JP2023089821A - Photosensitive composition and uses thereof - Google Patents

Abstract

To provide a photosensitive composition that can be used to produce a cured film which offers a superior pattern shape and exhibits superior solvent resistance and high-temperature high-humidity resistance even after low-temperature post-baking.SOLUTION: The above problem is cleared by a photosensitive composition containing a near-infrared absorbing pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), the polymerizable compound (C) containing a polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure.SELECTED DRAWING: Figure 1

Description

The present invention relates to photosensitive compositions containing near-infrared absorbing dyes.

CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), which are solid-state imaging devices for color images, are used in video cameras, digital cameras, smartphones, and the like. 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 visibility correction, and an infrared cut filter or the like is arranged. An infrared cut filter is manufactured, for example, using a composition containing a near-infrared absorbing dye.

Conventionally, an infrared cut filter has been used as a flat film, but in recent years, it has been studied to form a pattern on the infrared cut filter by photolithography. In the photolithography method, a photosensitive composition is applied to a glass substrate, the solvent is removed from the coating by drying, and the coating is exposed to active energy rays (i-rays) through a photomask having a desired pattern shape. etc.) is irradiated and cured (hereinafter referred to as exposure), then the unexposed area is washed and removed (hereinafter referred to as development), and then the cured film is sufficiently cured by heat treatment (hereinafter referred to as post-bake ) can form a pattern.

Post-baking is usually carried out at a temperature of 200 to 250° C. for about 10 to 60 minutes to promote curing and increase the resistance of the cured film. However, since the near-infrared absorbing dye has low heat resistance and tends to lose near-infrared absorbing ability during post-baking, post-baking is performed at a low temperature. Therefore, the curing of the film tends to be insufficient, and there is a problem that the solvent resistance of the cured film and the resistance in a high-temperature and high-humidity environment are deteriorated.

Methods of obtaining sufficient resistance even with low-temperature post-baking include, for example, increasing the amount of active radicals generated, that is, using or increasing the amount of highly sensitive photopolymerization initiators, and increasing the amount of exposure. It's here. However, in these methods, there is a problem that the reaction progresses to the portion covered with the mask, the line width of the pattern becomes large, and the pattern of desired size cannot be obtained.
In addition, heat dripping is less likely to occur during post-baking at a low temperature, and the cross-sectional shape of the pattern tends to deteriorate. In particular, a composition containing a near-infrared absorbing dye has a problem in that it is difficult to obtain a desired pattern shape because active energy rays are easily transmitted therethrough.

Patent Document 1 discloses an invention in which a fine pattern is formed using 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. ing. Further, Patent Document 2 discloses an invention of a pattern-forming composition containing an infrared absorbing dye and a resin having a glass transition temperature of 150 to 300°C.

Japanese Patent Application Laid-Open No. 2010-160380 WO2019/058882

However, with the compositions described in Patent Documents 1 and 2, it was difficult to obtain a good pattern shape, and the resistance of the cured film could not be satisfied by low-temperature post-baking.

An object of the present invention is to provide a photosensitive composition capable of forming a cured film having excellent pattern shape and excellent solvent resistance and high temperature and high humidity resistance even after low-temperature post-baking.

The present invention is a photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C) and a photopolymerization initiator (D),
The polymerizable compound (C) relates to a photosensitive composition containing a polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure.

According to the present invention, it is possible to provide a photosensitive composition capable of forming a cured film having excellent pattern shape and excellent solvent resistance and high temperature and high humidity resistance even after low-temperature post-baking. Moreover, the present invention can provide a cured film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor.

FIG. 1 shows a schematic cross-sectional view of an image display device provided with the cured film of the present invention. FIG. 2 shows a schematic cross-sectional view of a solid-state imaging device provided with the cured film of the present invention. FIG. 3 shows a schematic cross-sectional view of an infrared sensor provided with the cured film of the present invention.

Hereinafter, embodiments for implementing the photosensitive composition of the present invention will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and can be modified and implemented within a range that can solve the problems.

In the present invention, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" are each unless otherwise specified. , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide” . "C.I." means a color index (C.I.; published by The Society of Dyers and Colorists). A polymerizable unsaturated group is an ethylenically unsaturated double bond.
Regarding the molecular weight of the compound in the present invention, for a low-molecular compound whose molecular weight can be specified, it is a value calculated by calculation or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and a compound having a molecular weight distribution. is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.
A monomer is a compound that forms a resin upon polymerization. A monomer is an unreacted state and a monomeric unit is a state in which a monomer forms a resin after polymerization.
A polymerizable compound is a compound that forms a film by polymerization.
Condensed ring structure means a structure in which two or more rings share a side in a one-to-one relationship, and an aromatic condensed ring structure in which at least one ring is an aromatic ring, and all rings are aliphatic rings is called an aliphatic condensed ring structure.

<Photosensitive composition>
The photosensitive composition of the present invention is a photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C) and a photopolymerization initiator (D),
The polymerizable compound (C) is characterized by containing a polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure.

Although the mechanism by which the photosensitive composition having the above structure can solve the problems of the present invention is not clear, it is speculated as follows. Polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure compared to penta- or hexa-functional (meth)acrylates that have been widely used for forming patterns by conventional photolithography. Since the number of cross-linking sites is small and the reaction is mild, even if a highly sensitive photoinitiator is used or the exposure dose is increased, the reaction does not easily proceed to the area covered by the mask, and a pattern of the desired width can be obtained. Infer. In addition, since the crosslink density in the cured film is low, it is likely to be softened by heat, and it is presumed that heat dripping occurs even in post-baking at a low temperature and the cross-sectional shape of the pattern becomes good. Moreover, since it has a ring structure, it is speculated that a rigid structure is formed with a low cross-linking density, and a highly resistant cured film can be obtained.

[Near-infrared absorbing dye (A)]
The photosensitive composition of the present invention contains a 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). may Also, a near-infrared absorbing pigment and a near-infrared absorbing dye may be used in combination. Near-infrared absorbing pigments are preferred from the viewpoint of heat resistance.
In the present invention, the solubility of the near-infrared absorbing pigment in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

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

Cyanine compounds, WO 2006/006573, WO 2010/073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; JP-A-4-23868, JP-A-06-192584, JP-A-2000-63691, International Publication No. 2014/208514, etc.; No., JP-A-2009-29955, International Publication No. 2018/186490, etc.; Monium compounds, JP-A-2005-336150, JP-A-2007-197492, JP-A-2008-88426, etc.; anthraquinone compounds, JP-A-62-903, JP-A-1-172458, etc. Pyrrolopyrrole compounds include JP-A-2009-263614, JP-A-2010-90313, JP-A-2011-068731, JP-A-2014-130348, International Publication No. 2015/166873, etc.; , JP 2011-132361, JP 2016-142891, WO 2017/135359, WO 2018/225837, JP 2019-001987, WO 2020/054718, International Publication No. 2021/029195 and the like; the croconium compound includes compounds described in International Publication No. 2019/021767 and the like.

(squarylium compound)
The squarylium compound is preferably a compound represented by the following general formula (1).
General formula (1)

In general formula (1), R ¹ to R ⁴ each independently represent 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 , —SO ₂ R ²³ , —SO ₂ OR ²⁴ , —NHSO ₂ R ²⁵ , —SO ₂ NR ²⁶ R ²⁷ , —B(OR ²⁸ ) ₂ , and —NHBR ²⁹ R ³⁰ . R ¹⁰ to R ³⁰ each independently represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and aralkyl group. When R ¹² of —COOR ¹² is a hydrogen atom (ie, carboxyl group), the hydrogen atom may be dissociated (ie, carbonate group) or may be in a salt state. Also, when R ²⁴ of —SO ₂ OR ²⁴ is a hydrogen atom (ie, sulfo group), the hydrogen atom may be dissociated (ie, sulfonate group) or in a salt state. In addition, R ¹ and R ² , R ³ and R ⁴ may combine with each other to form a ring.

The “substituent” includes 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 , —SO ₂ R ¹¹³ , —SO ₂ OR ¹¹⁴ , —NHSO ₂ R ¹¹⁵ or — SO ₂ NR ¹¹⁶ R ¹¹⁷ can be mentioned.
R ¹⁰⁰ to R ¹¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group. When R ¹⁰² of —COOR ¹⁰² is a hydrogen atom (ie, carboxyl group), the hydrogen atom may be dissociated (ie, carbonate group) or may be in a salt state. In addition, when R ¹¹⁴ of —SO ₂ OR ¹¹⁴ is a hydrogen atom (ie, sulfo group), the hydrogen atom may be dissociated (ie, sulfonate group) or in a salt state.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-12, and particularly preferably 1-8. The alkyl group may be linear, branched or cyclic.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. Alkenyl groups may be linear, branched or cyclic.
The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. Alkynyl groups may be linear, branched or cyclic.
The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms.
The alkyl portion of the aralkyl group is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the above aryl group. The aralkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, and particularly preferably 7 to 25 carbon atoms.
The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring with 2 to 8 condensed numbers, and particularly preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1-3. A heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. A heteroaryl group is preferably a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3-30, more preferably 3-18, particularly preferably 3-12.
Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, and aralkyl groups may have a substituent or may be unsubstituted. Examples of the substituent include the "substituent" described above.

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

general formula (2)

In general formula (2), R ⁵ to R ⁸ each independently represent 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 , —SO ₂ R ⁶³ , —SO ₂ OR ⁶⁴ , —NHSO ₂ R ⁶⁵ or —SO ₂ NR ⁶⁶ R ⁶⁷ , —B(OR ⁶⁸ ) ₂ , and —NHBR ⁶⁹ R ⁷⁰ . R ⁵⁰ to R ⁷⁰ each independently represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and aralkyl group. When R ⁵² of —COOR ⁵² is hydrogen (ie, carboxyl group), the hydrogen atom may be dissociated (ie, carbonate group), or it may be in the form of a salt. Also, when R ⁶⁴ of —SO ₂ OR ⁶⁴ is a hydrogen atom (ie, sulfo group), the hydrogen atom may be dissociated (ie, sulfonate group) or in a salt state. Also, R ⁵ and R ⁶ and R ⁷ and R ⁸ may combine with each other to form a ring.

A "substituent" has the same meaning as the above-mentioned "substituent".

Specific examples of the squarylium compound are shown below. In addition, this invention is not limited to these.

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

General formula (3)

In general formula (3), 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, and R ² and R ³ may combine with 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, and R ⁴ is It may be covalently or coordinately bonded to at least one selected from the group consisting of R ^1x , R ^1y and R ³ , and each of R ^{4x and} R ^4y independently represents a substituent. General formula (3) is described, for example, in JP-A-2009-263614, JP-A-2011-68731, and International Publication No. 2015/166873.

R ^1x and R ^1y are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. In addition, the alkyl group, aryl group and heteroaryl group represented by R ^1x and R ^1y may have a substituent or may be unsubstituted. Examples of substituents include alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, —OCOR ¹¹ , —SOR ¹² , —SO ₂ R ¹³ and the like. R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heteroaryl group. Further, examples of substituents include substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among them, preferred substituents are alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, -OCOR ¹¹ , -SOR ¹² and -SO ₂ R ¹³ . As the groups represented by R ^1x and R ^1y , an alkoxy group having a branched alkyl group or an aryl group having a group represented by —OCOR ¹¹ as a substituent is preferable. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

At least one of R ² and R ³ is preferably an electron-withdrawing group, more preferably R ² represents an electron-withdrawing group and R ³ represents a heteroaryl group. A heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring with 2 to 8 condensed numbers, more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. Heteroatoms include, for example, nitrogen atoms, oxygen atoms, and sulfur atoms. Heteroaryl groups preferably have one or more nitrogen atoms. Two R ² groups in general formula (3) may be the same or different. Two R ³ groups in formula (3) may be the same or different.

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 is represented by a hydrogen atom, an alkyl group, an aryl group, or -BR ^4x R ^4y is more preferred, and a group represented by —BR ^4x R ^4y is particularly preferred. 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 R ⁴ groups in general formula (3) may be the same or different.

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. Further, the pyrrolopyrrole compound, for example, paragraphs 0016 to 0058 of JP-A-2009-263614, paragraphs 0037-0052 of JP-A-2011-68731, paragraphs 0014-0027 of JP-A-2014-130343, international publication Compounds described in paragraphs 0010-0033 of 2015/166873. In addition, this invention is not limited to these.

(naphthalocyanine compound)
The naphthalocyanine compound is preferably a compound represented by the following general formula (4).

general formula (4)

In general formula (4), X ₁ to X ₈ and Y ₁ to Y ₈ each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an optionally substituted alkyl group, or a substituent. optionally substituted aryl group, optionally substituted cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted phthalimidomethyl group, or optionally substituted sulfamoyl represents a group. In addition, X ₁ to X ₈ may each independently combine with each other to form an aromatic ring which may have a substituent. However, any one or more of X ₁ and X ₂ , X ₃ and X ₄ , X ₅ and X ₆ , X ₇ and X ₈ are bonded to each other to form an aromatic ring which may have a substituent.
Z is a polymer site containing a monomer unit represented by the following general formula (5) or a phosphorus compound site represented by the following general formula (6), and * is a bond with Al.

The "alkyl group" of the alkyl group optionally having a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, and an n-hexyl group. , n-octyl group, stearyl group, 2-ethylhexyl group, and other linear or branched alkyl groups. "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-tetrafluoro propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

The "aryl group" of the aryl group optionally having a substituent includes, for example, a phenyl group, a naphthyl group, an anthryl group and the like.
"Aryl group having a substituent" includes, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2- aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-amino Anthraquinonyl group and the like can be mentioned.

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

The "heterocyclic group" of the optionally substituted heterocyclic group includes pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group and the like. The "heterocyclic group having a substituent" includes 3-methylpyridyl group, N-methylpiperidyl group, N-methylpyrrolyl group and the like.

The "alkoxyl group" of the alkoxyl group which may have a substituent is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, Linear or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy groups can be mentioned.
The "substituted alkoxyl group" includes, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditri fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

The "aryloxy group" of the aryloxy group optionally having a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, etc.
"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- A chlorophenoxy group and the like can be mentioned.

The "alkylthio group" of the alkylthio group optionally having a substituent is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, and the like. is mentioned.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

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.
"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. .

The substituents 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, and a substituent which may have aryl group, optionally substituted cycloalkyl group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group, substituted An arylthio group optionally having a group is exemplified.

general formula (5)

In general formula (5), X is -CONH-R ²⁵ -, -COO-R ²⁶ -, -CONH-R ²⁷ -O-, -COO-R ²⁸ -O-. R ²⁵ to R ²⁸ are an alkylene group optionally linked by —O—, —CO—, —COO—, —OCO—, —CONH—, or —NHCO— between carbon atoms, or represents an arylene group. R ³¹ represents hydrogen or a methyl group.

Examples of the alkylene group include methylene group, ethylene group, propylene group and butylene group. Arylene groups include, for example, phenylene, naphthylene, biphenylene, terphenylene and anthrylene groups.

The monomer units represented by the general formula (5) are, for example, (2-(meth)acryloyloxyethyl)acid phosphate, (2-(meth)acryloyloxypropyl)acid phosphate, (2-(meth)acryloyloxyisopropyl ) obtained by polymerizing a monomer such as acid phosphate. It can also be obtained by copolymerizing a monomer other than these monomers (hereinafter also referred to as other monomers) in combination.

Other monomers include, for example, (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, vinyl Alcohol esters, styrenes, (meth)acrylonitrile, acid group-containing monomers, thermally crosslinkable group-containing monomers, and the like can be mentioned.

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

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

general formula (6)

In general formula (6), R ²⁹ and R ³⁰ each independently represent a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted It represents an alkoxyl group or an optionally substituted aryloxy group, and R ²⁹ and R ³⁰ may combine with each other to form a ring.

"Alkyl group" of alkyl group optionally having substituent(s), "aryl group" of aryl group optionally having substituent(s), "alkoxyl group" of alkoxyl group optionally having substituent(s), substituent Examples of the "aryloxy group" of the aryloxy group which may have are the same as those exemplified in the explanation of the general formula (4).

In general formula (6), from the viewpoint of dispersibility and color characteristics, at least one of R ²⁹ and R ³⁰ is an aryl group optionally having a substituent or an aryloxy group optionally having a substituent is preferred, both R ²⁹ and R ³⁰ are more preferably an aryl group or an aryloxy group, and both R ²⁹ and R ³⁰ are more preferably a phenyl group or a phenoxy group.

The naphthalocyanine compound is more preferably a compound represented by the following general formula (7).

general formula (7)

In general formula (7), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an optionally substituted alkyl group, or a substituent. optionally substituted aryl group, optionally substituted cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted phthalimidomethyl group, or optionally substituted sulfamoyl represents a group.
Z is a polymer site containing a monomer unit represented by general formula (5) or a phosphorus compound site represented by general formula (6), and * is a bond with Al.

an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted phthalimide A methyl group or a sulfamoyl group which may have a substituent is as described in the general formula (4) above.

In general formula (7), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ are preferably hydrogen atoms, halogen atoms, or optionally substituted alkoxyl groups from the viewpoint of dispersibility and color properties.

Specific examples of the naphthalocyanine compound are shown below. In addition, this invention is not limited to these.

(indigo compound)
The indigo compound is preferably a compound represented by the following general formula (8) and/or general formula (9).

General formula (8) General formula (9)

In general formulas (8) and (9), X ₁ to X ₄₀ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, alkoxyl group optionally having substituent(s), aryloxy group optionally having substituent(s), arylalkyl group optionally having substituent(s), cycloalkyl group optionally having substituent(s) , optionally substituted alkylthio group, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted represents an arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, --SO ₃ H; --COOH; and monovalent to trivalent metal salts of these acidic groups; and alkylammonium salts. M represents a metal atom.

The "alkyl group" of the alkyl group optionally having a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, and an n-hexyl group. , n-octyl group, stearyl group, 2-ethylhexyl group, and other linear or branched alkyl groups. "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-tetrafluoro propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

The "aryl group" of the aryl group optionally having a substituent includes, for example, a phenyl group, a naphthyl group, an anthryl group and the like.
"Aryl group having a substituent" includes, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2- aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-amino Anthraquinonyl group and the like can be mentioned.

The "alkoxyl group" of the alkoxyl group which may have a substituent is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, Linear or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy groups can be mentioned.
The "substituted alkoxyl group" includes, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditri fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

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

"Optionally substituted arylalkyl group" includes, for example, benzyl group, 2-phenylpropan-yl group, styryl group, diphenylmethyl group, triphenylmethyl group and the like.

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

The "alkylthio group" of the alkylthio group optionally having a substituent is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, and the like. is mentioned.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

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.
"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. .

The "alkylamino group" of the optionally substituted alkylamino group 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.

The "arylamino group" of the arylamino group optionally having a substituent is, 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-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like.

Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of acidic groups include —SO ₃ H and —COOH, and examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. mentioned. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. and quaternary alkylammonium salts of.

Preferred substituents for X ₁ to X ₄₀ among the above substituents include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and --SO ₃ H.

M represents a metal atom. Metal atoms include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, Ba, and the like. Among them, a divalent metal atom is preferable, and Zn, Co, and Ni are more preferable.

Specific examples of the indigo compound are shown below. In addition, this invention is not limited to these.

The near-infrared absorbing dye (A) can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use at least two types of compounds having different maximum absorption wavelengths. As a result, the waveform of the absorption spectrum is broadened compared to the case where one type of near-infrared absorbing dye (A) is used, and near-infrared rays in a wide wavelength range can be absorbed.

The content of the near-infrared absorbing dye (A) is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition, from the viewpoint of near-infrared absorbing property. .

[Other near-infrared absorption compounds]
The photosensitive composition of the present invention can contain a compound having near-infrared absorbing ability (hereinafter also referred to as other near-infrared absorbing compound) other than the near-infrared absorbing dye (A). Other near-infrared absorbing compounds include, for example, indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, and metal oxides such as copper, nickel, silver, and gold. Particles or metal particles may be mentioned.

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

The alkali-soluble resin (B) may be any resin that dissolves in an alkali developer, and known resins can be used. For example, (meth)acrylic resin, styrene resin, styrene/acrylic resin, α-olefin/(anhydride) maleic acid copolymer, styrene/styrenesulfonic acid copolymer, ethylene/(meth)acrylic acid copolymer, epoxy Resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamide-imide resins, cyclic olefin resins, and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 4,000 to 40,000, more preferably 5,000 to 35,000, from the viewpoint of developability. Moreover, the value of Mw/Mn (number average molecular weight) is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to substrates and development solubility.

The acid value of the alkali-soluble resin (B) is preferably 30-200 mgKOH/g, more preferably 40-180 mgKOH/g. Adhesion to substrates and development solubility are improved by a moderate acid value.

The content of the alkali-soluble resin (B) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition.

Alkali-soluble resin (B) can be used alone or in combination of two or more.

The alkali-soluble resin (B) may contain a resin having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2) from the viewpoint of pattern shape and low-temperature post-baking resistance. preferable. As a result, curing proceeds even after post-baking at a low temperature, and the resistance of the cured film is improved.

The alkali-soluble resin having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2) is a block isocyanate group-containing monomer, an acidic group-containing monomer, and optionally copolymerized with them. It can be obtained by copolymerizing with other possible monomers.

[Blocked isocyanate group-containing monomer unit (b1)]
The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of the isocyanate group-containing monomer is protected with a thermally detachable compound (hereinafter also referred to as a blocking agent).

Examples of isocyanate group-containing monomers 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. An equimolar reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

Blocking agents 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. .

Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime, cyclohexanone oxime, benzophenone oxime, etc. Methylethylketoxime is preferred.
Lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam and the like.
Phenolic compounds include, for example, phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol , p-nitrophenol and the like, and 3,5-xylenol, methyl 2-hydroxybenzoate and methyl 4-hydroxybenzoate are preferred.
Alcohol compounds include, for example, methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol.
Examples of amine compounds include diphenylamine, phenylnaphthylamine, aniline, carbazole and the like.
Active methylene compounds include, for example, 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 and the like, with 3,5-dimethylpyrazole being preferred.
Mercaptan compounds include, for example, butyl mercaptan, thiophenol, tert-dodecyl mercaptan and the like.
Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole and the like.
Examples of imide compounds include succinimide, maleimide, maleimide, and phthalimide.
Urea compounds include, for example, urea, thiourea, ethylene urea, and the like.
Examples of imine compounds include ethyleneimine and polyethyleneimine.
Bisulfite compounds include, for example, sodium bisulfite and potassium bisulfite. These blocking agents can be used alone or in combination of two or more.

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. At least one compound selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferable from the viewpoint of deprotection reaction.

Examples of blocked isocyanate group-containing monomers include the following compounds. In addition, this invention is not limited to these.

Commercial products of blocked isocyanate group-containing monomers include Karenz MOI-DEM (desorption temperature of blocking agent: 85-95°C) and MOI-BP (desorption temperature of blocking agent: 105-95°C) manufactured by Showa Denko Co., Ltd. 115° C.), MOI-BM (desorption temperature of blocking agent: 125 to 135° C.), and the like.

The content of the blocked isocyanate group-containing monomer unit (b1) is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, of the total constituent units of the alkali-soluble resin, from the viewpoint of resistance to low-temperature post-baking. preferable.

[Acidic group-containing monomeric unit (b2)]
The acidic group of the acidic group-containing monomer includes, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like. Among these, a carboxyl group is preferred.

Examples of acidic group-containing monomers include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, anhydrous Maleic acid, fumaric acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamide-2- Methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate and the like.

From the viewpoint of pattern shape, the content of the acidic group-containing monomer unit (b2) is preferably 1 to 50 mol %, more preferably 5 to 40 mol %, of the total constituent units of the alkali-soluble resin.

An alkali-soluble resin having a blocked isocyanate group-containing monomeric unit (b1) and an acidic group-containing monomeric unit (b2) contains the blocked isocyanate group-containing monomeric unit (b1) and the acidic group-containing monomeric unit (b2 ) may have monomeric units other than For example, a hydroxyl group-containing monomer unit (b3), an aliphatic condensed ring structure-containing monomer unit (b4), an epoxy group-containing monomer unit (b5), a polymerizable unsaturated group-containing monomer unit (b6) , and other monomer units (b7). Among these, it is preferable to have a hydroxyl group-containing monomer unit (b3) and an aliphatic condensed ring structure-containing monomer unit (b4) from the viewpoint of resistance to low-temperature post-baking.
It is presumed that the presence of the hydroxyl group-containing monomeric unit (b3) facilitates the elimination of the blocking agent from the blocked isocyanate group-containing monomeric unit (b1), thereby facilitating curing at a low temperature. It is assumed that the isocyanate groups and hydroxyl groups from which the blocking agent has been eliminated react with each other to further improve the resistance.
It is speculated that having the aliphatic condensed ring structure-containing monomer unit (b4) enables the formation of a rigid cured film and further improves the resistance.

[Hydroxyl group-containing monomer unit (b3)]
Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2- Hydroxyethylphthalic acid and the like can be mentioned.

The ratio of the blocked isocyanate group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b3) is preferably 10:90 to 50:50, 15:85 to 45, from the viewpoint of resistance to low-temperature post-baking. :55 is more preferred.

[Aliphatic condensed ring structure-containing monomer unit (b4)]
Aliphatic condensed ring structure-containing monomers, for example, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , adamantyl (meth)acrylate and the like. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[Epoxy group-containing monomer unit (b5)]
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.

[Polymerizable Unsaturated Group-Containing Monomer Unit (b6)]
The polymerizable unsaturated group-containing monomer unit (b6) includes, for example, units introduced by the following methods (i) to (iii).

<Method (i)>
There is a method (i) in which the above-mentioned epoxy group-containing monomer is added to the acidic group of the acidic group-containing monomer unit (b2).

<Method (ii)>
There is a method (ii) in which the above-mentioned acidic group-containing monomer is added to the epoxy group of the resin having the epoxy group-containing monomer unit (b5).

A unit obtained by further reacting an acid anhydride with a hydroxyl group produced by the reactions of methods (i) and (ii) is also preferable as the polymerizable unsaturated group-containing monomer unit (b6).

Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

<Method (iii)>
There is a method (iii) in which the hydroxyl group of the resin having the hydroxyl group-containing monomer unit (b3) is reacted with the isocyanate group of the isocyanate group-containing monomer.

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

[Other monomer units (b7)]
Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert- Butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of nonylphenol, EO- or PO-modified paracumylphenol acrylic acid esters such as (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate;
aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene;
(Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine ;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4 '-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N -(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(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- N-substituted maleimides such as 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) )] and bis-2-propenoate. These monomers can be used alone or in combination of two or more.

[Polymerizable compound (C)]
(Polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure)
The photosensitive composition of the present invention includes, as the polymerizable compound (C), a polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure (hereinafter also simply referred to as a polymerizable compound (C1)). include.

The ring structure may be an aromatic ring structure, a heterocyclic ring structure, or a condensed ring structure, but a condensed ring structure is preferred from the viewpoint of pattern shape and resistance to low-temperature post-baking.
Moreover, the condensed ring structure is preferably an aliphatic condensed ring structure in which all rings are aliphatic rings.

From the viewpoint of the pattern shape, the molecular weight of the polymerizable compound (C1) is preferably 500 or less, more preferably 200 or more and 500 or less. In addition, molecular weight is a formula weight or a weight average molecular weight.

The content of the polymerizable compound (C1) is preferably 50% by mass or more, more preferably 50 to 100% by mass, more preferably 60 to 100% by mass in 100% by mass of the polymerizable compound (C) from the viewpoint of pattern shape. Especially preferred.

The polymerizable compound (C1) may be appropriately synthesized or may be a commercially available product.

The polymerizable compound (C1) includes, for example, tricyclodecanedimethanol diacrylate (molecular weight 304), tricyclodecanedimethanol dimethacrylate (molecular weight 332), 1,3-adamantanediol diacrylate (molecular weight 276), 1,3 -Adamantanediol dimethacrylate (molecular weight 304), 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (molecular weight 546) and other polymerizable compounds having a condensed ring structure;
Polymerizable compounds having a heterocyclic structure such as dioxyglycol diacrylate (molecular weight 326), dioxyglycol dimethacrylate (molecular weight 354), isocyanuric acid diacrylate with two EO modifications (molecular weight 369);
Bisphenol A diacrylate with 3 EO modifications (molecular weight 380), bisphenol A diacrylate with 3 PO modifications (molecular weight 394), bisphenol A diacrylate with 4 EO modifications (molecular weight 512), EO modification Examples thereof include polymerizable compounds having an aromatic ring structure such as bisphenol A diacrylate (molecular weight: 776) having 10 nuclei. Among these, tricyclodecanedimethanol diacrylate (molecular weight 304) and tricyclodecanedimethanol dimethacrylate (molecular weight 332) having an aliphatic condensed ring structure are preferred.

Commercially available products of the polymerizable compound (C1) include, for example, Shin-Nakamura Chemical Co., Ltd. NK ester A-DCP, DCP, A-DOG, ABE-300, A-BPE-4, A-BPE-10, A- BPP-3, A-BPEF, OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd., Miwon Specialty Chemical Co., Ltd. , Ltd. Miramer HR6060, HR6100, HR6200 and the like.

(Polymerizable compound (C2))
The photosensitive composition of the present invention includes, as the polymerizable compound (C), a polymerizable compound (C2) other than the polymerizable compound (C1) (hereinafter, simply polymerizable compound (C2) ) can be contained.

The polymerizable compound (C2) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, phenol EO-modified ( meth) acrylate, 2-ethylhexyl EO-modified (meth) acrylate, N-acryloyloxyethyl hexahydrophthalimide, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Polymerizable compounds having one (meth)acryloyl group such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate;
1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl Having two (meth)acryloyl groups such as glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. polymerizable compound;
trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, etc. A polymerizable compound having three (meth)acryloyl groups;
Polymerizable compounds having four (meth)acryloyl groups such as ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate;
Polymerizable compounds having five (meth)acryloyl groups such as dipentaerythritol penta(meth)acrylate;
Polymerizable compounds having six (meth)acryloyl groups, such as dipentaerythritol hexa(meth)acrylate, and the like can be mentioned.
Also included are polymerizable compounds having an acidic group, polymerizable compounds having a urethane bond, polymerizable compounds having a dendrimer structure or hyperbranched structure, and lactone-modified polymerizable compounds.

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

The content of the polymerizable compound (C) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition.

[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.

The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexylphenyl 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- Acetophenone compounds such as butanone;
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(trichloro methyl)-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 triazines such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine system compound;
1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole oxime compounds such as 3-yl]-, 1-(O-acetyloxime);
Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds;

Commercially available products include Omnirad 907, 369E and 379EG manufactured by IGM Resins as acetophenone compounds, Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds, and IRGACURE OXE-01 and 02 manufactured by BASF as oxime compounds. , 03, 04, N-1919 manufactured by ADEKA, NCI-730, 831, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365 manufactured by Changzhou New Material Co., Ltd. , 610, 3054, 3057, Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306 manufactured by Daito Chemix, EOX-01 etc.
In addition, JP 2019-507108, JP 2019-528331, etc., acetophenone compounds described in JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-037223, Also included are oxime compounds described in JP-A-2010-215575, JP-A-2011-020998, WO 2015/036910, WO 2021/175855, and the like.

When the photosensitive composition of the present invention contains a coloring agent (F) described later, it preferably contains an oxime compound as a photopolymerization initiator (D).

As the oxime compound, for example, the following compounds are preferable. In addition, this invention is not limited to these.

chemical formula (16)

Methods for producing the compounds of chemical formulas (10) to (16) are not particularly limited, and known methods can be used. For example, JP 2004-534797, JP 2008-80068, JP 2012-526185, WO 2015/036910, WO 2015/152153, JP 2016-504270, Methods described in JP-A-2017-512886, JP-A-2017-523465, JP-A-2021-011486 and the like can be mentioned.

From the viewpoint of resistance to low-temperature post-baking, the oxime-based compound is more preferably one or more selected from the group consisting of compounds of chemical formulas (10) to (16), and consists of compounds of chemical formulas (12) to (14). One or more selected from the group is particularly preferred.

A photoinitiator (D) can be used individually or in combination of 2 or more types.

The content of the photopolymerization initiator (D) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the near-infrared absorbing dye (A).

[Thiol-based chain transfer agent (E)]
The photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (E) from the viewpoint of pattern shape and resistance to low-temperature post-baking. When the thiol-based chain transfer agent (E) is used in combination with the photopolymerization initiator (D), thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after irradiation with active energy rays, and curing is accelerated.

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

Polyfunctional thiols are, for example, hexanedithiol, decanedithiol, 1,4-butanedi-rubisthiopropionate, 1,4-butanedi-rubisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercapto tris(2-hydroxyethyl) isocyanurate propionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

Thiol-based chain transfer agents (E) can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent (E) is preferably 0.1 to 1.0% by mass based on 100% by mass of the non-volatile content of the photosensitive composition, from the viewpoint of pattern shape and resistance to low-temperature post-baking. 0.2 to 0.8% by mass is more preferable.

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

The coloring agent (F) may be either a pigment or a dye, and can be used in combination.

(pigment)
Pigments are preferably compounds classified as pigments in the Color Index.
Red pigments include, for example, C.I. 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, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance, C.I. I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, the pigment described in Patent No. 6368844 is preferable, C. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more preferable.

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

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

Green pigments include, for example, C.I. 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 and the like. Among these, C.I. I. Pigment Green 36, 58, 59, 62, 63 are preferred.

Blue pigments include, for example, C.I. 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 and the like. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

Purple pigments include, for example, C.I. 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 and the like. Among these, C.I. I. Pigment Violet 19, 23 are preferred.

Black pigments include, for example, C.I. I. Pigment Black 1, 6, 7, 12, 20, 21, 31, 32, 33, 34 and the like. Further, compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, JP-A-1-170601, JP-A-2-34664 and the like are also included.

When the photosensitive composition of the present invention is used for an infrared transmission filter, two or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments and violet pigments are used as the colorant (F). and exhibiting a black color.

Examples of combinations that exhibit black include the following aspects.
(1) Contains a yellow pigment and a purple pigment.
(2) It contains a red pigment, a yellow pigment, and a purple pigment.
(3) Contains a red pigment, a yellow pigment, and a blue pigment.
(4) Contains a red pigment, a yellow pigment, and a green pigment.
(5) Contains a yellow pigment, a blue pigment, and a purple pigment.
(6) Contains a red pigment, a yellow pigment, a blue pigment, and a violet pigment.
(7) Contains a yellow pigment, a blue pigment, a green pigment, and a purple pigment.

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

Table 1 shows the preferred mass ratio (% by mass) of each pigment in each aspect.

Among pigments, inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, and the like.

(dye)
Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Moreover, these derivatives and lake pigments obtained by turning dyes into lakes are also included.

The acid dye preferably has an acidic group such as sulfonic acid or carboxylic acid. Salt-forming compounds, which are salts of acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds, are also preferred. A salt-forming compound, which is a salt of a resin component having these functional groups and an acid dye, is also preferred. Moreover, the salt-forming compound is sulfonamidated to be modified into a sulfonic acid amide compound, thereby easily obtaining a photosensitive composition having excellent resistance (light resistance and solvent resistance).
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent resistance (light resistance and solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance and solvent resistance) and affinity with pigments. In salt-forming compounds of basic dyes, anion components that act as counter ions include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and halogenated carbonization compounds. A salt-forming compound obtained by salt-forming an anion compound having a conjugate base of an organic acid having a hydrogen group and an acid dye is preferred. It should be noted that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples include dye structures derived from dyes selected from dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, A dye structure derived from a dye selected from quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes. A dye structure derived from the selected dye is more preferred.

Colorant (F) can be used alone or in combination of two or more.

The content of the coloring agent (F) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition.

(Refinement of pigment)
It is preferable to use the pigment after miniaturization. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution-precipitation can be used. Among these, the salt milling treatment by the kneader method, which is one type of wet grinding, is preferable. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

The salt milling process involves heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanical kneading, it is washed with water to remove water-soluble inorganic salts and water-soluble organic solvents. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt to be 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 the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. 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 and the like 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, based on 100 parts by mass of the pigment.

If necessary, a resin may be added to the salt milling treatment. The type of the resin is not particularly limited, and includes natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. Among these, those that are solid at room temperature, water-insoluble, and partially soluble in the above organic solvents are preferred. The amount of the resin to be added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[Dispersion resin (G)]
The photosensitive composition of the present invention can contain a dispersing resin (G). The dispersing resin (G) is used for the purpose of stably dispersing the near-infrared absorbing dye (A) and the colorant (F) in the photosensitive composition.

The dispersing resin (G) is preferably a resin having an adsorptive group that has a high affinity for the near-infrared absorbing dye (A) or the coloring agent (F). The adsorptive group preferably has one or more of a basic group and an acidic group.

Basic groups include, for example, groups containing nitrogen atoms such as primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles.

Examples of acidic groups include carboxyl groups, phosphoric acid groups and sulfonic acid groups.

Resin species of the dispersing resin (G) include, for example, urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups and salts thereof, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin such as polyvinylpyrrolidone and water-soluble polymer compounds, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide/propylene oxide addition compounds, phosphoric acid ester-based compounds, and the like.

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

Commercial products of the dispersing resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by BYK-Chemie Japan. 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, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Nippon Lubrizol Co., Ltd. ,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., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan Ajinomoto Fine Techno's Ajisuper PA111, PB711, PB821, PB822, PB824, etc., JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, international Publication No. 2008/007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007 -23195, JP-A-1996-143651, and the like.

Dispersing resin (G) can be used alone or in combination of two or more.

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

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

The dye derivative (H) is not particularly limited, and examples thereof include dye derivatives having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. The dye derivative (H) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxyl group, or a phosphoric acid group; and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Organic dyes include, for example, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazineindigo compounds, triazine compounds, benzimidazolone compounds, benzo Indole compounds such as isoindole, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, threne compounds, metal complex compounds, azo compounds such as azo, disazo and polyazo, squarylium compounds , and phthalocyanine compounds.

Specifically, diketopyrrolopyrrole dye derivatives, for example, JP 2001-220520, WO 2009/081930, WO 2011/052617, WO 2012/102399, JP 2012/102399, 2017-156397, phthalocyanine dye derivatives are, for example, JP 2007-226161, WO 2016/163351, JP 2017-165820, Japanese Patent No. 5753266, anthraquinone dye derivatives, For example, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009/025325 , quinacridone dye derivatives, for example, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine dye derivatives, for example, JP-A-2011-162662, Thiazine indigo-based dye derivatives, for example, JP-A-2007-314785, triazine-based dye derivatives, for example, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922 , JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, benzoisoindole-based dye derivatives, for example, JP-A-2009-57478, quinophthalone-based dye derivatives, for example , JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, naphthol dye derivatives, for example, JP-A-2012-208329, JP JP-A-2014-5439, azo dye derivatives, for example, JP-A-2001-172520, JP-A-2012-172092, squarylium-based dye derivatives, for example, International Publication No. 2020/054718, etc. compound. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

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

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

Sensitizers (I) include, for example, chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzyl and camphorquinone, benzoin compounds, and fluorene. polymethines such as polymethine-based compounds, naphthoquinone-based compounds, anthraquinone-based compounds, xanthene-based compounds, thioxanthene-based compounds, xanthone-based compounds, thioxanthone-based compounds, coumarin-based compounds, ketocoumarin-based compounds, cyanine-based compounds, merocyanine-based compounds, and oxonol-based compounds dyes, acridine-based compounds, azine-based compounds, thiazine-based compounds, oxazine-based compounds, indoline-based compounds, azulene-based compounds, azulenium-based compounds, squarylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, Tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds compounds, tetraphylline-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, organic ruthenium complexes, benzophenone-based compounds, and the like. Among these, thioxanthone-based compounds and benzophenone-based compounds are preferred from the viewpoint of pattern formation.

(Thioxanthone-based compound)
Thioxanthone compounds include, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like. Among these, 2,4-diethylthioxanthone is preferred.

(benzophenone compound)
Examples of benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

Sensitizer (I) can be used alone or in combination of two or more.

The content of the sensitizer (I) is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, based on 100 parts by mass of the photopolymerization initiator (D).

[Thermosetting compound (J)]
The photosensitive composition of the present invention preferably contains a thermosetting compound (J). As a result, the thermosetting compound (J) is crosslinked by post-baking, and the near-infrared absorbing dye (A) can be inhibited from generating agglomerated foreign matter, which is likely to occur in a high-temperature, high-humidity environment.

The thermosetting compound (J) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Thermosetting compounds (J) include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferable, and epoxy compounds are more preferable, from the viewpoint of suppressing foreign substances.

(epoxy compound)
The epoxy compound preferably has a structure having an aromatic ring and/or an aliphatic ring, and more preferably has a structure having an aliphatic ring from the viewpoint of suppressing the generation of foreign matter. It is preferred that the epoxy group is attached to the aromatic ring and/or the aliphatic ring via a single bond or a linking group. As the linking group, an alkylene group, an arylene group, -O-, -NR- (R represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group), - Examples include SO ₂ -, -CO-, -O-, and -S-. In the case of a structure having an alicyclic ring, the epoxy group is more preferably bound to the alicyclic ring via a single bond.

The number of epoxy groups in the epoxy compound is preferably 2 to 50, more preferably 5 to 50, particularly preferably 10 to 30, from the viewpoint of suppressing foreign matter.

The epoxy equivalent of the epoxy compound is preferably 50-400 g/eg, more preferably 100-200 g/eg. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of epoxy group.

Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted polycondensates of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol Polymers with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol , biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) and polycondensates, 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, glycidyl amine-based epoxy resins , glycidyl ester-based epoxy resins, and the like.

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, EPPN-201, 501H, 502H manufactured by Nippon Kayaku, EOCN-102S, 103S, 104S, 1020 Epikote 1004, 1256 manufactured by Japan Epoxy Resin Co., Ltd., JER1032H60, 157S65, 157S70, 152, 154, Celoxide 2021 manufactured by Daicel Chemical Industries, EHPE-3150, Denacol manufactured by Nagase ChemteX Corporation EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, Nissan Chemical Industries TEPIC-L, H, S, DIC EPICLON 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP -5000, HP-6000, HP-9500 and the like.

The content of the epoxy compound is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the non-volatile matter of the photosensitive composition, from the viewpoint of suppressing foreign substances.

(oxetane compound)
Oxetane compounds are known compounds having an oxetane group. Oxetane compounds include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Monofunctional oxetane compounds include, for example, (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-(triethoxy silyl)propoxy]methyl}oxetane and the like.

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

Bifunctional oxetane compounds include, for example, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3 -ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)- 5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, 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-oxetanyl) methyl) ether and the like.

Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

Trifunctional or higher oxetane compounds 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 phenolic novolak resins described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30 can be mentioned.

The content of the oxetane compound is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition, from the viewpoint of suppressing foreign substances.

A thermosetting compound (J) can be used individually or in combination of 2 or more types.

[Curing agent (curing accelerator)]
The photosensitive composition of the present invention can be used together with a curing agent (curing accelerator) to assist curing of the thermosetting compound (J). Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. Curing agents include, for example, amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and their salts (e.g., 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 (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

Curing agents can be used alone or in combination of two or more.

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 (J).

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

The polymerization inhibitor (K) is, for example, 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 and other alkylcatechol compounds, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 alkylresorcinol compounds such as -propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc. phosphine compounds, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

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

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

The ultraviolet absorber (L) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylate-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. compounds and the like.

Benzotriazole compounds include, for example, 2-(5methyl-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-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of branched and linear alkyl esters of C7-9, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 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-benzotriazole 2- yl)phenyl]propionate.

Commercial products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, Adekastab LA-29, LA-31RG, LA manufactured by ADEKA. -32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

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, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 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- and tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

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, Adekastab LA-46, LA-F70 manufactured by ADEKA, and Sun Chemical Co., Ltd. CYASORB UV-1164 and the like.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 5-sulfonic acid-3, water temperature, 2-hydroxy-4-n-octo xybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octa decyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. .

Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Chemicals, SEESORB 101, 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical. be done.

Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like.

The content of the ultraviolet absorber (L) is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[Antioxidant (M)]
The photosensitive composition of the invention can contain an antioxidant (M). The antioxidant (M) is a photopolymerization initiator (D) and a thermosetting compound (J) in the photosensitive coloring composition that are oxidized and yellowed by the thermal process during thermal curing and ITO annealing. prevent.

Antioxidants (M) include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

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), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3 ,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2′ -methylenebis(6-t-butyl-4-ethylphenol), 2,2′-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis (dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[ 3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanedi-rubis[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) - includes phenol and the like.

Commercial products include, for example, ADEKA's Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, and Chemipro's KEMINOX 101, 179, 76, 9425. , IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., etc. mentioned.

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-butane tetracarboxylate, 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, polycondensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 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)decanedioate -4-piperidinyl) ester, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1, 1 dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl 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 ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6- hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide and the like mentioned.

Commercially available products are, for example, ADEKA's ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 , LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, Cyasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3529, UV-3853 and the like.

Phosphorus antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4' -Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 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-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-t-butyl-6-methylphenyl) and the like.

Commercial products include, for example, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. -EPQ and the like.

Sulfur antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′- ditridecyl 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 and the like.

Commercially available products include, for example, ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei.

Antioxidants (M) can be used alone or in combination of two or more.

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

[Leveling agent (N)]
The photosensitive composition of the invention can contain a leveling agent (N). This further improves the wettability and dryability of the substrate during coating. Examples of the leveling agent (N) include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Commercially available products are, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 manufactured by BYK Chemie, 378, 3455, UV3510, 3570, Toray Dow Corning FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical 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 and the like.

Fluorosurfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

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

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxytetraoleic acid Ethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamides, alkylimidazolines, and the like.

Commercially available products are, for example, Kao 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, Rhodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31 manufactured by ADEKA, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based (co)polymer Polyflow-No. 75, No. 90, No. 95 and the like.

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

Commercially available products include, for example, Acetamine 24, Kotamine 24P, 60W, 86P conch manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos, Adeka Hope YES-25, Adekacol TS-230E, PS-440E and EC-8600 manufactured by ADEKA.

Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Commercially available products include Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

A leveling agent (N) can be used individually or in combination of 2 or more types.

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

[Storage stabilizer (O)]
The photosensitive composition of the present invention can contain a storage stabilizer (O). This stabilizes the viscosity of the photosensitive composition over time. Storage stabilizers (O) include, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenyl and the like. organic phosphines, phosphites, and the like.

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

[Adhesion improver (P)]
The photosensitive composition of the present invention can contain an adhesion improver (P). This improves the adhesion between the cured film and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography.

Examples of the adhesion improver (P) include silane coupling agents and the like. Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; Examples include silane coupling agents such as sulfides and isocyanates such as 3-isocyanatopropyltriethoxysilane.

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

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

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

The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diol. Acetate, 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, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate , dibasic acid esters, and the like. Among these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. are preferred from the viewpoint of pigment dispersibility and alkali-soluble resin solubility. Alcohols such as glycol acetates and diacetone alcohol, and ketones such as cyclohexanone are preferred.

From an environmental point of view, the photosensitive composition of the present invention preferably does not substantially contain organic solvents such as aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). “Substantially not contained” means that the content in the photosensitive composition is 100 mass ppm or less, preferably 50 mass ppm or less, and more preferably 10 mass ppm or less.

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

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

When the total amount of the specific metal elements is within the above range, the photosensitive composition is excellent in dispersion stability and sensitivity even after long-term storage. Further, a cured product prepared using a photosensitive composition having a total amount of specific metal elements within the above range is excellent in heat resistance and generates little foreign matter even when heated.

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

The content of the specific metal element can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

In the photosensitive composition of the present invention, it is preferable to reduce the content of metal elements other than the specific metal elements from the viewpoint of storage stability and suppression of foreign matter generation. Examples of metals other than the specific metal elements include Mn, Cs, Ti, Co, Ni, Si, Pd, and the like.

[Water content]
The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

A photosensitive composition having a water content within the above range is excellent in dispersion stability and sensitivity even after storage over time.

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

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

[Method for producing photosensitive composition]
The photosensitive composition of the present invention is prepared into a dispersion by, for example, adding a near-infrared absorbing dye (A), a dispersing resin (G), an organic solvent (Q), and the like and performing a dispersion treatment. After that, the dispersion can be produced by blending and mixing the alkali-soluble resin (B), the polymerizable compound (C), the photopolymerization initiator (D), and the like. The timing of blending each material is arbitrary. Moreover, a dispersion|distribution process can also be performed in multiple times.

A dispersing machine for performing dispersion treatment includes, 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.

The average dispersed particle size (secondary particle size) of the near-infrared absorbing dye (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A suitable particle size facilitates obtaining a photosensitive composition with high dispersion stability.

The method for measuring the average dispersed particle size (secondary particle size) is, for example, using a Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs the dynamic light scattering method (FFT power spectrum method), and the particle permeability is measured by the absorption mode. The particle shape is assumed to be non-spherical, and the D50 particle diameter is defined as the average diameter. It is preferable to use the organic solvent used for dispersion as the diluent solvent for the measurement, and to measure the ultrasonically treated sample immediately after the sample preparation, because it is easy to obtain results with little variation.

The photosensitive composition is separated by means of centrifugation, filtration with a sintered filter, membrane filter, or the like to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and contaminants. It is preferable to remove the dust that has accumulated. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or more, more preferably no particles of 0.3 μm or less.

<Cured film>
The cured film of the invention is a cured product of the photosensitive composition of the invention. Curing is performed by subjecting the film formed by coating to exposure or the like.

[Method for producing cured film]
The method for producing the cured film is not particularly limited. For example, the step (1) of coating a photosensitive composition on a substrate to form a layer of the composition, and patternwise exposing the layer through a mask. It can be produced by performing the step (2), the step (3) of alkali-developing the unexposed portion to form a patterned cured film, and the step (4) of heat-treating (post-baking) the pattern. In the present invention, it is preferable to form the cured film at a temperature of 150° C. or less throughout the entire process.

The method for producing a cured film will be described in detail below.

(Step (1))
In the step (1) of forming a layer of the composition, the photosensitive composition is coated on 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, a resin substrate, a silicon substrate, and the like. Examples of resin substrates include polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, polyimide substrates, and the like. An organic light emitting layer may be formed on these substrates. The silicon substrate may have, for example, an imaging element such as a CCD or CMOS formed on its surface. In addition, if necessary, an undercoat layer may be provided on the substrate for improving adhesion with the upper layer, preventing diffusion of substances, and flattening the surface of the substrate.
The layer thickness is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5.0 μm.

(Step (2))
In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. A cured film is thus obtained.
Examples of active energy rays used for exposure include ultraviolet rays such as g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), and i-line (wavelength: 365 nm). Light with a wavelength of 300 nm or less can also be used. Light with a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), and the like.
In addition, the exposure may be performed by continuously irradiating the light, or by repeating the irradiation and resting of the light in a cycle of a short time (for example, millisecond level or less) (pulse exposure). .

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

The developing method includes, for example, a dip method, a spray method, a paddle method, and the like. The developing temperature is preferably 15 to 40°C. In addition, it is preferable to wash with pure water after alkali development.

(Step (4))
In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature for post-baking is preferably 150° C. or lower. The lower limit of the heating temperature is not particularly limited as long as curing can be accelerated, but 50° C. or higher is preferable. Also, the heating time is preferably 5 minutes to 2 hours.

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

<Image display device>
The cured film of the present invention can be used in image display devices. Examples of the image display device include a liquid crystal display device and an organic EL display device. The form used for the image display device is not particularly limited, but it can be used as a color filter, a black matrix, a light shielding filter, or an infrared cut filter.
The black matrix is a solid-state imaging device, a black edge provided at the periphery of an image display device such as a liquid crystal display device, a grid-shaped and / or striped black portion between red, blue, and green pixels, Dot and/or linear black patterns for TFT light shielding may be used.

An example of the image display device of the present invention will be described. An image display device comprises the cured film of the present invention and a light source. As a light source, a cold cathode fluorescent lamp (CCFL) and a white LED can be used. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view showing a configuration example of an image display device provided with 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 facing each other with a gap therebetween, and a liquid crystal LC is enclosed between them.

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

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

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

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 .

The liquid crystal LC is aligned according to drive modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

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

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

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 .

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5/I3 ) has a spectral characteristic of 0.1 to 1.3, and a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and the range of 530 nm to 580 nm has a second emission intensity peak wavelength (λ2) within, and the ratio (I2/I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less A white LED light source (LED2) with a is preferred.

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

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

<Solid-state image sensor>
The cured film of the present invention can be used for solid-state imaging devices. The form used for the solid-state imaging device is not particularly limited, but for example, a plurality of photodiodes constituting the light receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor) on a substrate, and A mode having a light-receiving element made of polysilicon or the like and having the cured film of the present invention on the light-receiving element formation surface side or the opposite side of the formation surface is exemplified. 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.

As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging device 201 and a transparent cover glass 203 that is held above the solid-state imaging device 201 and seals the solid-state imaging device 201. there is Further, a lens layer 211 is provided over the cover glass 203 with spacers 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 , light diffusion weakens the light condensing effect of the lens material 212 , reducing the amount of light that reaches the imaging unit 202 . Also, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 211 is provided with the cured film 214 of the present invention to shield light.

The solid-state imaging device 201 photoelectrically converts an optical image formed by an imaging unit 202 serving as a light-receiving surface thereof, and outputs it as an image signal. This solid-state imaging device 201 has a laminated substrate 205 in which two substrates are laminated. The laminated substrate 205 is composed of a rectangular chip substrate 206 and a circuit substrate 207 of the same size.

An imaging unit 202 is provided in the central portion of the surface of the chip substrate 206 . In addition, when stray light enters the peripheral region of the imaging unit 202, a dark current (noise) is generated from the circuits in this peripheral region. .

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

External connection terminals 209 are provided on the rear surface of the circuit board 207 at positions substantially below the respective electrode pads 208 . Each external connection terminal 209 is connected to an electrode pad 208 via a through electrode 210 vertically penetrating through the laminated substrate 205 . In addition, each external connection terminal 209 is connected to a control circuit for controlling driving of the solid-state imaging device 201 and an image processing circuit for performing image processing on an imaging signal output from the solid-state imaging device 201 via wiring (not shown). It is connected.

<Infrared sensor>
The cured film of the present invention can be used for infrared sensors. 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. An infrared sensor 300 shown in FIG. 3 includes a solid-state imaging device 310 .

An imaging area provided on the solid-state imaging device 310 is configured by combining an infrared cut filter 311 and a color filter 312 .
The infrared cut filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm).
The color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light region. For example, pixels of red (R), green (G), and blue (B) are formed. A color filter or the like is used.

Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 is arranged that allows transmission of the light of the wavelength that has passed through the infrared transmission filter 313. As shown in FIG.
The infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared rays of a specific wavelength, and includes the above-described near-infrared absorption pigment (A) and the colorant (F) as a red pigment, A cured film of the present invention containing two or more pigments selected from the group consisting of yellow pigments, blue pigments, green pigments and violet pigments can be used. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

A microlens 315 is arranged on the incident light side of the color filter 312 and the infrared transmission filter 313 . A planarization film 316 is formed to cover the microlenses 315 .

Although the resin film 314 is arranged in the form shown in FIG.

The cured film of the present invention can be used as a light shielding film such as the edge and / or side of the surface of the infrared cut filter 311, and if it is used for the inner wall of the infrared sensor device, it can be used for internal reflection and / or meaningless light to the light receiving part. can be prevented from entering, and the sensitivity can be improved.

According to this infrared sensor, since image information can be captured at the same time, it is possible to perform motion sensing, etc., by recognizing an object whose motion is to be detected. In addition, since distance information can be obtained with this infrared sensor, it is possible to take an image including 3D information. Furthermore, this infrared sensor can also be used as a biometric sensor.

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

The cured film of the present invention can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members imparting light shielding properties and antireflection properties.
Examples of micro LEDs and micro OLEDs include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

Moreover, the cured film of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for optical filters and optical films used in quantum dot displays, as well as members imparting light shielding properties and antireflection properties.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these. In addition, "part" is "mass part" and "%" is "mass%".
In addition, in the present invention, non-volatile matter or non-volatile matter concentration refers to the mass residue after standing in an oven at 230° C. for 30 minutes.

Prior to Examples, each measuring method will be described.

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

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40 ° C. , using a tetrahydrofuran (THF) solution as an eluent and measuring at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. A molecular weight is a polystyrene conversion value.

(Acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution and stir to dissolve uniformly. (manufactured) to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile content of the resin solution.

(Amine value of resin)
The amine value of the resin is a value obtained by converting the total amine value (mgKOH/g) measured according to the method of ASTM D 2074 into non-volatile matter.

<Production of near-infrared absorbing dye (A)>
(Near-infrared absorbing dye (A-1))
40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed with 400 parts of toluene and mixed in a nitrogen gas atmosphere. The mixture was heated with stirring and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. 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 200 parts of hexane was added while stirring the resulting reaction mixture. After filtering the resulting black-brown precipitate, it was washed with hexane, ethanol and acetone in turn and dried under reduced pressure to obtain a near-infrared absorbing dye (A-1) represented by the following chemical formula (17). rice field. 50 parts of the obtained near-infrared absorbing dye (A-1), 500 parts of sodium chloride and 60 parts of diethylene glycol were placed in a gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 12 hours. Next, the kneaded mixture is put into hot 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, dried at 80°C for a day and night, and pulverized. Thus, a fine near-infrared absorbing dye (A-1) was obtained.

chemical formula (17)

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

chemical formula (18)

(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 three 34 parts of aluminum chloride was mixed and stirred, and after the temperature was raised, 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 was added to 1,500 parts of concentrated sulfuric acid in a reaction vessel under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution is poured into 1,000 parts of cold water at 3°C, and the precipitate formed is filtered, washed with water, washed with an aqueous 2.5% sodium hydroxide solution, washed with water in this order, and dried. Compound b was obtained.
5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50°C. After adding 10 parts of compound b little by little to this solution, the mixture was stirred at 90° C. for 120 minutes. For confirmation of the end point of the reaction, for example, the reaction liquid was dropped onto a filter paper, and the end point was set at the point where the bleeding disappeared. Subsequently, this reaction solution is poured into 2,000 parts of water, and the resulting precipitate is filtered, washed with water in this order, dried, and mixed with a compound represented by the following chemical formula (19) (mixing ratio: obtained a near-infrared absorbing dye (A-3) with n1:n2:n3:n4=7:19:59:15).
A micronized near-infrared absorbing dye (A-3) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (19)

(Near-infrared absorbing dye (A-4))
A near-infrared absorbing dye (A-4) represented by the following chemical formula (20) was obtained according to the description of International Publication No. 2019/058882.
A fine near-infrared absorbing dye (A-4) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (20)

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

chemical formula (21)

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B-1) solution)
100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, stirred while replacing with nitrogen, and heated to 78°C. bottom. Next, Karenz MOI-DEM (manufactured by Showa Denko malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino] which is a monomer containing a blocked isocyanate group carbonyl]-1,3-diethyl ester) 25.2 parts, 20.7 parts of methacrylic acid as an acidic group-containing monomer, 31.2 parts of 2-hydroxyethyl methacrylate as a hydroxyl group-containing monomer, aliphatic condensation A mixture of 37.5 parts of dicyclopentanyl methacrylate, which is a ring structure-containing monomer, and 27.0 parts of methyl methacrylate, which is another monomer unit, and 12.0 parts of 2,2′-azobis(2,4 -Dimethylvaleronitrile) (polymerization initiator) was added and dissolved in 50 parts of PGMAc and dropped into the flask from the dropping funnel. After completion of dropping, the mixture was stirred at 78°C for 3 hours.
Thereafter, PGMAc was added so that the non-volatile content was 40% by mass to prepare an alkali-soluble resin (B-1) solution. The alkali-soluble resin (B-1) had an acid value of 74 mgKOH/g and a weight average molecular weight of 8,000.

(Alkali-soluble resin (B-2) and (B-3) solution))
Alkali-soluble resins (B-2) and (B-3) were synthesized by changing the compounding type and amount so that the composition and mol% ratio shown in Table 2 were obtained, and PGMAc was added to reduce the nonvolatile content to 40% by mass. and

<Production of colorant (F)>
(Micronized green pigment (F-1))
C. I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3,000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then heated to 80°C. The green pigment (F-1) was obtained by drying overnight and pulverizing.

(Refined red pigment (F-2))
C. I. Pigment Red 254 (100 parts), sodium chloride (1,200 parts) and diethylene glycol (120 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a fine red pigment (F-2).

(Micronized blue pigment (F-3))
C. I. Pigment Blue 15:6 (100 parts), sodium chloride (1,000 parts), and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50° C. for 12 hours. This mixture is poured into 3,000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. The mixture was dried overnight and pulverized to obtain a finely divided blue pigment (F-3).

(Micronized yellow pigment (F-4))
C. I. Pigment Yellow 138 (100 parts), sodium chloride (800 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 12 hours. This mixture is poured into 3000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then kept at 80°C for a day and night. By drying and pulverizing, a finely divided yellow pigment (F-4) was obtained.

(Micronized purple pigment (F-5))
C. I. Pigment Violet 23 (100 parts), sodium chloride (800 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 12 hours. This mixture is poured into 3000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then kept at 80°C for a day and night. A finely divided purple pigment (F-5) was obtained by drying and pulverizing.

<Production of dispersion resin (G)>
(Dispersion resin (G-1) solution)
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer. After stirring for 1 hour, the inside of the system was replaced 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 are charged, and the temperature is raised to 110° C. under a nitrogen stream to form the first block (B block). Polymerization started. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the temperature was maintained at 110° C. under a nitrogen atmosphere. Stir and continue the reaction. Two hours after the addition, the polymerization solution was sampled and non-volatile content was measured. After confirming 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. The polymerization was terminated by cooling to obtain a dispersion resin (G-1) having an amine value of 169.8 mgKOH/g per non-volatile content. After cooling to room temperature, a sample of about 2 g was dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added so that the non-volatile content was 30% by mass. (G-1) A solution was prepared.

(Dispersion resin (G-2) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the 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., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured. % or more, the reaction solution was cooled to room temperature to stop the polymerization, and a dispersion resin (G-2) having an amine value per non-volatile content of 57 mgKOH/g was obtained. PGMAc was added to dilute the non-volatile content to 30% by mass to obtain an AB block polymer dispersion resin (G-2) solution.

(Dispersion resin (G-3) solution)
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 introduced into a reaction vessel equipped with a gas inlet tube, a temperature control, a condenser and a stirrer, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution of 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100° C. for 7 hours. . After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction solution is cooled to room temperature to stop the polymerization, and the acid value per nonvolatile content is 70 mgKOH / g Dispersing resin ( G-3) was obtained. PGMAc was added and diluted so that the nonvolatile content was 30% by mass in the measurement of the nonvolatile content, to obtain a dispersion resin (G-3) solution.

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 1.5 mm. It was filtered through a 0 μm filter to prepare Dispersion 1. Organic solvent (Q-1) is PGMAc.
Near infrared absorbing dye (A-1): 15.0 parts Dispersion resin (G-1) solution: 20.0 parts Organic solvent (Q-1): 65.0 parts

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

<Production 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 a photosensitive composition 1.
Dispersion 1: 15.0 parts Dispersion 3: 20.0 parts Alkali-soluble resin (B-1) solution: 8.0 parts Polymerizable compound (C1-1): 6.0 parts Photopolymerization initiator (D- 1): 0.2 parts Photopolymerization initiator (D-2): 0.1 parts Thiol chain transfer agent (E-1): 0.05 parts Thermosetting compound (J-1): 0.7 parts Leveling agent (N): 1.0 parts Organic solvent (Q): 48.95 parts

[Examples 2 to 27, Comparative Examples 1 and 2]
(Photosensitive compositions 2 to 29)
Photosensitive compositions 2 to 29 were prepared in the same manner as in Example 1 except that the photosensitive composition 1 of Example 1 was changed to the raw materials and amounts shown in Tables 4-1 to 4-3.

The raw materials listed in Tables 4-1 to 4-3 are as follows.

[Polymerizable compound (C)]
(Polymerizable compound (C1))
C1-1: tricyclodecanedimethanol diacrylate (molecular weight 304, aliphatic condensed ring structure)
C1-2: 1,3-adamantanediol diacrylate (molecular weight 276, aliphatic condensed ring structure)
C1-3: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (molecular weight 546, aromatic condensed ring structure)
C1-4: Bisphenol A diacrylate with 3 EO modifications (molecular weight 380, aromatic ring structure)
C1-5: Bisphenol A diacrylate with 4 EO modifications (molecular weight 512, aromatic ring structure)

(Polymerizable compound (C2))
C2-1: neopentyl glycol diacrylate C2-2: mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate C2-3: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate

[Photoinitiator (D)]
D-1: The compound of the above chemical formula (12) D-2: Omnirad 907 (manufactured by IGM Resins, acetophenone compound)

[Thiol-based chain transfer agent (E)]
E-1: pentaerythritol tetrakis (3-mercaptopropionate)

[Thermosetting compound (J)]
J-1: EHPE-3150 (manufactured by Daicel, a compound having an aliphatic ring with about 15 epoxy groups)

[Leveling agent (N)]
N-1: BYK-330 (manufactured by BYK-Chemie)
N-2: Megafac F-554 (manufactured by DIC)
1 part of each of (N-1) and (N-2) above was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution as a leveling agent (N).

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

<Evaluation of photosensitive composition>
The obtained photosensitive compositions 1 to 29 (Examples 1 to 27, Comparative Examples 1 and 2) were evaluated as follows. Table 5 shows the evaluation results.

[Adhesion evaluation]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to light at an intensity of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp through a photomask having a stripe pattern with a width of 5 to 25 μm in increments of 5 μm. Thereafter, the substrate was developed by spraying with an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., washed with deionized water, and air-dried. The coating with each photosensitive composition was developed in the shortest possible time for pattern formation without residual development.
The obtained patterns with widths of 5, 10, 15, 20 and 25 μm on the substrate were observed with an optical microscope to confirm the minimum line width of the remaining patterns. The evaluation criteria are as follows, and 3 or more is regarded as 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: Fine lines do not remain.

[Line width evaluation]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed through a photomask with a stripe pattern of 100 μm width using a high-pressure mercury lamp at two levels of illumination intensity of 30 mW/cm ² and exposure amounts of 50 mJ/cm ² and 100 mJ/cm ² . . After that, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., washed with deionized water, and air-dried. The resulting substrate was post-baked in a clean oven at 150° C. for 60 minutes to obtain an evaluation substrate.
The resulting evaluation substrate was measured for line width (CD ₅₀ ) at an exposure dose of 50 mJ/cm ² and line width (CD ₁₀₀ ) at 100 mJ/cm ² using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon. The difference in line width (ΔCD) due to the difference in exposure amount was obtained from the equation (1). The evaluation criteria are as follows, and 3 or more is considered practical.
Formula (1): ΔCD = CD ₁₀₀ - CD ₅₀
5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6 μm or more

[Cross-sectional shape evaluation]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to light at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² through a photomask having a stripe pattern with a width of 100 μm using a high-pressure mercury lamp. After that, the substrate was spray-developed using an aqueous developer containing 0.12% by mass of nonionic surfactant and 0.04% by mass of potassium hydroxide at 23° C., washed with deionized water, and air-dried. . The resulting substrate was post-baked in a clean oven at 150° C. for 60 minutes to obtain an evaluation substrate.
Spray development was carried out for the shortest possible time for pattern formation without development residue for each photosensitive composition film.
The cross-sectional shape of the pattern was confirmed using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Tech Co., Ltd.). For the evaluation, a cross-sectional SEM image of a striped pattern with a width of 100 μm was captured, and the cross-sectional shape was evaluated by measuring the taper angle between the substrate and the end of the cross-section of the pattern. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of 30 degrees or more and less than 40 degrees, or 60 degrees or more and less than 70 degrees 2: Taper angle of 20 degrees or more and less than 30 degrees, or 70 degrees or more and less than 90 degrees 1: Taper angle less than 20 degrees or 90 degrees or more

[Solvent resistance evaluation]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling this substrate to room temperature, it was exposed to ultraviolet light through a photomask having a stripe pattern of 100 μm width using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . Furthermore, after cooling this substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., and then washed with deionized water. , air dried. Then, it was post-baked in a clean oven at 150° C. for 60 minutes to obtain a substrate for evaluation.
The resulting substrate for evaluation was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, washed with deionized water, air-dried, and a stripe pattern portion with a width of 100 μm was observed with an optical microscope. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: No change in appearance and color.
4: Slight wrinkles, etc., but no change in color.
3: Some wrinkles or the like occur, but there is no change in color.
2: Wrinkles and the like are generated on the entire surface, and the color is slightly faded.
1: Peeling and discoloration occurred.

[Evaluation of high temperature and high humidity resistance]
The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) of 100 mm long×100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness would be 2.0 μm. and dried on a hot plate at 70° C. for 1 minute. Then, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . Further, after cooling this substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., and washed with deionized water. and air-dried. The resulting substrate was post-baked in a clean oven at 150° C. for 60 minutes to obtain an evaluation substrate.
The obtained substrate was stored for 200 hours under conditions of a temperature of 85° C. and a humidity of 85%. After storage, the number of foreign substances on the pattern was counted using an optical microscope. The evaluation criteria are as follows, and 3 or more is practical.
5: The number of foreign substances is less than 5 4: The number of foreign substances is 5 or more and less than 10 3: The number of foreign substances is 10 or more and less than 15 2: The number of foreign substances is 15 or more and less than 20 1: 20 or more foreign objects

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

Claims (12)

A photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C) and a photopolymerization initiator (D),
The photosensitive composition, wherein the polymerizable compound (C) comprises a polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure. 2. The photosensitive composition according to claim 1, wherein the polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure has a molecular weight of 500 or less. 3. The photosensitive composition according to claim 1, wherein said ring structure is a condensed ring structure. Any of claims 1 to 3, wherein the content of the polymerizable compound (C1) having two (meth)acryloyl groups and a ring structure is 50% by mass or more in 100% by mass of the polymerizable compound (C). 1. The photosensitive composition according to claim 1. The alkali-soluble resin (B) according to any one of claims 1 to 4, comprising an alkali-soluble resin having a blocked isocyanate group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2). The photosensitive composition of The photosensitive composition according to any one of claims 1 to 5, further comprising a thiol chain transfer agent (E). The photosensitive composition according to any one of claims 1 to 6, further comprising a coloring agent (F). A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 7. An optical filter comprising the cured film according to claim 8 . An image display device comprising the cured film according to claim 8 . A solid-state imaging device comprising the cured film according to claim 8 . An infrared sensor comprising the cured film according to claim 8 .

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