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 that can form a cured film having excellent patternability, showing excellent resistance even to low-temperature baking, and containing few aggregates of foreign matter.SOLUTION: A photosensitive composition includes a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The resin (B) includes a resin (B1) including a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2).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] Solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor) are used in video cameras, digital cameras, smartphones, etc. Since silicon photodiodes sensitive to infrared rays are used in the light-receiving portions 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, the infrared cut filter has been used as a flat film, but in recent years, it has also been studied to form a pattern by a photolithography method. However, since the composition containing a near-infrared absorbing dye 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 has been a problem that the solubility in the developer decreases, the line width of the obtained pattern becomes thick, and a desired pattern cannot be obtained. 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 the photopolymerization initiator, and adjusting the exposure amount. For example, in the case of thick line width, there are methods 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, and reducing the exposure amount to reduce the 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 easily decreases during post-baking, heat treatment is performed at a low temperature. Therefore, there has been a problem that the solvent resistance of the cured film deteriorates more. In addition, the near-infrared absorbing dye has low dispersion stability, and when the obtained cured film is exposed to a high-humidity environment, there is also a problem that the near-infrared absorbing dye aggregates and foreign matters are generated.

[0004] Therefore, for example, 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 cannot satisfy all of pattern formability, cured film resistance at low-temperature baking, and foreign matter suppression at a certain level or higher.

[0007] An object of the present invention is to provide a photosensitive composition that is excellent in pattern formability, has excellent resistance even at low-temperature baking, and can form a cured film with few aggregated foreign matters.

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 resin (B) contains a resin (B1) having a block isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2).

Advantages of the Invention

[0009] According to the present invention described above, it is possible to provide a photosensitive composition that is excellent in pattern formability, has excellent resistance even at low-temperature baking, and can form a cured film with few aggregated foreign matters. 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)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” means “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. Also, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenic unsaturated double bond. Regarding the molecular weight of the compounds in the present invention, for low molecular weight compounds 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 compounds 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. A monomer is in an unreacted state, and a monomer unit is a state in which the monomer forms a resin after polymerization.

[0013] <Photosensitive Composition> A photosensitive composition according to an embodiment 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), wherein the resin (B) contains a resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2).

[0014] [Near-Infrared Absorbing Dye (A)] 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 in 100 g of propylene glycol monomethyl ether acetate at 25°C.

[0015] 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 aromatic rings, the near-infrared absorbing dyes (A) associate with each other, suppressing elution into the organic solvent.

[0016] The π-conjugated plane of the near-infrared absorbing dye (A) preferably contains 2 to 100 monocyclic or condensed aromatic rings, more preferably 3 to 50, still more preferably 4 to 40, and particularly preferably 5 to 30. Examples of the aromatic ring include 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.

[0017] The near-infrared absorbing dye (A) includes, for example, 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, one or more selected from the group consisting of naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferable, and indigo compounds, and / or naphthalocyanine compounds are more preferable.

[0018] Examples of cyanine compounds include International Publication No. 2006 / 006573, International Publication No. 2010 / 073857, JP-A No. 2013-241598, JP-A No. 2016-113501, JP-A No. 2016-113504, etc.; examples of phthalocyanine compounds include JP-A No. 4-23868, JP-A No. 06-192584, JP-A No. 2000-63691, International Publication No. 2014 / 208514, etc.; examples of naphthalocyanine compounds include JP-A No. 11-152414, JP-A No. 2000-86919, JP-A No. 2009-29955, International Publication No. 2017 / 002920, International Publication No. 2018 / 186490, etc.; examples of indigo compounds include JP-A No. 2012-224593, JP-A No. 2013-87233, JP-A No. 2013-230412, etc.; examples of immonium compounds include JP-A No. 2005-336150, JP-A No. 2007-197492, JP-A No. 2008-88426, etc.; examples of anthraquinone compounds include JP-A No. 62-903, JP-A No. 1-172458, etc.; examples of pyrrolopyrrole compounds include JP-A No. 2009-263614, JP-A No. 2010-90313, JP-A No. 2011-068731; examples of squarylium compounds include JP-A No. 2011-132361, JP-A No. 2016-142891, International Publication No. 2017 / 135359, International Publication No. 2018 / 225837, JP-A No. 2019-001987, International Publication No. 2020 / 054718, etc.; examples of croconium compounds include the compounds described in International Publication No. 2019 / 021767, etc.

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

[0020] In general formula (2), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 10 , -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 . R 10 ~R 30 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group which may have a substituent. In addition, when R 12 of -COOR 12 is hydrogen (that is, a carboxyl group), the hydrogen atom may dissociate (that is, a carbonate group) or may be in a salt state. Also, when R 24 of -SO2OR 24 is a hydrogen atom (that is, a sulfo group), the hydrogen atom may dissociate (that is, a sulfonate group) or may be in a salt state. Also, R1 and R 2 , R 3 and R 4 may combine with each other to form a ring.

[0021] 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 , -CONR 107 R 108 , -NHCONR 109 R 110 , -NHCOOR 111 , -SR 112 , -SO2R 113 , -SO2OR 114 , -NHSO2R 115 or -SO2NR 116 R 117 and the like. 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. Note that when R 102 in -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 in -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.

[0022] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of carbon atoms 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 part of the aralkyl group is the same as the above alkyl group. The aryl part 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 have substituents or may be unsubstituted. Examples of the substituents include the above-mentioned "substituents".

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

Chemical formula

[0024] In general formula (3), R 5 ~R 8Each is 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 、-SR 62 、-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 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 which may have a substituent. Note that when R 52 in -COOR 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, when R 64 in -SO2OR 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.

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

[0026] Specific examples of squarylium compounds are shown below. Note that the present invention is not limited thereto.

[0027]

Chem.

[0028]

Chem.

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

[0030] General formula (4)

Chem.

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

[0032] R 1x and R 1y each independently are preferably an aryl group or a heteroaryl group, more preferably an aryl group. Also, R1x and R 1y The alkyl group, aryl group, and heteroaryl group represented by may have substituents 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 13 each independently represents a hydrocarbon group or a heteroaryl group. Examples of the substituent also include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among these, 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 are preferred. R 1x and R 1y The group represented by is preferably an alkoxy group having a branched alkyl group or an aryl group having a group represented by -OCOR 11 as a substituent. The number of carbon atoms of the branched alkyl group is preferably 3 to 30, more preferably 3 to 20.

[0033] R 2 and R 3 At least one of is preferably an electron-withdrawing group, R 2 represents an electron-withdrawing group, and R 3More preferably, it represents a heteroaryl group. The electron-withdrawing group represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more, and examples thereof include a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfinyl group, an arylsulfinyl group, a heteroaryl group, etc. These electron-withdrawing groups may be further substituted. 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, and 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. Two Rs in the general formula (4) 2 may be the same or different from each other. Also, two Rs in the general formula (4) 3 may be the same or different from each other.

[0034] 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 and more preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by -BR 4x R 4y and particularly preferably a group represented by -BR 4x R 4y The substituent represented by R 4x R 4y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. Two Rs in the general formula (4) 4 may be the same or different from each other.

[0035] Specific examples of the pyrrolopyrrole compound are shown below. 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 International Publication No. 2015 / 166873. However, the present invention is not limited thereto.

[0036]

Chemical formula

[0037] (Naphthalocyanine compound) As the naphthalocyanine compound, a compound represented by the following general formula (5) is preferable.

[0038] General formula (5)

Chemical formula

[0039] In general formula (5), X1 to X8, Y l ~Y8 each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Further, X1 to X8 may each independently be bonded to each other to form an aromatic ring which may have a substituent. However, any one or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 are bonded to each other to form an aromatic ring which may have a substituent. Z is a polymer moiety containing a monomer unit represented by the following general formula (6) or a phosphorus compound moiety represented by the following general formula (7), and * is a bond to Al.

[0040] 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, etc. The "alkyl group having a substituent" includes, for example, 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, etc.

[0041] The "aryl group" of the aryl group which may have a substituent includes, for example, phenyl group, naphthyl group, anthryl group, etc. 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, etc.

[0042] The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes, for example, cyclopentyl group, cyclohexyl group, adamantyl group, etc. The "cycloalkyl group having a substituent" includes, for example, 2,5-dimethylcyclopentyl group, 4-tert-butylcyclohexyl group, etc.

[0043] Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, etc., and examples of the "heterocyclic group having a substituent" include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, etc.

[0044] The "alkoxyl group" of the alkoxyl group which may have a substituent includes, for example, a linear or branched alkoxyl group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyl oxy group, 2,3-dimethyl-3-pentyloxy, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, a 2-ethylhexyloxy group, etc. Examples of the "alkoxyl group having a substituent" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, a benzyloxy group, etc.

[0045] Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, etc. Examples of the "aryloxy group having a substituent" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

[0046] Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc. The "alkylthio group having a substituent" includes, for example, a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, and the like.

[0047] 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. The "arylthio group having a substituent" includes, for example, a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like.

[0048] 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.

[0049] General formula (6)

Chemical formula

[0050] In general formula (6), X is -CONH-R 25 -, -COO-R 26 -, -CONH-R 27 -O-, -COO-R 28 -O-, R 25 ~R 28 represents an alkylene group or an arylene group in which the carbon atoms are connected to each other by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. R 31 represents hydrogen or a methyl group.

[0051] 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.

[0052] The polymer moiety containing the monomer unit represented by the general formula (6) is obtained, for example, by polymerizing monomers such as (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, and (2-(meth)acryloyloxyisopropyl) acid phosphate. In addition, monomers other than these monomers (hereinafter also referred to as other monomers) can be used in combination and copolymerized.

[0053] Examples of the 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.

[0054] The weight average molecular weight of the polymer moiety is preferably from 5,000 to 20,000, more preferably from 8,000 to 15,000. Having an appropriate molecular weight improves the optical properties and heat resistance.

[0055] The glass transition temperature (Tg) of the polymer moiety is preferably from -50 to 150°C, more preferably from 20 to 80°C. An appropriate Tg improves the optical properties.

[0056] General formula (7)

Chemical formula

[0057] In general formula (7), R 29 and R 30Each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R 29 and R 30 may be bonded to each other to form a ring.

[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 general formula (5).

[0059] From the viewpoints of dispersibility and color characteristics, in the general formula (7), 29 at least one of R 30 and R 29 is preferably 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 30 and R 29 are an aryl group or an aryloxy group, and it is even more preferable that both R 30 and R

[0060] The naphthalocyanine compound is more preferably a compound represented by the following general formula (8).

[0061] General formula (8)

Chemical formula

[0062] In the general formula (8), Y9 to Y 16 , R8 to R 21Each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z is a polymer moiety containing a monomer unit represented by the general formula (6) or a phosphorus compound moiety represented by the general formula (7), and * is a bond to Al.

[0063] 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 the general formula (5).

[0064] In the general formula (8), Y9 to Y 16 , R8 to R 21 From the viewpoints of dispersibility and color characteristics, a hydrogen atom, a halogen atom, or an alkoxyl group which may have a substituent is preferable.

[0065] Specific examples of the naphthalocyanine compound are shown below. However, the present invention is not limited thereto.

[0066]

Chemical formula

[0067]

Chemical formula

[0068]

Chemical formula

[0069]

Chem.

[0070] (Indigo compound) The indigo compound is preferably a compound represented by the following general formula (9) or / and general formula (10).

[0071] General formula (9) General formula (10)

Chem.

[0072] In general formula (9) and general formula (10), X1 to X 40 are each independently 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.

[0073] 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, etc. The "alkyl group having a substituent" includes, for example, 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, etc.

[0074] The "aryl group" of the aryl group which may have a substituent includes, for example, phenyl group, naphthyl group, anthryl group, etc. 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, etc.

[0075] 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, etc. 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.

[0076] The "aryloxy group" of the aryloxy group which may have a substituent includes, for example, phenoxy group, naphthoxy group, anthryloxy group and the like, 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.

[0077] 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.

[0078] The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes, for example, cyclopentyl group, cyclohexyl group, adamantyl group and the like. The "cycloalkyl group having a substituent" includes, for example, 2,5-dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

[0079] The "alkylthio group" of the alkylthio group which may have a substituent includes, for example, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like. The "alkylthio group having a substituent" includes, for example, methoxyethylthio group, aminoethylthio group, benzylaminoethylthio group, methylcarbonylaminoethylthio group, phenylcarbonylaminoethylthio group and the like.

[0080] The "arylthio group" of the arylthio group which may have a substituent includes, for example, phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group and the like. Examples of the "arylthio group having a substituent" include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

[0081] 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.

[0082] 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.

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

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

[0085] Among the above substituents, X1 to X 40 Preferred substituents include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and -SO3H.

[0086] M represents a metal atom. Examples of the metal atom include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, Ba, and the like. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred.

[0087] Hereinafter, specific examples of the indigo compound are shown. Note that the present invention is not limited thereto.

[0088]

Chemical formula

[0089]

Chemical formula

Chemical formula

Chemical formula

[0090] 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 two or more 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 is broadened and near-infrared rays in a wide wavelength range can be absorbed.

[0091] From the viewpoint of near-infrared absorption property, the content of the near-infrared absorbing dye (A) is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0092] [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.

[0093] [Resin (B)] The resin (B) is used, for example, for the purpose of dispersing the near-infrared absorbing dye (A) and the like in the photosensitive composition and for the purpose of imparting resistance to the cured film. 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. The resin (B) includes a resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2), and a resin (B2) not having a blocked isocyanate group-containing monomer unit (b1).

[0094] (Resin (B1)) The photosensitive composition of the present invention contains a resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2) (hereinafter, also simply referred to as resin (B1)). Thereby, even in post-baking at 130 ° C or lower, curing proceeds and the resistance of the cured film is improved.

[0095] The method for producing the resin (B1) is not particularly limited, and known methods can be used. For example, it can be obtained by copolymerizing a monomer that forms a blocked isocyanate group-containing monomer unit (b1), a monomer that forms an acidic group-containing monomer unit (b2), and optionally other copolymerizable monomers.

[0096] [[Blocked Isocyanate Group-Containing Monomer Unit (b1)]] The blocked isocyanate group-containing monomer is a compound in which the isocyanate group in the isocyanate group-containing monomer is protected with a compound that desorbs by heat (hereinafter, also referred to as a blocking agent). The desorption temperature of the blocking agent is preferably 70 to 150 ° C, more preferably 80 to 135 ° C.

[0097] Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, methacryloyl isocyanate, and the like. Also, an equimolar reaction product of 2-hydroxyalkyl (meth) acrylate and a diisocyanate compound can be used. Among these, 2-isocyanatoethyl (meth) acrylate and 2-isocyanatopropyl (meth) acrylate are preferred.

[0098] Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0099] Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, etc. Examples of the phenol compound include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, carbazole, etc. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. Diethyl malonate is preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc. 3,5-dimethylpyrazole is preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, etc. Examples of imide compounds include succinimide, maleimide, maleic imide, phthalimide, etc. Examples of urea compounds include urea, thiourea, ethylene urea, etc. Examples of imine compounds include ethylene imine, polyethylene imine, etc. Examples of bisulfite compounds include sodium bisulfite, potassium bisulfite, etc.

[0100] The blocking agent can be used alone or in combination of two or more.

[0101] The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. From the viewpoints of the protection reaction and the deprotection reaction, more preferably at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0102] Examples of the monomer containing a blocked isocyanate group include, for example, the following compounds. The present invention is not limited thereto.

[0103]

Chemical formula

[0104] Commercially available products of the monomer containing a blocked isocyanate group include Karenz MOI-DEM (desorption temperature of the blocking agent: 85 - 95 °C), MOI-BP (desorption temperature of the blocking agent: 105 - 115 °C), MOI-BM (125 - 135 °C), etc. manufactured by Showa Denko KK.

[0105] From the viewpoints of storage stability and low-temperature baking, the content of the monomer unit (b1) containing a blocked isocyanate group is preferably 1 to 50 mol%, more preferably 5 to 40 mol% in all the constituent units of the resin (B1).

[0106] Examples of the monomer unit containing an acidic group (b2) include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, and the like.

[0107] From the viewpoint of pattern formability, the content of the monomer unit containing an acidic group (b2) is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all the constituent units of the resin (B1).

[0108] The resin (B1) can contain a monomer unit containing a hydroxyl group (b3). Examples of the monomer containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, and the like.

[0109] The resin (B1) can contain a monomer unit containing an epoxy group (b4). ​​​Epoxy group-containing monomers include, for example, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, and the like.

[0110] [Polymerizable unsaturated group-containing monomer unit (b5)] Resin (B1) can contain a polymerizable unsaturated group-containing monomer unit (b5).

[0111] The method for incorporating a polymerizable unsaturated group-containing monomer unit (b5) into resin (B1) includes, for example, the following methods (i) to (iii).

[0112] [Method (i)] There is a method (i) in which an acidic group of an acidic group-containing monomer is added to the epoxy group of the epoxy group-containing monomer unit (b4) contained in resin (B1).

[0113] [Method (ii)] There is a method (ii) in which an epoxy group of an epoxy group-containing monomer is added to the acidic group of the acidic group-containing monomer unit (b2) contained in resin (B1).

[0114] In addition, a product obtained by reacting an acid anhydride with the hydroxyl group generated by the reactions of methods (i) and (ii) is also useful as the polymerizable unsaturated group-containing monomer unit (b5).

[0115] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0116] <Method (iii)> There is a method (iii) of reacting the isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the hydroxyl group-containing monomer unit (b3) contained in the resin (B1).

[0117] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

[0118] 〔Alicyclic hydrocarbon-containing monomer unit (b6)〕 The resin (B1) can contain an alicyclic hydrocarbon-containing monomer unit (b6). Examples of the alicyclic hydrocarbon-containing monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Among these, from the viewpoint of pattern formation, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0119] 〔Monomer unit (b7) formed from the monomer represented by the general formula (1)〕 The resin (B1) can contain a monomer unit (b7) formed from the monomer represented by the following general formula (1).

[0120] General formula (1)

Chemical formula

[0121] In general formula (1), R1 represents a hydrogen atom or a methyl group. R2 represents an alkylene group having 2 or 3 carbon atoms. n represents an integer from 1 to 15. When n is 2 or more, the plurality of R2s may be the same or different from each other.

[0122] Examples of the monomer represented by general formula (1) include ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate of paracumylphenol, and the like.

[0123] [Other monomer unit (b8)] Resin (B1) can contain monomer units other than (b1) to (b7) (hereinafter, also referred to as other monomer unit (b8)). Examples of other monomers include acrylic acid esters such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO) modified (meth)acrylate of phenol, EO or PO modified (meth)acrylate of nonylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene; (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; N-substituted maleimides such as phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine; Dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl) 2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl) 2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl) 2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more. Yes.

[0124] From the perspective of low-temperature baking, the weight-average molecular weight (Mw) of resin (B1) is preferably 5,000 to 40,000, more preferably 5,000 to 30,000.

[0125] From the perspective of pattern formation, the acid value of resin (B1) is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g.

[0126] From the viewpoints of pattern formability and low-temperature baking, the content of the resin (B1) is preferably 10% by mass or more, more preferably 10 to 90% by mass, based on 100% by mass of the resin (B).

[0127] (Resin (B2)) The resin (B2) is a resin (B2) having no monomer unit (b1) containing a blocked isocyanate group, and is a resin having at least one monomer unit selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the general formula (1), a resin (B3) of a dispersion resin other than the above resin, and other resins (B4) other than these. The photosensitive composition of the present invention can more effectively suppress agglomerated foreign matters by containing a resin having at least one monomer unit selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the general formula (1).

[0128] The resin having at least one monomer unit selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the general formula (1) can further contain monomer units other than (b6) and (b7). For example, the monomer units of (b2) to (b5) and (b8) described above can be mentioned.

[0129] From the viewpoint of suppressing agglomerated foreign matters, the weight average molecular weight (Mw) of the resin having at least one monomer unit selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the general formula (1) is preferably 5,000 to 40,000, more preferably 5,000 to 30,000.

[0130] From the viewpoint of suppressing agglomerated foreign matters, the acid value of the resin having at least one monomer unit selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the general formula (1) is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g.

[0131] The content of the resin having at least one monomer unit selected from the alicyclic hydrocarbon-containing monomer unit (b6) and the monomer unit (b7) formed from the monomer represented by the general formula (1) is preferably 10 to 90% by mass in 100% by mass of the resin (B) from the viewpoint of suppressing agglomerated foreign matters.

[0132] (Resin (B3)) The resin (B3) is a dispersion resin and is a resin other than the resin (B1) and the resin having at least one monomer unit selected from the alicyclic hydrocarbon-containing monomer unit (b6) and the monomer unit (b7) formed from the monomer represented by the general formula (1). The resin (B3) is preferably a resin having an adsorbing group with high affinity for the near-infrared absorbing dye (A). The adsorbing group preferably has at least one of a basic group and an acidic group, and more preferably has a basic group from the viewpoint of suppressing agglomerated foreign matters.

[0133] 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.

[0134] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0135] Examples of the resin type of the resin (B3) include 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 amidates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group and salts thereof, (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 addition compounds, phosphate ester-based, and the like.

[0136] The structure of the resin (B3) includes, for example, a random structure, a block structure, a graft structure, a comb structure, a star structure, etc. Among these, from the viewpoint of dispersion stability, a block structure or a comb structure is preferable.

[0137] The resin (B3) is, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc. manufactured by Big Chemie Japan Co., Ltd.; 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, etc. manufactured by Lubrizol Japan Co., Ltd.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF Japan Co., Ltd.; Ajisuper PA111, PB711, PB821, PB822, manufactured by Ajinomoto Fine-Techno Co., Ltd.,Examples of the resin include those described in PB824, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2012-255128, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, JP-A-2017-206689, JP-A-2019-095548, etc.

[0138] From the viewpoint of suppressing agglomerated foreign matters, the content of the resin (B3) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0139] (Other resin (B4)) The other resin (B4) is a resin other than the resin (B2) and the resin (B3). Examples of the other resin (B4) include (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, and the like.

[0140] The resin (B) can be used alone or in combination of two or more.

[0141] The content of the resin (B) 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.

[0142] [Polymerizable compound (C)] Examples of the polymerizable compound (C) include monomers and oligomers having a polymerizable unsaturated group. The polymerizable compound (C) forms a film by reaction. Examples of the polymerizable unsaturated group include vinyl groups of ethylenically unsaturated double bonds, (meth)allyl groups, (meth)acryloyl groups, and the like.

[0143] (Polymerizable compound (C1) having at least one group selected from a hydroxyl group and an acidic group) From the viewpoint of low-temperature baking, the photosensitive composition of the present invention preferably contains, as the polymerizable compound (C), a polymerizable compound (C1) having at least one group selected from a hydroxyl group and an acidic group (hereinafter, also simply referred to as polymerizable compound (C1). However, compounds having a dendrimer structure or a hyperbranched structure are excluded). Thereby, the isocyanate group from which the blocking agent has been eliminated reacts with the hydroxyl group or the acidic group, and the resistance is improved. Examples of the acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. Among these, a carboxyl group is preferable.

[0144] The polymerizable compound (C1) preferably has two or more polymerizable unsaturated groups, and more preferably three or more polymerizable unsaturated groups.

[0145] Examples of the polymerizable compound having a hydroxyl group include ethylene oxide-modified diacrylate isocyanurate, pentaerythritol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, etc. Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable.

[0146] Examples of the polymerizable compound having an acidic group include esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohols and (meth) acrylic acid with dicarboxylic acids; esterified products of polyvalent carboxylic acids with monohydroxyalkyl (meth) acrylates, etc. Polyhydric alcohols include, for example, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like. Dicarboxylic acids include, for example, malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like. Polycarboxylic acids include, for example, trimellitic acid, pyromellitic acid, and the like. Mono-hydroxyalkyl (meth) acrylates include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

[0147] Commercially available products of polymerizable compounds having an acidic group include Biscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521, etc. manufactured by Toagosei Co., Ltd.

[0148] The polymerizable compound (C1) can be used alone or in combination of two or more.

[0149] From the viewpoint of low-temperature baking, the content of the polymerizable compound (C1) is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the resin (B1).

[0150] (Polymerizable compound (C2) having a structure selected from a dendrimer structure or a hyperbranched structure) From the viewpoints of pattern formation and low-temperature baking, the photosensitive composition of the present invention more preferably contains, as the polymerizable compound (C), a polymerizable compound (C2) having a structure selected from a dendrimer structure or a hyperbranched structure (hereinafter, also simply referred to as the polymerizable compound (C2)). In particular, it is useful when containing a colorant (F) described later.

[0151] A polymerizable compound having a dendrimer structure has a chemical structure in which branching is regularly repeated from the chemical structure constituting the core (hereinafter also referred to as the core part) to the outside, and a polymerizable unsaturated group is bonded to the terminal thereof, and has a spherical and highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to the dendrimer structure. Therefore, generally, compared with a linear polymerizable compound, the distance between the polymerizable unsaturated groups in the molecule is close and the density is high, so it is less affected by oxygen inhibition, reacts sufficiently by exposure, and even when the amount of photoinitiator or the exposure amount is small or in the case of low-temperature baking, it can react sufficiently and a cured film with higher resistance can be obtained.

[0152] From the viewpoints of pattern formability and low-temperature baking, the polymerizable compound (C2) more preferably has an average of 6 to 18 polymerizable unsaturated groups.

[0153] From the viewpoints of pattern formability and low-temperature baking, the polymerizable unsaturated group of the polymerizable compound (C2) is preferably at least one selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, and more preferably a (meth)acryloyl group.

[0154] As the polymerizable compound (C2), those synthesized as appropriate may be used, or commercially available products may be used.

[0155] As a method 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 polymerizable unsaturated group to the inside, and a combination of these two are known. For example, using the convergent method, in 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 substituents of two types in one molecule. For example, hyperbranched polyester can be obtained by polycondensation using 3,5-dihydroxybenzoic acid as a raw material. In this case, although a hydroxyl group exists at the terminal, a polymerizable compound having a hyperbranched structure can be obtained by reacting (meth)acrylic acid therewith.

[0156] Commercially available products of the polymerizable compound (C2), for example, commercially available products of compounds having a dendrimer structure or a hyperbranched structure include, for example, "Viscote #1000" (dendrimer structure, average number of acryloyl groups 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., "Miramer SP-1106" (dendrimer structure, average number of acryloyl groups 18), "Miramer SP-1108" (dendrimer structure, average number of acryloyl groups 13) manufactured by Miwon Specialty Chemical Co., Ltd., "CN2301" (hyperbranched structure, average number of acryloyl groups 9), "CN2302" (hyperbranched structure, average number of acryloyl groups 16), "CN2303" (hyperbranched structure, average number of acryloyl groups 6), "CN2304" (hyperbranched structure, average number of acryloyl groups 18) manufactured by Sartomer Co., Ltd., "Etercure6361-100" (hyperbranched structure, average number of acryloyl groups 8), "Etercure6362-100" (hyperbranched structure, average number of acryloyl groups 12), "Etercure6363" (hyperbranched structure, average number of acryloyl groups 16), "EtercureDR-E522" (hyperbranched structure, average number of acryloyl groups 15) manufactured by Eternal Materials Co., Ltd., and the like.

[0157] The polymerizable compound (C2) can be used alone or in combination of two or more.

[0158] From the viewpoints of pattern formability and low-temperature baking, the content of the polymerizable compound (C2) is preferably 30% by mass or more in 100% by mass of the polymerizable compound (C).

[0159] (Other polymerizable compound (C3)) The polymerizable compound (C) can contain a polymerizable compound other than the polymerizable compound (C1) and the polymerizable compound (C2) (hereinafter also referred to as other polymerizable compound (C3)).

[0160] Examples of the other polymerizable compound (C3) include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9 - bis[4-(2 - hydroxyethoxy)phenyl]fluorene diacrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO - modified tri(meth)acrylate, trimethylolpropane EO - modified tri(meth)acrylate, isocyanuric acid EO - modified di(meth)acrylate, isocyanuric acid EO - modified tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,6 - hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, urethane (meth)acrylate and other various acrylic acid esters and methacrylic acid esters, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N - vinylformamide, acrylonitrile, etc.

[0161] Commercially available products of other polymerizable compounds (C3) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, T-1420(T), RP-1040, DPEA-12, D-310, DPCA-20, DCPA-30, DCPA-60, DPCA-120 manufactured by Nippon Kayaku Co., Ltd.; Aronix M-208, M-211B, M-220, M-225, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460 manufactured by Toagosei 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, 1605 manufactured by Daicel Ornex Co., Ltd.; AH-600, UA-306H, UA-306T, UA-306I, UA-510H manufactured by Kyoeisha Chemical Co., Ltd., and the like.

[0162] Other polymerizable compounds (C3) can be used alone or in combination of two or more.

[0163] The content of the polymerizable compound (C) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0164] [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.

[0165] 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-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; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc. can be mentioned.

[0166] 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, etc. manufactured by Daito Chemicals can be mentioned. In addition, oxime compounds described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, WO2015 / 036910, etc. can also be mentioned.

[0167] 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).

[0168] Specific examples of the oxime compound include, for example, the following. Note that the present invention is not limited to these.

[0169]

Chemical formula

Chemical formula

[0170] The method for producing the compounds of chemical formulas (11) to (17) 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, WO 2015 / 036910, WO 2015 / 152153, JP-T-2016-504270, JP-T-2017-512886, JP-T-2017-523465, JP-A-2021-011486, etc. can be mentioned.

[0171] 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).

[0172] [Sensitizer (E)] The photosensitive composition of the present invention can contain a sensitizer (E).

[0173] 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, polymethine dyes such as coumarin compounds, ketocoumarin compounds, 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, organoruthenium complexes, or benzophenone compounds, etc. Among these, from the viewpoints of developability and pattern formability, thioxanthone compounds (E1) or benzophenone compounds (E2) are preferred.

[0174] (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.

[0175] (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.

[0176] The sensitizer (E) can be used alone or in combination of two or more.

[0177] From the viewpoint of 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).

[0178] [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.

[0179] The colorant (F) may be either a pigment or a dye, and they can be used in combination.

[0180] (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 No. 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 No. 2014-134712, and the pigments described in Patent No. 6368844 are preferred, and C.I. Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are more preferred.

[0181] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, and the like.

[0182] Yellow pigments include, for example, pigments described in 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, JP-A-2012-226110, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A-2012-226110 are preferred.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] Examples of combinations that exhibit 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.

[0189] In the aspect of (1) above, for example, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment contains C.I. Pigment Violet 23. In the aspect of (2) above, for example, the red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment contains C.I. Pigment Violet 23. In the aspect of (3) above, for example, the red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the blue pigment contains one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6. In the aspect of (4) above, for example, the red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the green pigment contains one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63. In the aspect of (5) above, for example, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment contains one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment contains C.I. Pigment Violet 23. In the above aspect (6), for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment is C.I. Pigment Violet 23.

[0190] Among the above aspects (1) to (6), from the viewpoint of light shielding property, the aspect (5) is preferable.

[0191] Among the aspects of the above (5), it is more preferable that the yellow pigment contains C.I. Pigment Yellow 139, the blue pigment contains C.I. Pigment Blue 15:6, and the purple pigment contains C.I. Pigment Violet 23.

[0192] Table 1 shows the preferable mass ratios (mass %) of each organic pigment in each aspect.

[0193]

Table 1

[0194] Among the 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, navy blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc.

[0195] (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.

[0196] The acid dye preferably has an acidic group such as a sulfonic acid or a carboxylic acid. Further, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferred. Further, a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye is also preferred. Further, the salt-forming compound is easily converted into 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 acid dye and a compound having an onium base is also preferred because it is excellent in resistance (light resistance, solvent resistance). Note that as the compound having an onium base, a resin having a cationic group is preferred.

[0197] The basic dye can be used as it is, but a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it is excellent in resistance (light resistance, solvent resistance) and affinity with a pigment. Further, as the anion component acting as a counterion in the salt-forming compound of the 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 acid dye are preferred. Note that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

[0198] 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 their metal complex dyes, etc.

[0199] 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.

[0200] The colorant (F) can be used alone or in combination of two or more.

[0201] 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.

[0202] (Micronization of Pigment) The pigment is preferably used in a micronized form. The micronization 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 preferred. The average primary particle size determined by TEM (transmission electron microscope) of the micronized pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

[0203] The 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 heating 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 washing with water. 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 the salt milling treatment of the pigment, a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0204] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, and sodium sulfate, and sodium chloride (table salt) is preferred 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.

[0205] 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 is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent 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.

[0206] 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, those that are solid at room temperature, preferably water-insoluble, and preferably partially soluble in the above organic solvent are preferred. The addition amount of the resin is preferably 2 to 200 parts by mass, per 100 parts by mass of the pigment.

[0207] [Dye Derivative (G)] The photosensitive composition of the present invention can contain a dye derivative (G).

[0208] The dye derivative (G) is not particularly limited, and examples include dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (G) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, a phosphate group, etc., and amine salts thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and a compound 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.

[0209] Specifically, examples of diketopyrrolopyrrole-based pigment derivatives include those described in JP-A No. 2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A No. 2017-156397; examples of phthalocyanine-based pigment derivatives include those described in JP-A No. 2007-226161, WO 2016 / 163351, JP-A No. 2017-165820, Patent No. 5753266; examples of anthraquinone-based pigment derivatives include 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; examples of quinacridone-based pigment derivatives include those described in JP-A No. 48-54128, JP-A No. 03-9961, JP-A No. 2000-273383; examples of dioxazine-based pigment derivatives include those described in JP-A No. 2011-162662; examples of thiazine indigo-based pigment derivatives include those described in JP-A No. 2007-314785; examples of triazine-based pigment derivatives include 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; examples of benzoisoindole-based pigment derivatives include those described in JP-A No. 2009-57478; examples of quinophthalone-based pigment derivatives include those described in JP-A No. 2003-167112, JP-A No. 2006-291194, JP-A No. 2008-31281, JP-A No. 2012-226110; examples of naphthol-based pigment derivatives include those described in JP-A No. 2012-208329, JP-A No. 2014-5439; examples of azo-based pigment derivatives include those described in JP-A No. 2001-172520, JP-A No. 2012-172092; examples of acidic substituents include those described in JP-A No. 2004-307854; examples of basic substituents include 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.

[0210] The dye derivative (G) can be used alone or in combination of two or more.

[0211] [Thermosetting compound (H)] The photosensitive composition of the present invention can contain a thermosetting compound (H). Thereby, the thermosetting compound (H) reacts in the heating step, and the crosslinking density increases, so the heat resistance is improved.

[0212] The thermosetting compound (H) may be a low molecular compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferred.

[0213] (Epoxy compound (H1)) The epoxy compound (H1) includes, for example, polycondensates of bisphenols (such as bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (such as phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (such as formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthalaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (such as dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α’,α’-benzenedimethanol, biphenyldimethanol, α,α,α’,α’-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α,α’-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

[0214] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, Inc., EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 manufactured by Japan Epoxy Resins Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154, Celloxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S, etc. manufactured by Nissan Chemical Industries, Ltd.

[0215] The content of the epoxy compound (H1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0216] (Oxetane compound (H2)) The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0217] Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, and the like.

[0218] Commercially available products include, for example, OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 212 manufactured by Toagosei Co., Ltd., and the like.

[0219] Examples of the difunctional oxetane compounds include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether, and the like.

[0220] Examples of the commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0221] Oxetane compounds having three or more functional groups include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, oxetane-modified phenol novolak resins described in Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0222] The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0223] Melamine compounds are compounds having a melamine ring structure. Melamine compounds are preferably methylol-type or ether-type compounds, and more preferably melamine compounds having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Appropriate numbers of methylol groups and ether groups make it easy to obtain heat resistance without excess or deficiency.

[0224] Commercially available products include, for example, Nikkalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 manufactured by Sanwa Chemical Co., Ltd., Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Sytrex Industries Co., Ltd., and the like.

[0225] Among these, Nikkalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 manufactured by Nippon Sytrex Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferable in terms of increasing the crosslink density.

[0226] The thermosetting compound (H) can be used alone or in combination of two or more.

[0227] [Hardener (Hardening Accelerator)] In order to assist the curing of the thermosetting compound (H), a curing agent (curing accelerator) can be used in combination with the photosensitive composition of the present invention. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.), and the like.

[0228] The curing agent can be used alone or in combination of two or more.

[0229] 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 (H).

[0230] [Thiol-based chain transfer agent (I)] The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with the photopolymerization initiator (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.

[0231] The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0232] 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 included.

[0233] The thiol-based chain transfer agent (I) can be used alone or in combination of two or more.

[0234] The content of the thiol-based chain transfer agent (I) is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass, based on 100 parts 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.

[0235] [Polymerization inhibitor (J)] The photosensitive composition of the present invention can contain a polymerization inhibitor (J).

[0236] The polymerization inhibitor (J) is, for example, an alkylcatechol compound 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, an alkylresorcinol compound 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, an alkylhydroquinone compound such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, a phosphine compound such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, a phosphine oxide compound such as trioctylphosphine oxide, triphenylphosphine oxide, a phosphite compound such as triphenylphosphite, trisnonylphenylphosphite, pyrogallol, phloroglucin, and the like.

[0237] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0238] [Ultraviolet absorber (K)] The photosensitive composition of the present invention can contain an ultraviolet absorber (K).

[0239] The ultraviolet absorber (K) 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, etc.

[0240] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0241] Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, Ltd., Adeka Stab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA Corporation, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

[0242] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and the like.

[0243] Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, Ltd., Adeka Stab LA-46, LA-F70 manufactured by ADEKA Corporation, CYASORB UV-1164 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0244] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0245] Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cypro Kasei Co., Ltd., Adeka Stab 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0246] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0247] The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator (D) and the ultraviolet absorber (K).

[0248] [Antioxidant (L)] The photosensitive composition of the present invention can contain an antioxidant (L). The antioxidant (L) prevents yellowing caused by oxidation of the photopolymerization initiator (D) and the thermosetting compound (H) in the photosensitive coloring composition during heat curing or 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 the amount of the photopolymerization initiator (D) is increased or the thermosetting compound is blended, 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 (L) is preferably a compound that does not contain a halogen atom.

[0249] The antioxidant (L) includes, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0250] Hindered phenol antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. can be mentioned.

[0251] Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation, Keminox 101, 179, 76, 9425 manufactured by Chemipro Kasei Co., Ltd., Irganox 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790, CY-2777 manufactured by Sankyo Chemical Co., Ltd., etc.

[0252] Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, the polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], the ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis〔4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl〕-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyrperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyrperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0253] Commercially available products include, for example, AdekaStab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Ltd.; and Cyasorb-UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0254] Phosphorus-based antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyldiphosphonite, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylenebis(4,6-di-t-butylphenyl) phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc.

[0255] Commercially available products include, for example, Adeka Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation, IRGAFOS 168 manufactured by BASF Japan Ltd., Hostanox P-EPQ manufactured by Clariant Chemicals, etc.

[0256] Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc.

[0257] Commercially available products include, for example, Adeka Stab AO-412S, AO-503 manufactured by ADEKA Corporation, Keminox PLS manufactured by Chemipro Kasei Co., Ltd., etc.

[0258] The antioxidant (L) can be used alone or in combination of two or more.

[0259] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile components of the photosensitive composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0260] [Leveling agent (M)] The photosensitive composition of the present invention can contain a leveling agent (M). Thereby, the wettability and drying property with respect to the substrate during coating are further improved. Examples of the leveling agent (M) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc.

[0261] Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or terminals.

[0262] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd.; 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.

[0263] Examples of the fluorosurfactant include a surfactant or a leveling agent having a fluorocarbon chain.

[0264] Commercially available products include, for example, 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.; Phthalgent 602A manufactured by Neos Corporation.

[0265] 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 distyrylphenyl 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.

[0266] 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, Aminon 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.

[0267] Examples of cationic surfactants include alkylamine salts and quaternary alkylammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0268] Commercially available products include, for example, Kao's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0269] 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, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate esters, and the like.

[0270] 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.

[0271] 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.

[0272] Commercially available products include Anhtol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0273] The leveling agent (M) can be used alone or in combination of two or more.

[0274] The content of the leveling agent (M) 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.

[0275] [Storage Stabilizer (N)] The photosensitive composition of the present invention can contain a storage stabilizer (N). Thereby, the viscosity of the photosensitive composition over time is stabilized. Examples of the storage stabilizer (N) 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 and the like.

[0276] The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye (A).

[0277] [Adhesion improver (O)] The photosensitive composition of the present invention can contain an adhesion improver (O). 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.

[0278] The adhesion promoter (O) includes, for example, silane coupling agents. Examples of silane coupling agents include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; amino silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and the hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl silanes such as p-styryltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane; sulfide silanes such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane.

[0279] The adhesion promoter (O) can be used alone or in combination of two or more.

[0280] The content of the adhesion promoter (O) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the near-infrared absorbing dye (A).

[0281] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0282] The organic solvent (P) 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 and the like. 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 preferred.,

[0283] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0284] <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 resin (B), an organic solvent (P), etc. and performing a dispersion treatment to produce a dispersion. Then, the resin (B), the polymerizable compound (C), the photoinitiator (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.

[0285] Dispersion machines that perform dispersion processing include, for example, 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, etc.

[0286] 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 with high dispersion stability is easily obtained when it has an appropriate particle diameter.

[0287] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using Microtrac UPA-EX150 of Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power-spectrum method), set the particle permeability to the absorption mode, the particle shape to non-spherical, and the D50 particle diameter as the average diameter. As the dilution solvent for measurement, use the organic solvents used for dispersion respectively. 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.

[0288] 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 with 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.

[0289] [Cured film] The cured film of the present invention is a cured product of the photosensitive composition of the present invention, and the formed film is cured by exposure or the like.

[0290] [Manufacturing method of 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) applying a photosensitive composition onto a substrate to form a layer of the composition; (2) exposing the layer in a pattern through a mask; (3) subjecting the unexposed portion to alkali development to form a patterned cured film; and (4) heat-treating (post-baking) the pattern. In the present invention, it is preferable to perform the production of the cured film at a temperature of 150°C or lower throughout all the steps, and more preferably at a temperature of 130°C or lower.

[0291] Hereinafter, the method for manufacturing the cured film will be described in detail.

[0292] (Step (1)) In the 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. If necessary, it is dried (pre-baked) at a temperature of 50 to 100°C for 10 to 120 seconds using an oven, hot plate, or the like. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an imaging element such as a CCD or a CMOS formed on its surface. Further, a primer layer may be provided on the substrate, if necessary, for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface. The film thickness of the layer is preferably applied so as to be 0.05 to 10.0 μm after drying, and more preferably so as to be 0.3 to 5 μm.

[0293] (Step (2)) In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, a cured film is obtained. Examples of the radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0294] (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 into an aqueous alkali solution, and only the cured portion remains to obtain a patterned cured film. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved.

[0295] Examples of the development method include the dip method, spray method, paddle method, etc. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferably washed with pure water.

[0296] (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 150°C or lower, more preferably 130°C or lower. Also, the heating time is preferably about 5 minutes to 1 hour, more preferably about 5 minutes to 30 minutes.

[0297] [Optical Filter] The optical filter of the present invention has a cured film. Examples of the optical filter include an infrared cut filter, an infrared transmission filter, etc. The optical filter of the present invention can be manufactured by the same method as the above-described cured film.

[0298] [Image Display Device] The image display device of the present invention has a cured film. When used in an image display device, the use of the cured film is not particularly limited, and examples include a color filter and 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 stripe-shaped black portions between red, blue, and green pixels, and dot-shaped and / or linear black patterns for TFT light shielding, etc.

[0299] 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 therebetween.

[0300] 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.

[0301] 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).

[0302] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is further formed thereon, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0303] 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.

[0304] 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 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.

[0305] 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).

[0306] Covering the color filter 22, a transparent protective film (not shown) is formed as necessary, and further on 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.

[0307] 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.

[0308] Examples of white LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, or 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 maximum within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm. Also, 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 being 0.2 or more and 0.7 or less is preferred.

[0309] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0310] Examples of LED2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0311] [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, there is no particular limitation. For example, on a substrate, there are 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 a form having the cured film of the present invention on the light-receiving element formation surface side or the side opposite to the formation surface can be mentioned. FIG. 2 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device provided with the cured film of the present invention.

[0312] 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 effect of light collection by the lens material 212 is weakened due to light diffusion, and the light reaching the imaging unit 202 is reduced. In addition, noise is also 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.

[0313] The solid-state imaging element 201 photoelectrically converts an optical image formed at the imaging unit 202, which is the light-receiving surface thereof, 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.

[0314] The imaging unit 202 is provided at the central portion of the surface of the chip substrate 206. Further, 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.

[0315] A plurality of electrode pads 208 are provided at the edge portion 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.

[0316] On the back surface of the circuit board 207, external connection terminals 209 are provided at positions substantially below the respective electrode pads 208. Each external connection terminal 209 is connected to the 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).

[0317] [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 an 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.

[0318] 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 a specific wavelength 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.

[0319] A resin film 314 that can transmit light having a wavelength that has passed 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, and a cured film obtained by curing the photosensitive composition of the present invention containing two or more pigments selected from the group consisting of red pigment, yellow pigment, blue pigment, green pigment, and purple pigment can be used. The infrared transmission filter 113 preferably shields light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.

[0320] A microlens 315 is disposed on the incident light side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.

[0321] 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.

[0322] According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like for recognizing an object to be detected for motion is possible. Further, according to this infrared sensor, since distance information can be obtained, photographing of an image including 3D information is also possible. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

[0323] 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 the 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.

[0324] In addition, the cured film of the present invention can also be used in applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is 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 micro LEDs and micro OLEDs include those described in JP-T-2015-500562 and JP-T-2014-533890.

[0325] 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 for quantum dot displays.

Examples

[0326] 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 content concentration refers to the mass residue after standing in an oven at 230°C for 30 minutes.

[0327] Prior to the examples, each measurement method will be described.

[0328] 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.

[0329] (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. Using HLC-8220GPC (manufactured by Tosoh Corporation) 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 measurement was carried out at an oven temperature of 40 °C, using a tetrahydrofuran (THF) solution as the eluent, and at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 mass% of the above eluent and 20 microliters were injected. The molecular weight is in terms of polystyrene conversion value.

[0330] (Acid value of the resin) To 0.5 - 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 carried out using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0331] (Amine value of the resin) The amine value of the resin is the value obtained by converting the total measured amine value (mgKOH / g) into non-volatile content in accordance with the method of ASTM D 2074.

[0332] (Production of near-infrared absorbing dye (A)) (Near-infrared absorbing dye (A-1)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 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 reaction system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene 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 separating the obtained black-brown precipitate by filtration, 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 (18) 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 one day and night and pulverized to obtain a micronized near-infrared absorbing dye (A-1).

[0333] Chemical formula (18)

Chemical formula

[0334] (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 dark brown solid obtained by distilling toluene 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 filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorbing dye (A-2) represented by the following chemical formula (19). A micronized near-infrared absorbing dye (A-2) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0335] Chemical formula (19) [Chemical formula]

[0336] (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 raising the temperature, 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, 140 parts of compound a were added to 1,500 parts of concentrated sulfuric acid in a reaction vessel 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 were added to 200 parts of N-methylpyrrolidone, and after thorough stirring and mixing, the mixture was heated to 50°C. To this solution, 10 parts of compound b were 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 near-infrared absorbing dye (A-3) which is a mixture (mixing ratio: n1:n2:n3:n4 = 7:19:59:15) represented by the following chemical formula (20). A micronized near-infrared absorbing dye (A-3) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0337] Chemical formula (20)

Chemical formula

[0338] (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 (21) was obtained. A micronized near-infrared absorbing dye (A-4) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0339] Chemical formula (21)

Chemical formula

[0340] (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 dropwise 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 into an organic layer and water using dichloromethane, and the organic layer was concentrated to obtain 14.6 parts of compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and after raising the temperature, 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 (mixing ratio: dimer: trimer: tetramer = 81:17:2) of compounds represented by the following chemical formula (22). A micronized near-infrared absorbing dye (A-5) was obtained in the same manner as the near-infrared absorbing dye (A-1).

[0341] Chemical formula (22)

Chemical formula

[0342] <Production of resin (B)> (Resin (B1-1) solution) Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 257.3 g of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed. After that, while purging with nitrogen, the mixture was stirred and heated to 78°C. Next, 22.4 parts of dicyclopentanyl methacrylate, which is a monomer forming an alicyclic hydrocarbon-containing monomer unit (b6), 17.2 parts of methacrylic acid, which is a monomer forming an acidic group-containing monomer unit (b2), 49.8 parts of methyl methacrylate, which is a monomer forming other monomer units (b8), and 63.0 parts of Calenz MOI-DEM (2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester of malonic acid, manufactured by Showa Denko KK), which is a monomer forming a blocked isocyanate group-containing monomer unit (b1), were added to a mixture. And a solution prepared by adding and dissolving 11.0 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) in 78.7 g of PGMAc 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 (B1-1) solution. The resin (B1-1) had an acid value of 111 mgKOH / g and a weight average molecular weight of 9,500.

[0343] (Resin (B1-2) to (B1-11) solutions) Resins (B1-2) to (B1-11) were synthesized so as to have the molar ratios of the respective components described in Table 2, and PGMAc was added to make the nonvolatile content 40% by mass.

[0344]

Table 2

[0345] The curens MOI-BP described in Table 2 is 2-(3,5-diethylpyrazol-1-yl)carbonylaminoethyl methacrylate manufactured by Showa Denko K.K., and the curens MOI-BM is 2-[O-(1'-methylpropylideneamino)carboxamido]ethyl methacrylate manufactured by Showa Denko K.K. Also, GMA+AA represents a polymerizable unsaturated group-containing monomer unit (b5) obtained by adding acrylic acid (hereinafter also referred to as AA) to the epoxy group of glycidyl methacrylate (hereinafter also referred to as GMA).

[0346] (Resin (B2-1) solution) 196 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer, which was a reaction vessel. The temperature was raised to 80 °C, and after replacing the inside of the reaction vessel with nitrogen, a mixture of 20.2 parts of methacrylic acid, which is an acidic group-containing monomer, 21.8 parts of 2-hydroxyethyl methacrylate, which is a hydroxyl group-containing monomer, 38.9 parts of Aronix M-110 (para-cumylphenol ethylene oxide-modified acrylate manufactured by Toagosei Co., Ltd.), which is a monomer forming the monomer unit (b7), 39.0 parts of benzyl methacrylate, which is another monomer, 35.8 parts of n-butyl methacrylate, and 1.0 part of 2,2'-azobisisobutyronitrile was added dropwise through the dropping tube over 2 hours. After completion of the dropping, the reaction was further carried out for 3 hours. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added so that the non-volatile content became 40% by mass, and a resin (B2-1) solution was prepared. The acid value was 81 mgKOH / g, and the weight average molecular weight was 28,000.

[0347] (Resins (B2-2) and (B2-3) solutions) Resins (B2-2) and (B2-3) were synthesized so as to have the molar ratios of the respective components described in Table 3, and PGMAc was added to make the non-volatile content 40% by mass.

[0348]

Table 3

[0349] The GMA+AA+THPA described in Table 3 represents a polymerizable unsaturated group-containing monomer unit (b5) obtained by reacting the hydroxyl groups of GMA+AA with tetrahydrophthalic anhydride (hereinafter also referred to as THPA).

[0350] (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 to displace the system 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 in 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, and 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 heated and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added so that the non-volatile content became 30% by mass to prepare a resin (B3-1) solution.

[0351] (Resin (B3-2) solution) A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine. While flowing nitrogen, it 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, and the temperature was raised to 110 °C under a nitrogen stream 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., FUNCRYL FA-711MM) as the second block (A block) monomer were added to this reactor, and it 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 was 30% by mass 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.

[0352] (Resin (B3-3) solution) Into a reaction vessel equipped with a gas inlet tube, a temperature sensor, 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 had been half-esterified, and the reaction was terminated. PGMAc was added for dilution so that the non-volatile content was 30% by mass as measured by non-volatile content measurement, and a resin (B3-3) solution having an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

[0353] <Production of polymerizable compound (C)> (Polymerizable compound (C1-5)) 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, and the temperature was raised to 70 °C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the 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. Next, 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 was 50% by mass, and a polymerizable compound (C1-5) having an acidic group was obtained.

[0354] <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 material was put into 3,000 parts of warm water and stirred with a high-speed mixer for 1 hour while heating to 70 °C to make it into a slurry state. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for one day and night and pulverized to obtain a micronized green pigment (F-1).

[0355] (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 put into warm water and stirred with a high-speed mixer for 1 hour while heating to about 80 °C to make it into a slurry state. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for one day and night and pulverized to obtain a micronized red pigment (F-2).

[0356] (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 put 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 make it into a slurry state. 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).

[0357] (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 filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80 °C for a whole day and night and pulverized to obtain a finely divided yellow pigment (F-4).

[0358] (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 filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80 °C for a whole day and night and pulverized to obtain a finely divided purple pigment (F-5).

[0359] <Manufacture 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

[0360] (Dispersions 2 to 11) Dispersions 2 to 11 were prepared in the same manner as Dispersion 1 except that the raw materials and amounts described in Table 4 were changed.

[0361]

Table 4

[0362] <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): 4.4 parts Polymerizable Compound (C1-5): 2.0 parts Other Polymerizable Compound (C3-1): 3.6 parts Photopolymerization Initiator (D-3): 0.5 part Benzophenone-based Compound (E2-1): 0.5 part Leveling Agent (M): 1.0 part Organic Solvent (P): 38.0 parts

[0363] [Examples 2 to 39, Comparative Example 1] (Photosensitive Compositions 2 to 40) Photosensitive Compositions 2 to 40 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 5-1 to 5-4 were changed.

[0364]

Table 5-1

[0365]

Table 5-2

[0366]

Table 5-3

[0367]

Table 5-4

[0368] Regarding each of the raw materials described in Tables 5-1 to 5-4, it is as follows.

[0369] [Polymerizable Compound (C)] (Polymerizable Compound (C1) (C1-1) to (C1-4): Compounds with the following structure [Chemical formula]

[0370] (Polymerizable Compound (C2)) C2-1: Miramer SP-1106 (manufactured by Miwon Specialty Chemical, a polymerizable compound having a dendrimer structure with an average acryloyl group number of 18) C2-2: Etercure6361-100 (manufactured by Eternal Materials, a polymerizable compound having a hyperbranched structure with an average acryloyl group number of 8)

[0371] (Other Polymerizable Compound (C3)) (C3-1) to (C3-3): Compounds with the following structure [Chemical formula]

[0372] [Photoinitiator (D)] D-1: The compound of the above chemical formula (13) D-2: The compound of the above chemical formula (15) D-3: Omnirad 907 (manufactured by IGM Resins, an acetophenone-based compound)

[0373] [Sensitizer (E)] (Benzophenone-based Compound (E2)) E2-1: 4,4'-Bis(diethylamino)benzophenone

[0374] [Leveling Agent (M)] M-1: BYK-330 (manufactured by BYK-Chemie GmbH) M-2: Megafac F-551 (manufactured by DIC Corporation) The above (M-1) and (M-2) were each mixed in an amount of 1 part, and the resulting mixed solution dissolved in 98 parts of PGMAc was used as the leveling agent (M).

[0375] [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 The above (P-1) to (P-6) were each mixed in the above parts by mass to obtain the organic solvent (P).

[0376] [Evaluation of photosensitive composition] For the obtained photosensitive compositions 1 to 40 (Examples 1 to 39, Comparative Example 1), evaluation of pattern formability, solvent resistance, and foreign matter was performed by the following methods. The evaluation results are shown in Table 6.

[0377] [Pattern formability evaluation (1): Adhesion] The obtained photosensitive composition was spin-coated onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 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, through a photomask of stripe patterns with a width of 5 to 25 μm in 5-μm increments, the illuminance was 30 mW / cm 2 , 50 mJ / cm 2It was exposed. Then, this substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 130°C for 30 minutes. The spray development was carried out for each film of the photosensitive composition in the shortest time capable of forming a pattern without remaining development. Regarding the patterns with widths of 5, 10, 15, 20, and 25 μm on the obtained substrate, they were observed with an optical microscope, and the minimum line width of the remaining patterns was confirmed. The evaluation criteria are as follows, and 3 or more is considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: Fine lines of 25 μm remain. 1: No fine lines remain.

[0378] [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 the pattern formation evaluation (1). The evaluation was performed by capturing an SEM image of the cross-section of a stripe pattern with a width of 100 μm and measuring the taper angle between the substrate and the end of the pattern cross-section. The evaluation criteria are as follows, and 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

[0379] [Solvent resistance evaluation] The obtained photosensitive composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm by the spin coating method so that the film thickness after drying was 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, the ultraviolet light was irradiated through a photomask with a 100-μm-wide stripe pattern at 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 aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 °C, washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked in a clean oven at 130 °C for 30 minutes to obtain a substrate for evaluation. The obtained substrate was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 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 a value of 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.

[0380] [Foreign Matter Evaluation] The obtained photosensitive composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm by the spin coating method so that the dry film thickness was 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, the ultraviolet light was irradiated through a photomask with a 100-μm-wide stripe pattern at an illuminance of 30 mW / cm 2 ² and 50 mJ / cm 2Ultraviolet exposure was performed under the following conditions. Subsequently, the substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, then washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 130°C for 30 minutes. Subsequently, the substrate was stored for one week under the conditions of a temperature of 40°C and a humidity of 65%. After storage, the number of foreign substances on the pattern was measured. The evaluation was performed by surface observation using a metallurgical microscope "BX60" (manufactured by Olympus Corporation). The magnification was set to 500 times, and the number of foreign substances observable in five arbitrary fields by transmission was measured by integration. The evaluation criteria are as follows, and 3 or more is considered practical. 5: The number of foreign substances is less than 10 4: The number of foreign substances is 10 or more and less than 15 3: The number of foreign substances is 15 or more and less than 20 2: The number of foreign substances is 20 or more and less than 25 1: The number of foreign substances is 25 or more

[0381]

Table 6

Explanation of Symbols

[0382] 10 Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizer 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizer 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 hardening film 215 hardening 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 photopolymerization initiator (D), wherein the near-infrared absorbing dye (A) contains one or more selected from the group consisting of naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds, the resin (B) contains a resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2), the isocyanate group of the blocked isocyanate group-containing monomer unit (b1) has a structure protected by a blocking agent with a desorption temperature of 70 to 150°C, the polymerizable compound (C) contains a polymerizable compound (C1) having one or more groups selected from a hydroxyl group and an acidic group, the resin (B1) further has an alicyclic hydrocarbon-containing monomer unit (b6), a photosensitive composition.

2. A photosensitive composition comprising a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the near-infrared absorbing dye (A) contains one or more selected from the group consisting of naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds, the resin (B) contains a resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2), the isocyanate group of the blocked isocyanate group-containing monomer unit (b1) has a structure protected by a blocking agent with a desorption temperature of 70 to 150°C, the polymerizable compound (C) contains a polymerizable compound (C1) having one or more groups selected from a hydroxyl group and an acidic group, the resin (B) further contains a resin (B2) having no blocked isocyanate group-containing monomer unit (b1), and the resin (B2) is a resin having one or more monomer units selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the following general formula (1), a photosensitive composition. General formula (1) 【Chemical 1】 (In general formula (1), R1 represents a hydrogen atom or a methyl group. R2 represents an alkylene group having 2 or 3 carbon atoms. n represents an integer of 1 to 15. When n is 2 or more, a plurality of R2 may be the same or different.)

3. A photosensitive composition comprising a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The near-infrared absorbing dye (A) contains one or more selected from the group consisting of naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds. The resin (B) contains a resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2). The isocyanate group of the blocked isocyanate group-containing monomer unit (b1) has a structure protected by a blocking agent having a desorption temperature of 70 to 150°C. The polymerizable compound (C) contains a polymerizable compound (C1) having one or more groups selected from a hydroxyl group and an acidic group. The resin (B) further contains a resin (B3) having a blocked structure with a basic group (however, the resin (B3) is not included in the resin (B1)), the photosensitive composition.

4. The photosensitive composition according to any one of claims 1 to 3, wherein the isocyanate group of the blocked isocyanate group-containing monomer unit (b1) has a structure protected by one or more blocking agents selected from the group consisting of an oxime compound having a desorption temperature of 70 to 150°C, an active methylene compound having a desorption temperature of 70 to 150°C, and a pyrazole compound having a desorption temperature of 70 to 150°C.

5. The photosensitive composition according to any one of claims 1 to 4, wherein the content of the blocked isocyanate group-containing monomer unit (b1) is 1 to 40 mol% in all the constituent units of the resin (B1).

6. The photosensitive composition according to any one of claims 1 to 5, wherein the content of the resin (B1) is 10% by mass or more in 100% by mass of the resin (B).

7. The photosensitive composition according to claim 1 or 3, wherein the resin (B) further contains a resin (B2) not having the blocked isocyanate group-containing monomer unit (b1).

8. The photosensitive composition according to claim 7, wherein the resin (B2) is a resin having one or more monomer units selected from an alicyclic hydrocarbon-containing monomer unit (b6) and a monomer unit (b7) formed from a monomer represented by the following general formula (1). General formula (1) 【Chemical 1】 (In general formula (1), R １ represents a hydrogen atom or a methyl group. R ２ represents an alkylene group having 2 or 3 carbon atoms. n represents an integer of 1 to 15. When n is 2 or more, a plurality of R ２ may be the same or different from each other.)

9. The photosensitive composition according to any one of claims 1 to 8, wherein the polymerizable compound (C) contains a polymerizable compound (C2) having a structure selected from a dendrimer structure or a hyperbranched structure.

10. The photosensitive composition according to any one of claims 1 to 9, containing a colorant (F).

11. The photosensitive composition according to claim 10, wherein the colorant (F) contains two or more pigments selected from the group consisting of a red pigment, a yellow pigment, a blue pigment, a green pigment, and a purple pigment.

12. A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 11.

13. An optical filter having the cured film according to claim 12.

14. An image display device having the cured film according to claim 12.

15. A solid-state imaging device having the cured film according to claim 12.

16. An infrared sensor having the cured film according to claim 12.

Images