka Organic Chemical Industry Co., Ltd., a polymerizable compound having a dendrimer structure with a weight average molecular weight of 2,000 and an average number of acryloyl groups of 14) C1-3: Miramer SP-1106 (manufactured by Miwon Specialty Chemical, a polymerizable compound having a dendrimer structure with a weight average molecular weight of 1,630 and an average number of acryloyl groups of 18) C1-4: CN2301 (manufactured by SARTOMER, a polymerizable compound having a hyperbranched structure with a weight average molecular weight of 7,500 and an average number of acryloyl groups of 9) C1-5: CN2302 (manufactured by SARTOMER, a polymerizable compound having a hyperbranched structure with a weight average molecular weight of 1,500 and an average number of acryloyl groups of 16) C1-6: CN2304 (manufactured by SARTOMER, a polymerizable compound having a hyperbranched structure with a weight average molecular weight of 2,900 and an average number of acryloyl groups of 18)

[0336] (Other Polymerizable Compound (C2)) C2-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) C2-2: Aronix M-521 (manufactured by Toagosei Co., Ltd., an acrylate having an acid group with 5 polymerizable groups) C2-4: U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., a urethane acrylate having 15 polymerizable groups)

[0337] [Photoinitiator (D)] D-1: The compound of the above chemical formula (12) D-2: The compound of the above chemical formula (14) D-3: Omnirad 369 (manufactured by IGM Resins, acetophenone-based photoinitiator) D-4: Omnirad 907 (manufactured by IGM Resins, acetophenone-based photoinitiator)

[0338] [Sensitizer (E)] E2-1: 4,4'-Bis(diethylamino)benzophenone

[0339] [Leveling agent (M)] M-1: BYK-330 (manufactured by BYK-Chemie) M-2: Megafac F-551 (manufactured by DIC) Above, (M-1) and (M-2) were each mixed in 1 part and dissolved in 98 parts of PGMAc to obtain a mixed solution as the leveling agent (M).

[0340] [Organic solvent (P)] P-1: 30 parts of propylene glycol monomethyl ether acetate P-2: 30 parts of cyclohexanone P-3: 10 parts of ethyl 3-ethoxypropionate P-4: 10 parts of propylene glycol monomethyl ether P-5: 10 parts of cyclohexanol acetate P-6: 10 parts of dipropylene glycol methyl ether acetate Above, (P-1) to (P-6) were each mixed in the above parts by mass to obtain an organic solvent (P).

[0341] [Evaluation of the photosensitive composition] For the obtained photosensitive compositions 1 to 41 (Examples 1 to 39, Comparative Examples 1 and 2), the evaluation of developability, pattern formability, and cured film resistance was carried out by the following methods. The evaluation results are shown in Table 5.

[0342] [Evaluation of developability] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, the substrate was exposed through a photomask with a 100-μm-wide stripe pattern under the conditions of an illuminance of 30 mW / cm 2 and 40 mJ / cm 2 . Further, after cooling this substrate to room temperature, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, then washed with ion-exchanged water and air-dried. The obtained substrate was post-baked in a clean oven at 130°C for 20 minutes to form a stripe-like pattern on the substrate. The pattern was observed with an optical microscope, and the presence or absence of development residues in the unexposed areas and chipping was evaluated. The evaluation criteria are as follows, and 3 or more is considered practical. 5: There were no development residues in the unexposed areas and no pattern chipping. 4: Slight development residues occurred in the unexposed areas or slight pattern chipping occurred. 3: Slight development residues occurred in the unexposed areas and slight pattern chipping occurred. 2: A large amount of development residues occurred in the unexposed areas or a large amount of pattern chipping occurred. 1: A large amount of development residues occurred in the unexposed areas and a large amount of pattern chipping occurred.

[0343] [Pattern Formability Evaluation (1): Linearity] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, the substrate was exposed through a photomask with a 50-μm-wide stripe pattern under the conditions of an illuminance of 30 mW / cm 2 and 40 mJ / cm 2Exposure was carried out under the conditions. Thereafter, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 °C, then washed with ion-exchanged water and air-dried. The obtained substrate was post-baked in a clean oven at 130 °C for 20 minutes to obtain a substrate for pattern shape evaluation. The obtained substrate for pattern shape evaluation was evaluated by measuring the maximum and minimum widths of the stripe patterns at 10 locations using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation and calculating the average. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0344] [Pattern formation evaluation (2): Cross-sectional shape] Using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Technologies Corporation), the cross-sectional shape of the pattern was confirmed on the substrate prepared in Pattern formation evaluation (1). The evaluation was performed by capturing a SEM image of the cross-section of a stripe pattern with a width of 100 μm and measuring the taper angle between the base material and the end of the pattern cross-section. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Taper angle is 40 degrees or more and less than 50 degrees 4: Taper angle is 50 degrees or more and less than 60 degrees 3: Taper angle is 30 degrees or more and less than 40 degrees, or 60 degrees or more and less than 70 degrees 2: Taper angle is 20 degrees or more and less than 30 degrees, or 70 degrees or more and less than 90 degrees 1: Taper angle is less than 20 degrees, or 90 degrees or more

[0345] [Hardened film resistance evaluation (1): Solvent resistance] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, ultraviolet light was irradiated through a photomask with a 100-μm-wide stripe pattern under the conditions of an illuminance of 30 mW / cm 2 ² and 50 mJ / cm 2 ². Further, after cooling this substrate to room temperature, it was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 °C, washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked in a clean oven at 130 °C for 20 minutes to obtain a substrate for evaluation. The obtained substrate was immersed in N-methylpyrrolidone at room temperature for 30 minutes, then washed with ion-exchanged water and air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, and 3 or more is considered practical. 5: No change in appearance or color. 4: Slight wrinkles or the like occur, but there is no change in color. 3: Wrinkles or the like occur in part, but there is no change in color. 2: Wrinkles or the like occur over the entire surface, and it fades slightly. 1: Peeling or fading occurs.

[0346] [Hard Film Resistance Evaluation (2): Heat Cycle] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, ultraviolet light was irradiated through a photomask with a 100-μm stripe pattern under the conditions of an illuminance of 30 mW / cm 2 ² and 50 mJ / cm 2It was exposed. Then, this substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked in a clean oven at 130°C for 20 minutes to obtain a heat cycle resistance evaluation substrate. Thereafter, the heat cycle resistance evaluation substrate was subjected to 500 cycles of temperature rise and fall cycles of 10 minutes at -20°C and 10 minutes at 100°C. The evaluation criteria are as follows, and 3 or more is practical. 5: No abnormality in appearance after 500 cycles 4: Slight cracking and / or peeling occurs after 500 cycles 3: Cracking and / or peeling occurs partially after 500 cycles 2: Cracking and / or peeling occurs after 200 cycles 1: Cracking and / or peeling occurs after 100 cycles

[0347]

Table 5

Explanation of Signs

[0348] 10 Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal 200 Solid-state imaging device 201 Solid-state imaging element 202 Imaging unit 203 Cover glass 204 Spacer 205 Laminated substrate 206 Chip substrate 207 Circuit board 208 Electrode pad 209 External connection terminal 210 Through electrode 211 Lens layer 212 Lens material 213 Support 214 Hardened film 215 Hardened film 300 Infrared sensor 310 Solid-state imaging device 311 Infrared cut filter 312 Color filter 313 Infrared transmission filter 314 Resin film 315 Microlens 316 Flat film

Claims

1. A photosensitive composition comprising a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photoinitiator (D), wherein the resin (B) has an aromatic ring-containing monomer unit (b1) and a polymerizable group-containing monomer unit (b2), and the resin (B) includes a resin (B1) in which the glass transition temperature of the homopolymer of the aromatic ring-containing monomer unit (b1) is 80°C or higher, in all the constituent units of the resin (B1), the content of the aromatic ring-containing monomer unit (b1) in which the glass transition temperature of the homopolymer is 80°C or higher is 5 to 30 mol%, and the content of the polymerizable group-containing monomer unit (b2) is 15 to 90 mol%, and the polymerizable compound (C) includes a polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure.

2. The photosensitive composition according to Claim 1, wherein the weight average molecular weight of the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure is 1,000 to 30,000.

3. The photosensitive composition according to Claim 1 or 2, wherein the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure has an average of six or more polymerizable groups.

4. The photosensitive composition according to any one of Claims 1 to 3, wherein the content of the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure is 50% by mass or more in 100% by mass of the polymerizable compound (C).

5. The photosensitive composition according to any one of Claims 1 to 4, wherein the near-infrared absorbing dye (A) has a π-conjugated plane containing a monocyclic or condensed-ring aromatic ring.

6. The photosensitive composition according to any one of Claims 1 to 5, which contains a colorant (F).

7. The photosensitive composition according to Claim 6, wherein the colorant (F) contains two or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments, and purple pigments.

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 having the cured film according to Claim 8.

10. An image display device having the cured film according to Claim 8.

11. A solid-state imaging device having the cured film according to Claim 8.

12. An infrared sensor having the cured film according to Claim 8.

Images