JP2023109532A - Photosensitive composition, cured film using the same, optical filter, image display device, solid-state image sensor, and infrared sensor - Google Patents

Abstract

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

Description

The present invention relates to a photosensitive composition containing a near-infrared absorbing pigment.

2. Description of the Related Art 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, mobile devices with camera functions, 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 of the infrared cut filter by photolithography. A photosensitive composition used for forming a pattern is usually used after being stored for several weeks to several months after production. In that case, there were problems such as changes in viscosity and sensitivity and generation of aggregates due to differences in storage environment and period. When the viscosity and sensitivity of the photosensitive composition change, variations in film thickness, developability, pattern shape, etc. occur, and the quality of the infrared cut filter deteriorates. In particular, when the near-infrared absorbing dye is a pigment, there is a problem that it is difficult to disperse and the stability tends to deteriorate during storage.

In addition, since the infrared cut filter is used in a high temperature and high humidity environment, it is required to have high resistance under high temperature and high humidity.

For example, Patent Document 1 discloses a resin composition containing an organic pigment, a resin and a solvent, and having Na atoms of 0.01 to 50 ppm by mass based on the total solid content. Further, Patent Document 2 discloses a resin composition containing a near-infrared absorbing dye, a silane coupling agent having an amino group, and a poly(amide)imide resin.

WO2018/142804 JP 2016-118772 A

However, the resin compositions described in Patent Documents 1 and 2 were not able to satisfy storage stability and resistance under high temperature and high humidity at the same time.

An object of the present invention is to provide a photosensitive composition which is excellent in storage stability and capable of forming a cured film having excellent resistance under high temperature and high humidity.

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

ADVANTAGE OF THE INVENTION According to said invention, the photosensitive composition which is excellent in storage stability and can form the cured film which has the outstanding resistance under high temperature and high humidity can be provided. 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 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with a cured film.

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.
Further, with respect to the molecular weight of the compound in the present invention, for low molecular weight compounds whose molecular weight can be specified, it is a value calculated by calculation (formula weight), or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), For a compound having a molecular weight distribution, it 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.

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

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.

Near-infrared absorbing pigments are difficult to disperse and have poor storage stability. In particular, compounds having a π-conjugated plane containing a monocyclic or condensed aromatic ring tend to associate and aggregate due to interactions between the π-conjugated planes, and the storage stability tends to worsen. However, by including a specific amount of a compound having an aromatic ring as an organic solvent, the compound having an aromatic ring is oriented to the compound having a π-conjugation plane containing a monocyclic or condensed aromatic ring, resulting in π-conjugation. We speculate that the storage stability is improved by suppressing the interaction between the planes.
Moreover, it is preferable to control the content of the specific metal and the content of water in the photosensitive composition of the present invention. According to this aspect, the reaction of the photopolymerization initiator during storage is suppressed, and the generation of aggregates and changes in viscosity and sensitivity are suppressed even after storage.

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

A compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring is a compound having a maximum absorption at a wavelength of 700 to 2,000 nm, and from the viewpoint of light resistance, heat resistance, and resistance to high temperature and high humidity. Therefore, the solubility in water at 25° C. and 100 g of propylene glycol monomethyl ether acetate is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

The π-conjugated plane preferably contains 2 to 100 monocyclic or condensed aromatic rings, more preferably 3 to 50, even more preferably 4 to 40, and 5 to 30. It is particularly preferable to contain one. Aromatic rings include, for example, benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, peptalene ring, indacene ring, perylene ring, pentacene ring, quaterrylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, and chrysene ring. , triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, Examples include pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, indole ring, isoindole ring, carbazole ring, and condensed rings having these rings.

Compounds having a π-conjugated plane containing a monocyclic or condensed aromatic ring include, for example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds. etc. Among these, from the viewpoint of light resistance, heat resistance, and resistance to high temperature and high humidity, it is preferable to include at least one selected from the group consisting of squarylium compounds, pyrrolopyrrole compounds, naphthalocyanine compounds and indigo compounds. Phthalocyanine compounds are more preferred.

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.; JP, JP 2009-29955, WO 2017/002920, WO 2018/186490, etc.; indigo compound, JP 2013-230412, etc.; 336150, JP 2007-197492, JP 2008-88426, etc.; anthraquinone compounds, JP-A-62-903, JP-A-1-172458, etc.; 2009-263614, JP-A-2010-90313, JP-A-2011-068731; the squarylium compound is disclosed in JP-A-2011-132361, JP-A-2016-142891, WO2017/135359, International Publication No. 2018/225837, JP-A-2019-001987, International Publication No. 2020/054718, etc.; croconium compounds include compounds described in International Publication No. 2019/021767, etc.

(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 . The group represented by R ^1x and R ^1y is preferably an alkoxy group having a branched alkyl group or an aryl group having a group represented by —OCOR ¹¹ as a substituent. The 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 preferably a hydrogen atom, an alkyl group, an aryl group, or -BR ^4x R ^4y A group represented by —BR ^4x R ^4y is particularly preferable. 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 having at least one central element selected from the group consisting of Al, Ga and In. The naphthalocyanine compound is preferably, for example, 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.
_M1 represents Al, Ga, or In.
Z represents a ligand having one or more coordination sites for _M1 .

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.

_M1 is preferably Al from the viewpoint of near-infrared absorptivity, storage stability, and resistance under high temperature and high humidity.

The ligand represented by Z is a ligand having at least one selected from a coordination site that coordinates anion to _M1 and a coordination site that coordinates to _M1 with a lone pair. mentioned. A coordination site coordinated by an anion may be dissociated or non-dissociated. The ligand may be a ligand having one coordination site for _M1 , or a ligand having two or more coordination sites for _M1 .

From the viewpoint of storage stability, Z is preferably a ligand having a phosphorus atom. Z is preferably a ligand having a hydrophobic group from the viewpoint of resistance to high temperature and high humidity. Among them, Z is more preferably a ligand having a phosphorus atom and a hydrophobic group.
In addition, a hydrophobic group represents a group with low affinity for water. Groups with low affinity for water include optionally substituted alkyl groups, optionally substituted aryl groups, optionally substituted alkoxy groups, and optionally substituted aryloxy groups. etc. Alkyl groups and alkoxy groups preferably have 1 to 30 carbon atoms. The aryl group and the aryloxy group preferably have 6 to 30 carbon atoms. A halogen atom, a nitro group, a nitrile group, etc. are mentioned as a substituent.

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

general formula (5)

In general formula (5), R ²⁹ and R ³⁰ each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxyl group. or represents an aryloxy group which may have a substituent. * is a bond with _M1 .

"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 (5), from the viewpoint of resistance to high temperature and high humidity, at least one of R ²⁹ and R ³⁰ is an aryl group optionally having a substituent or an aryl group optionally having a substituent An oxy group is preferable, both R ²⁹ and R ³⁰ are more preferably an aryl group or an aryloxy group, and both R ²⁹ and R ³⁰ are particularly preferably a phenyl group or a phenoxy group.

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

general formula (6)

In general formula (6), 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.
_M2 represents Al, Ga, and In.
Z represents a ligand having one or more coordination sites for _M2 .

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 (6), 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 storage stability.

_M2 is preferably Al from the viewpoint of near-infrared absorptivity, storage stability, and resistance under high temperature and high humidity.

Z is as described in general formula (4) above.

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 (7) and/or general formula (8).

In general formulas (7) and (8), 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.

Acidic groups include —SO ₃ H and —COOH. Examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts and aluminum salts. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, 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 includes Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, Ba and the like. Among these, 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.

Compounds having a π-conjugated plane containing a monocyclic or condensed aromatic ring 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 as compared with the case of using only one type, and near-infrared rays in a wide wavelength range can be absorbed.

[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 pigment (A). Other near-infrared absorbing compounds, for example, JP-A-2013-076926, JP-A-2015-068945, WO 2017/135300, JP-A-2019-174813, near-infrared absorbing dyes described in, oxidation Examples include metal oxide particles or metal particles such as indium tin, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, copper, nickel, silver, and gold.

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

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

(Lactone-modified polymerizable compound)
A lactone-modified polymerizable compound is a compound having a lactone-modified structure in its molecule. The lactone-modified polymerizable compound includes polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethritol, tripentaerythritol, glycerin, diglycerol, and trimetholmelamine, and ( It is obtained by esterifying meth)acrylic acid and ε-caprolactone or other lactone compounds.

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

(Polymerizable compound having an acidic group)
Polymerizable compounds having an acidic group include, for example, esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid, and dicarboxylic acids; Examples include esterified products with meth)acrylates. In addition, the polymerizable compound having an acidic group is a compound having no urethane bond.

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

Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, itaconic phthalate, and the like.

Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid.
Monohydroxyalkyl (meth)acrylates, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and the like.

Commercial products of polymerizable compounds having an acidic group include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, M- manufactured by Toagosei Co., Ltd. 521 and the like.

(Polymerizable compound having urethane bond)
The polymerizable compound having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, or a polyfunctional isocyanate obtained by reacting a polyhydric alcohol with a hydroxyl group-containing (meth)acrylate. ) urethane (meth)acrylate obtained by reacting acrylate, and the like.

The hydroxyl group-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta (Meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate. , their burettes, isocyanate nurates, trimethylolpropane adducts, and the like.

A polymerizable compound having a urethane bond may further have an acidic group from the viewpoint of developability. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among them, a carboxyl group is preferred. note that,

A method of introducing an acidic group into a polymerizable compound having a urethane bond, for example, first reacts the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate. Then, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.

Mercapto compounds having a carboxyl group include, for example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

Commercially available polymerizable compounds having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., and UA manufactured by Shin-Nakamura Chemical Co., Ltd. -1100H, U-6LPA, UA-33H, U-10HA, U-15HA, EBECRYL1290 and KRM8452 manufactured by Daicel Ornex.

(Polymerizable compound having a tertiary amine structure)
Polymerizable compounds having a tertiary amine structure include, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and (meth)acrylate compounds. A Michael addition reaction product of (X) and an amine compound (Y) can be mentioned.

(Meth)acrylate compounds (X) are, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ) acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra (Meth)acrylates, trimethylolpropane alkylene oxide-modified tri(meth)acrylates, ditrimethylolpropane alkylene oxide-modified tri- and tetra-(meth)acrylates, pentaerythritol alkylene oxide-modified tri- and tetra-(meth)acrylates, diglycerin alkylene oxide-modified tri-(meth)acrylates and tetra(meth)acrylates, dipenterythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylates.
Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide and butylene oxide.
The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

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

Amine compounds (Y) include, for example, n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m- primary amines such as aminophenol and p-aminophenol;
Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, 4 - secondary amines such as anilinephenol;

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

The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and known methods can be used. For example, methods described in International Publication No. 2006/075754, Japanese Patent Publication No. 2008-545859, Japanese Patent Application Laid-Open No. 2017-066347, and the like can be mentioned.

A polymerizable compound having a tertiary amine structure may have an acidic group and/or a hydroxyl group. Methods for introducing an acidic group and/or a hydroxyl group include, for example, a method of using a compound having an acidic group and/or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y); A method of adding an acid anhydride and the like can be mentioned.

Commercially available polymerizable compounds having a tertiary amine structure include, for example, Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

(Polymerizable compound having dendrimer structure or hyperbranched structure)
A polymerizable compound having a dendrimer structure has a chemical structure in which the chemical structure constituting the core (hereinafter also referred to as the core portion) is regularly and repeatedly branched to the outside, and a polymerizable unsaturated group is bonded to the terminal thereof. It is spherical and has a highly controlled chemical structure and molecular weight. A hyperbranched structure has a chemical structure similar to that of a dendrimer.

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

(Other polymerizable compounds)
Other polymerizable compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) ) acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A Diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated Various acrylic and methacrylic esters such as melamine (meth)acrylate, epoxy (meth)acrylate, urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like. EO is an abbreviation for ethylene oxide, and PO is an abbreviation for propylene oxide.

Other commercially available polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R- 684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, Toagosei Aronix M-303, M-305, M-306, M-309, M- 310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, MT-3549, Viscoat #310HP, #335HP, #700, #295, #330, #360 manufactured by Osaka Organic Chemical Industry Co., Ltd., #GPT, #400, #405, OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd., Miwon Specialty Chemical Co., Ltd. , Ltd. Miramer HR6060, 6100, 6200, Shin Nakamura Chemical Co., Ltd. NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, A-9300, Daicel Allnex Co. EBECRYL40 , 130, 140, 145 and the like.

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

The content of the polymerizable compound (B) 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 (C)]
The photosensitive composition of the present invention contains a photoinitiator (C). Thereby, the photosensitive composition can be cured by irradiation with active energy rays.

The photopolymerization initiator (C) 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, 379EG manufactured by IGM Resins as acetophenone compounds, Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds, and IRGACURE OXE-01 manufactured by BASF Japan as oxime compounds. 02, 03, 04, N-1919 manufactured by ADEKA, NCI-730, 831, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380 manufactured by Changzhou Tenryu New Material Co., Ltd. 365, 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 and the like.
In addition, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, JP 2011-020998, International Publication 2015/036910, International Oxime-based compounds described in Publication No. 2021/175855 and the like are also included.

(Compound represented by general formula (9))
The photosensitive composition of the present invention preferably contains a compound represented by the following general formula (9) as a photopolymerization initiator (C) from the viewpoint of storage stability and resistance under high temperature and high humidity.

general formula (9)

(In general formula (9), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ₃ represents a hydrogen atom or a monovalent substituent; show.)

R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms may be linear, branched, cyclic, or a combination thereof, such as methyl, ethyl, propyl, isopropyl, butyl. group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group and the like. be done. Among them, straight-chain alkyl groups having 3 to 8 carbon atoms are preferable, and straight-chain alkyl groups having 4 to 6 carbon atoms are more preferable from the viewpoint of pattern shape.

R ₃ represents a hydrogen atom or any monovalent substituent.
Examples of monovalent substituents include alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group; F, Cl, Br, I and the like. a halogen atom; an acyl group having 1 to 20 carbon atoms; an alkyl ester group having 1 to 20 carbon atoms; an alkoxycarbonyl group having 1 to 20 carbon atoms; a halogenated alkyl group having 1 to 20 carbon atoms; Aromatic ring group having 4 to 20 numbers; Amino group; Aminoalkyl group having 1 to 20 carbon atoms; Hydroxyl group; Nitro group; Cyano group; and the like. Examples of the substituent that the benzoyl group or thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and the like. . Among them, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred, from the viewpoint of radical generation efficiency.

Examples of the method for producing the compound represented by the general formula (9) include the methods described in JP-T-2019-507108, JP-T-2019-528331, and the like.

Specific examples of the compound represented by formula (9) are shown below. In addition, this invention is not limited to these.

Among the compounds of the chemical formulas (10) to (13), the compound of the chemical formula (10) is preferable from the viewpoint of storage stability and resistance under high temperature and high humidity.

The compounds represented by formula (9) can be used singly or in combination of two or more.

The content of the photopolymerization initiator (C) is preferably 0.5 to 20% by mass in 100% by mass of the non-volatile content of the photosensitive composition from the viewpoint of storage stability and resistance under high temperature and high humidity. ~10% by mass is more preferred.

[Organic solvent (D)]
(Compound having an aromatic ring)
The photosensitive composition of the present invention contains, as an organic solvent (D), 0.005 to 0.5 parts by weight per 100 parts by weight of a compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring. Including compounds with aromatic rings.

Examples of compounds having an aromatic ring include toluene, xylene, benzene, trimethylbenzene, ethylbenzene, propylbenzene, 1-methylbenzene, butylbenzene, 1-phenylhexane, 1,2-diethylbenzene, chlorobenzene and benzyl alcohol. be done. Among these, toluene is preferable from the viewpoint of storage stability.

A compound having an aromatic ring can be used alone or in combination of two or more.

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

(Organic Solvents Other Than Compounds Having Aromatic Rings)
The photosensitive composition of the invention preferably contains an organic solvent other than the compound having an aromatic ring.

Organic solvents other than compounds having an aromatic ring include, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1 ,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3 ,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxy butanol, 3-methoxybutyl acetate, 4-heptanone, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-propyl acetate, N-methylpyrrolidone, γ-butyrolactone, isobutyl alcohol, isophorone, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol mono Propyl 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 mono Propyl 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, acetic acid Examples include propyl and dibasic acid esters. Among these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetates such as ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone kind is preferred.

Organic solvents other than compounds having an aromatic ring can be used alone or in combination of two or more.

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

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

In the present invention, the silane coupling agent (E) is a compound having a hydrolyzable group and other functional groups. A hydrolyzable group is a group that directly bonds to a silicon atom and forms a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups, and the like. Among these, an alkoxy group is preferable. The alkoxy group is preferably a methoxy group from the viewpoint of resistance to high temperature and high humidity.
Functional groups other than the above include, for example, epoxy group, amino group, vinyl group, (meth)acryloyl group, isocyanate group, isocyanurate group, mercapto group, oxetanyl group, styryl group, and ureido group. Among these, epoxy group, (meth)acryloyl group, isocyanurate group, and mercapto group are preferable, and epoxy group and (meth)acryloyl group are more preferable, from the viewpoint of resistance under high temperature and high humidity.

Silane coupling agents (E) are, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid xypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane and the like. .

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

Also, the silane coupling agent (E) may be of polymer type. The polymer type includes polysiloxane type and organic polymer type.

The polysiloxane type is a silane coupling agent in which a hydrolyzable group and other functional groups are bonded to a polymer having a polysiloxane skeleton in its main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805 and X-41-1810 manufactured by Shin-Etsu Silicone Co., Ltd.

The organic polymer type is a silane coupling agent in which a hydrolyzable group and other functional groups are bonded to an organic polymer whose main chain is an organic structure. Organic polymer type commercial products are X-12-1048, X-12-1050, X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-972F, X-12-9845, X-12-9845, X-12-1154, X-12-972F, X -12-1159L and the like.

Silane coupling agents (E) can be used alone or in combination of two or more.

The content of the silane coupling agent (E) is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment (A) from the viewpoint of storage stability and resistance under high temperature and high humidity. , more preferably 0.5 to 5 parts by mass.

[Alkali-soluble resin (F)]
The photosensitive composition of the present invention can contain an alkali-soluble resin (F). As a result, various resistances of the cured film are improved.

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

The alkali-soluble resin (F) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. Alkali-soluble groups include, for example, carboxyl groups, phosphoric acid groups, sulfonic acid groups, hydroxyl groups, phenolic hydroxyl groups, etc. Among these, carboxyl groups are preferred.
Also, the alkali-soluble resin (F) can contain thermosetting groups such as epoxy groups, oxetanyl groups, and isocyanate groups. The isocyanate group may be protected with a thermally detachable compound (blocking agent).

(Non-photosensitive alkali-soluble resin)
Non-photosensitive alkali-soluble resins include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, Alternatively, isobutylene/(anhydrous) maleic acid copolymer and the like can be mentioned. Among these, acrylic resins having acidic groups and styrene/styrenesulfonic acid copolymers are preferred.

(Photosensitive alkali-soluble resin)
A photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. The photosensitive alkali-soluble resin is preferably, for example, a resin synthesized by the method (i) or (ii) shown below. By curing with active energy rays, the resin is three-dimensionally crosslinked to improve the crosslink density and resistance.

[Method (i)]
Method (i), for example, first synthesizes a polymer of an epoxy group-containing monomer and other monomers. Next, there is a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer, and reacting the formed hydroxyl group with a polybasic acid anhydride to obtain a photosensitive alkali-soluble resin.

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylates can be mentioned. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate Acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonyl Phenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, nonylphenol (Meth)acrylates such as PO-modified (meth)acrylates of
(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 ;
styrene or styrenes such as α-methylstyrene;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedi maleimide, 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 -N-substituted maleimides such as 6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, a phosphate group-containing unit such as a compound obtained by reacting a hydroxyl group of a hydroxyl group-containing monomer described later with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid mers.

Monocarboxyl group-containing monomers are, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, cyano-substituted and monocarboxylic acids such as monocarboxylic acids.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. In addition, if necessary, tricarboxylic anhydrides such as trimellitic anhydride and tetracarboxylic dianhydrides such as pyromellitic anhydride can be used to hydrolyze remaining anhydride groups.

As a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Next, there is a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin.

[Method (ii)]
Method (ii) synthesizes polymers of, for example, hydroxyl group-containing monomers, monocarboxyl group-containing monomers, and other monomers. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

Hydroxyl group-containing monomers, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylates or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate; In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because foreign substances are less likely to form in the coating. In terms of photosensitivity, glycerol mono(meth)acrylate is preferred.

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

As the monocarboxyl group-containing monomer and other monomers, those mentioned above can be used.

The raw materials used for synthesizing the photosensitive alkali-soluble resin can be used alone or in combination of two or more.

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

The weight average molecular weight (Mw) of the alkali-soluble resin (F) is preferably 4,000 to 50,000, more preferably 4,000 to 40,000, from the viewpoint of resistance. Also, the value of Mw/Mn is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to substrates and developability.

The acid value of the alkali-soluble resin (F) is preferably 30-200 mgKOH/g, more preferably 40-180 mgKOH/g. Adhesion to substrates and developability are improved by an appropriate acid value.

The content of the alkali-soluble resin (F) 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.

[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 pigment (A) 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 pigment (A). 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 storage 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, and the resins described in JP-A-1996-143651.

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

From the viewpoint of storage 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 pigment (A).

[Dispersing aid (H)]
The photosensitive composition of the present invention can contain a dispersing aid (H). Examples of the dispersing aid (H) include compounds having a structure in which a portion of a pigment is substituted with an acidic group, a basic group, a neutral group, a group having a salt structure, or the like. The dispersing aid (H) is a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, an amine salt thereof, or a sulfonamide group or a terminal having a basic substituent such as a tertiary amino group. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.

The dispersing aid (H) preferably has a structure derived from a compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring. Compounds having a π-conjugated plane containing a monocyclic or condensed aromatic ring include, for example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds. etc.

Examples of the dispersing aid (H) include compounds described in International Publication No. 2016/035695, International Publication No. 2017/146092, International Publication No. 2018/101189, and the like.

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

From the viewpoint of storage stability, the content of the dispersing aid (H) is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the near-infrared absorbing pigment (A).

[Colorant (I)]
The photosensitive composition of the present invention can contain a coloring agent (I). 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 (I) 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 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.

Specifically, the black pigment is 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 (I). and exhibiting a black color.

[Sensitizer (J)]
The photosensitive composition of the present invention preferably contains a sensitizer (J).

Sensitizers (J) 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.

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

The content of the sensitizer (J) is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (C).

[Thermosetting compound (K)]
The photosensitive composition of the present invention preferably contains a thermosetting compound (K). Thereby, the thermosetting compound (K) is crosslinked in the heat treatment step, and the resistance under high temperature and high humidity is improved.

The thermosetting compound (K) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Thermosetting compounds (K) 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 resistance under high temperature and high humidity.

(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 alkyl 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 epoxy compound is preferably a compound having 5 to 50 epoxy groups in the molecule, more preferably a compound having 10 to 30 epoxy groups.

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, etc. are mentioned.

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 non-volatile matter in the photosensitive composition.

(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.

A thermosetting compound (K) 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 (K). 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 (K).

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

The thiol-based chain transfer agent (L) is preferably a polyfunctional thiol having 2 or more thiol groups (SH groups), more preferably a polyfunctional thiol having 4 or more thiol groups (SH groups). 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 (L) can be used alone or in combination of two or more.

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

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

The polymerization inhibitor (M) 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, tri phosphine compounds such as benzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite;

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

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

The ultraviolet absorber (N) 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 C7-9 side chain and linear alkyl esters, 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-benzotriazol-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 (N) is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator (C) and the ultraviolet absorber (N).

[Antioxidant (O)]
The photosensitive composition of the invention can contain an antioxidant (O).

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

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

The content of the antioxidant (O) 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, spectral characteristics, and sensitivity are improved.

[Leveling agent (P)]
The photosensitive composition of the invention can contain a leveling agent (P). This further improves the wettability and dryability of the substrate during coating.

Examples of the leveling agent (P) 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 (P) can be used individually or in combination of 2 or more types.

The content of the leveling agent (P) 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 (Q)]
The photosensitive composition of the present invention can contain a storage stabilizer (Q). This stabilizes the viscosity of the photosensitive composition over time.

Storage stabilizers (Q) 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 (Q) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment (A).

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

When the total amount of the specific metal elements is within the above range, the photosensitive composition is excellent in stability and sensitivity even after storage. Further, an optical filter produced using a photosensitive composition having a total amount of specific metal elements within the above range produces less foreign matter even when heated.

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

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

The method for reducing the specific metal element contained in the photosensitive composition is not particularly limited. It is preferred to remove elements. In addition, it is also preferable to suppress the contamination from the apparatus for manufacturing the photosensitive composition, because the contamination from the apparatus is also included.

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

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

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

From the viewpoint of storage stability, the photosensitive composition of the present invention preferably has a reduced content of metal elements other than the specific metal element. Examples of metals other than the specific metal elements include Mn, Cs, Ti, Co, Si, Pd, and the like.

[Water content]
From the viewpoint of storage stability, 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 stability and sensitivity even after storage.

The content of water contained in the photosensitive composition is more preferably 1.5% by mass or less, particularly preferably 1.0% 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 stability and sensitivity are excellent even after storage.

A method for controlling the water content is not particularly limited, and a known method can be used. Examples thereof include a method of producing a photosensitive colored composition while blowing dry air, an inert gas, or a mixed gas thereof, and a method of adding molecular sieves and dehydrating after production. Among them, a method of manufacturing while blowing dry air, inert gas, or mixed gas thereof is preferable.

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

Although the mechanism is not clear, it is presumed that the reaction of the photopolymerization initiator (C) during storage was suppressed by reducing the amount of the specific metal element and the amount of water. In particular, it is useful when the silane coupling agent (E) is contained, and is presumed to have suppressed the reaction of the silane coupling agent (E).

[Method for producing photosensitive composition]
The photosensitive composition of the present invention is prepared by, for example, adding a near-infrared absorbing pigment (A), a dispersing resin (G) and an organic solvent (D), and performing dispersion treatment under dry air to produce a dispersion. do. After that, the polymerizable compound (B), the photopolymerization initiator (C), etc. are blended into the dispersion under dry air, and mixed. The timing of blending each material is arbitrary. Also, it is preferable to work in a humidity-controlled place to avoid contamination with water from the atmosphere.

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 pigment (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 filtered through a sintered filter or a membrane filter to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust. Removal is preferred. 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 present invention is a cured product of the photosensitive composition of the present invention, and the formed film is cured by exposure or the like.

[Method for producing cured film]
The method for producing the cured film is not particularly limited. For example, the step (1) of applying a photosensitive composition on a substrate to form a layer of the composition, and the step of patternwise exposing the layer through a mask. (2), the step (3) of forming a patterned cured film by developing the unexposed portion with alkali, and the step (4) of heat-treating (post-baking) the pattern.

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

(Step (1))
The step (1) of forming a layer of a photosensitive composition includes applying a photosensitive composition onto a 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 80 to 300.degree. Moreover, the heating time is preferably about 2 minutes to 1 hour.

<Optical filter>
The cured film of the present invention can be used for optical filters. The optical filter is preferably used as, 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. The form used for the image display device is not particularly limited, but it can be used in combination with a color filter containing a coloring agent.

When the cured film of the present invention and a color filter are used in combination, the color filter is preferably arranged on the optical path of the cured film of the present invention. It can be used as a laminate. In the laminate, the cured film and the color filter may or may not be adjacent in the thickness direction. When the cured film of the present invention and the color filter are not adjacent to each other, the cured film of the present invention may be formed on a substrate different from the substrate on which the color filter is formed. Further, other members (for example, microlenses, flattening films, etc.) may be present between the cured film of the present invention and the color filter.

Examples of image display devices include liquid crystal displays and organic EL displays.
For the definition of the image display device and the details of each image display device, see, for example, "Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

<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 transfer electrode made of polysilicon or the like is provided, and a light shielding film made of tungsten or the like is provided on the photodiode and the transfer electrode so that only the light receiving portion of the photodiode is opened. It has a device protective film made of silicon nitride or the like formed as described above, and has a cured film of the present invention on the device protective film. Furthermore, the configuration may be such that a condensing means (for example, a microlens or the like) is provided above the device protective film and below the cured film of the present invention.

<Infrared sensor>
The cured film of the present invention can be used for infrared sensors. The form used for the infrared sensor is not particularly limited. FIG. 1 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with a cured film of the present invention. The infrared sensor shown in FIG.

An imaging region provided on the solid-state imaging device 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

The infrared cut filter 111 can be formed using the photosensitive composition of the present invention, transmits light in the visible region (eg, light with a wavelength of 400 to 700 nm), and transmits light in the infrared region (eg, light with a wavelength of 400 to 700 nm). 800-1,300 nm light).

The color filter 112 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 113 and the solid-state imaging device 110, a resin film 114 is arranged that allows transmission of the light of the wavelength that has passed through the infrared transmission filter 113. As shown in FIG.

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

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

Although the resin film 114 is arranged in the form shown in FIG.

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.

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 used in micro LEDs and micro OLEDs.
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 used in quantum dot displays.

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, the non-volatile content or non-volatile content 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.

(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% by weight of the above eluent, and 20 microliters was injected. 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.

(Measurement of Content of Compound Having Aromatic Ring)
Using gas chromatography, the content of the compound having an aromatic ring contained in the photosensitive composition was measured.

(Measurement of specific metal element content)
Using an ICP emission spectrometer (ICPE-9800 manufactured by Shimadzu Corporation), the contents of Li, Na, K, Mg, Ca, Fe, and Cr contained in the photosensitive composition were measured.

(Water content measurement)
The content of water contained in the photosensitive composition was measured using a Karl Fischer titrator (Mitsubishi Chemical Co., Ltd., KF-06 volumetric titration moisture meter).

<Production of near-infrared absorbing pigment (A)>
(Compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
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 is washed with hexane, ethanol and acetone successively and dried under reduced pressure. A compound (A-1) having a π-conjugated plane was obtained.
50 parts of the obtained compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring, 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 60°C for 12 hours. Next, this kneaded product was put into 3,000 parts of ion-exchanged water, stirred for 1 hour while being heated to 70° C., and then filtered (washing step). After repeating this washing step three times, the mixture was dried at 80° C. overnight and pulverized to obtain a compound (A-1) having a π-conjugated plane containing a finely divided monocyclic or condensed aromatic ring. .

chemical formula (14)

(Compound (A-2) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and 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 formed precipitate 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 defined as the point where the bleeding disappeared. Subsequently, this reaction solution is poured into 2,000 parts of ion-exchanged water, and the resulting precipitate is filtered, washed with water in this order, and dried to obtain a mixture of compounds represented by the following chemical formula (15) ( The mixing ratio was n1:n2:n3:n4=7:19:59:15, and a compound (A-2) having a π-conjugated plane containing a monocyclic or condensed aromatic ring was obtained.
It was refined in the same manner as the compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring.

chemical formula (15)

(Compound (A-3) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
In a reaction vessel, 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and 40 parts of gallium trichloride The mixture was stirred and heated, and then 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 c.
Next, 159 parts of compound c 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. 120 parts of compound d are obtained.
4 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 d 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 ion-exchanged water, and the resulting precipitate is filtered, washed with water, dried, and dried to obtain a compound represented by the following chemical formula (16). A compound (A-3) having a π-conjugation plane containing a ring or condensed aromatic ring was obtained.
It was refined in the same manner as the compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring.

chemical formula (16)

(Compound (A-4) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
The same operation is performed except that 50 parts of indium trichloride is used instead of 40 parts of gallium trichloride used in the compound (A-3) having a π-conjugated plane containing a monocyclic or condensed aromatic ring. , a compound (A-4) having a π-conjugated plane containing a monocyclic or condensed aromatic ring represented by the following chemical formula (17) was obtained.
It was refined in the same manner as the compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring.

chemical formula (17)

(Compound (A-5) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
According to the description of Japanese Patent Application Publication No. 2017/002920, a compound (A-5) having a π-conjugated plane containing a monocyclic or condensed aromatic ring represented by the following chemical formula (18) was obtained.
It was refined in the same manner as the compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring.

chemical formula (18)

(Compound (A-6) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
According to the description of International Publication No. 2019/058882, a compound (A-6) having a π-conjugated plane containing a monocyclic or condensed aromatic ring represented by the following chemical formula (19) was obtained.
It was refined in the same manner as the compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring.

chemical formula (19)

(Compound (A-7) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
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. 14.6 parts of compound e was obtained by liquid-separating this with a dichloromethane and water and concentrating an organic layer.
In a reaction vessel, 13.5 parts of compound e, 9.0 parts of bis(2,4-pentanedionato)zinc (II), and 120 parts of tetrahydrofuran were mixed and stirred, and the 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 ion-exchanged water, dried, and mixed with a compound represented by the following chemical formula (20) (mixing ratio: dimer: trimer : tetramer = 81:17:2) to obtain a compound (A-7) having a π conjugation plane containing a monocyclic or condensed aromatic ring.
It was refined in the same manner as the compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring.

chemical formula (20)

(Compound (A-8) having a π-conjugated plane containing a monocyclic or condensed aromatic ring)
Compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring was refined by the following method.
50 parts of the obtained compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring, 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho), Kneaded at 60° C. for 12 hours. Next, this kneaded product was put into 3,000 parts of tap water, stirred at room temperature for 1 hour, and then filtered. Then, it was dried at 80° C. for a whole day and night and pulverized to obtain a compound (A-8) having a π-conjugated plane containing a finely divided monocyclic or condensed aromatic ring.

<Production of alkali-soluble resin (F)>
(Alkali-soluble resin (F-1) solution)
160 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was put into a reaction vessel equipped with a separable four-necked flask, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and the temperature was raised to 120°C while injecting nitrogen gas into the vessel. After heating, 109.25 parts of benzyl methacrylate, 24.11 parts of methacrylic acid, 22.03 parts of dicyclopentanyl methacrylate, and 3.6 parts of azobisisobutyronitrile as a polymerization initiator were added from the dropping tube at the same temperature. , PGMAc was added dropwise over 2.5 hours.
After the dropwise addition was completed, the mixture was stirred at 120° C. for another 2 hours. After that, PGMAc was added so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (F-1) solution. The alkali-soluble resin (F-1) had an acid value of 98 mgKOH/g and a weight average molecular weight of 17,000.

<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 the nonvolatile content was measured to confirm that the polymerization conversion rate of the second block (A block) was 98% or more in terms of the nonvolatile content, and the reaction solution was cooled to room temperature. Polymerization was stopped by cooling. As a result of GPC measurement, the polymer had a mass average molecular weight of 20,000, a molecular weight distribution Mw/Mn of 1.4, and a reaction conversion rate of 98.5%. Thus, a dispersion resin (G-1) having an amine value per non-volatile content of 169.8 mgKOH/g was obtained. After cooling to room temperature, a sample of about 2 g was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added so that the non-volatile content was 30% by mass to obtain a dispersion resin (G-1) solution. was prepared.

<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 (D-1) is PGMAc.
Compound (A-1) having a π-conjugated plane containing a monocyclic or condensed aromatic ring
: 15.0 parts Dispersion resin (G-1) solution: 20.0 parts Organic solvent (D-1): 65.0 parts

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

<Production of photosensitive composition>
[Example 1]
(Photosensitive composition 1)
While blowing dry air into a container, the following raw materials and toluene, which is a compound having an aromatic ring, were charged and stirred for 2 hours. Thereafter, the photosensitive composition 1 was obtained by filtering through a filter having a pore size of 1.0 μm.
Dispersion 1: 35.0 parts Polymerizable compound (B-1): 7.0 parts Photopolymerization initiator (C-1): 0.8 parts Organic solvent (D-1): 19.9 parts Organic solvent ( D-2): 5.0 parts Silane coupling agent (E-1): 0.1 parts Alkali-soluble resin (F-1) solution: 30.0 parts Sensitizer (J-1): 0.2 parts Thermosetting compound (K-1): 1.0 parts Leveling agent (P): 1.0 parts

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

[Examples 2 to 19, Comparative Examples 1 and 2]
(Photosensitive compositions 2 to 19, 21 and 22)
For the photosensitive composition 1 of Example 1, Table 2 shows the types of raw materials, the blending amount, and the amount of toluene with respect to 100 parts by mass of the compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring. Photosensitive compositions 2 to 19, 21 and 22 were prepared in the same manner as in Example 1 except that the procedure was changed, and the content of the specific metal element and the content of water were measured.

[Example 20]
(Photosensitive composition 20)
Photosensitive Composition 20 of Example 20 was prepared in the same manner as Photosensitive Composition 1 of Example 1, except that the dry air was not replaced.

Each raw material described in the table is as follows.

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

[Photoinitiator (C)]
(C-1): Compound (C-2) of the above chemical formula (10): Irgacure OXE-02 (manufactured by BASF)

[Organic solvent (D)]
(D-1): propylene glycol monomethyl ether acetate (D-2): ethyl 3-ethoxypropionate

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

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

[Thermosetting compound (K)]
(K-1): EHPE-3150 (manufactured by Daicel Corporation, 1,2-epoxy-4-(2-oxiranyl) cyclohexane addition of 2,2-bis(hydroxymethyl)-1-butanol having about 15 epoxy groups thing)

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

<Evaluation of photosensitive composition>
The obtained photosensitive compositions 1 to 22 were evaluated as follows. Table 3 shows the evaluation results.

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

[Storage stability evaluation (2): foreign matter]
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 to room temperature, it was exposed to ultraviolet rays using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² .
The number of foreign substances on the cured film was counted, and this was defined as the initial number of foreign substances. Measurement was carried out using a metallurgical microscope "BX60" (manufactured by Olympus System Co., Ltd.) at a magnification of 500 times, and the number of foreign particles observable in arbitrary five fields of view was counted by integration.
The photosensitive composition was placed in a sealed container and stored at 40° C. for 1 week. 2 or more is practical.
3: The number of foreign substances after storage is less than 120% of the initial number of foreign substances 2: The number of foreign substances after storage is in the range of 120% or more and less than 150% of the initial number of foreign substances 1: Foreign substances after storage is 150% or more of the initial number of foreign objects

[Storage stability evaluation (3): sensitivity]
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 to room temperature, it was exposed to ultraviolet light through a photomask using a high-pressure mercury lamp. After that, spray development is performed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with deionized water, air-dried, and placed in a clean oven at 230°C. C. for 30 minutes to form a striped pattern on the substrate.
The width of the formed pattern was measured using a scanning electron microscope, and this was defined as the initial pattern width.
The photosensitive composition was placed in a sealed container and stored at 40° C. for 1 week, and the pattern width of the photosensitive composition after storage was measured under the same conditions as in the initial evaluation, and evaluated according to the following criteria. 2 or more is practical.
3: The pattern width using the photosensitive composition after storage is in the range of 95 to 105% of the initial pattern width 2: The pattern width using the photosensitive composition after storage is 90 to 110% of the initial pattern width Range of 1: The pattern width using the photosensitive composition after storage is less than 90% or more than 110% of the initial pattern width

[High temperature and high humidity resistance evaluation (1): adhesion]
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 with an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp. 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 obtained substrate was then heat-treated in a clean oven at 200° C. for 30 minutes.
The resulting cured film was cut with a cutter knife in a 1 mm square grid pattern (100 squares) and stored for 2 hours at a temperature of 120° C. and a humidity of 100%. After storage, a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was strongly pressed and peeled off in the direction of about 180° C., and then the state of the lattice pattern was observed and the number of peeled lattice patterns was counted. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Less than 2 4: 2 or more and less than 5 3: 5 or more and less than 10 2: 10 or more and less than 15 1: 15 or more

[High temperature and high humidity resistance evaluation (2): spectral characteristics]
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 dry film thickness would be 2.0 μm. It was dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate, it was exposed to light with an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp.
Using a spectrophotometer (Hitachi High-Technologies Corporation U-4100), the absorbance of the obtained substrate was measured at the incident angle of 0° C. at the maximum absorption wavelength, and this was used as the initial value.
After that, the substrate was stored for 200 hours under conditions of a temperature of 120° C. and a humidity of 85%. After cooling, the absorbance was measured again, and this value was used as the value after storage, and the residual rate was determined by the following formula. The evaluation criteria are as follows, and 3 or more is practical.
Residual rate = (absorbance after storage) / (initial absorbance) x 100
5: Residual rate is 97% or more 4: Residual rate is 95% or more and less than 97% 3: Residual rate is 93% or more and less than 95% 2: Residual rate is 90% or more and less than 93% 1: Residual rate is 90% %less than

100 infrared sensor 110 solid-state imaging device 111 infrared cut filter 112 color filter 113 infrared transmission filter 114 resin film 115 microlens 116 flat film

Claims (12)

A photosensitive composition comprising a near-infrared absorbing pigment (A), a polymerizable compound (B), a photopolymerization initiator (C) and an organic solvent (D),
The near-infrared absorbing pigment (A) contains a compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring,
The organic solvent (D) contains a compound having an aromatic ring, and the content of the compound having an aromatic ring is 100 parts by mass of the compound having a π-conjugated plane containing the monocyclic or condensed aromatic ring. 0.005 to 0.5 parts by weight of the photosensitive composition. Furthermore, the total amount of metals Li, Na, K, Mg, Ca, Fe and Cr contained in the photosensitive composition is 300 mass ppm or less, and the water content is 2.0 mass% or less. A photosensitive composition according to claim 1 . 3. The compound according to claim 1 or 2, wherein the compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring is one or more selected from the group consisting of squarylium compounds, pyrrolopyrrole compounds, naphthalocyanine compounds and indigo compounds. A photosensitive composition as described. 4. The photosensitive composition according to claim 3, wherein the central element of said naphthalocyanine compound is one or more selected from the group consisting of Al, Ga and In. 5. The photosensitive composition according to claim 3, wherein the naphthalocyanine compound has a ligand containing a phosphorus atom. 6. The photosensitive composition according to claim 5, wherein the ligand containing a phosphorus atom is a ligand having a hydrophobic group. The photosensitive composition according to any one of claims 1 to 6, further comprising a silane coupling agent (E). 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 .