JP2022173080A - Photosensitive composition, and cured film, optical filter, image display device, solid-state imaging element, and infrared sensor using the photosensitive composition - Google Patents

Abstract

To provide a photosensitive composition capable of forming a cured film which is excellent in developability and pattern formability and has less aggregated foreign matter.SOLUTION: The photosensitive composition contains a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The polymerizable compound (C) contains a polymerizable compound (C1) having a urethane bond. The polymerizable compound (C) preferably further contains a polymerizable compound (C2) other than the polymerizable compound (C1) having a urethane bond.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive composition, a cured film using the same, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor.

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. However, a composition containing a near-infrared absorbing dye used for an infrared cut filter easily transmits active energy rays (i-line, etc.), so the line width of the pattern tends to increase, and the resolution and pattern shape deteriorate. Cheap. So far, as a method for solving the above problem, a method of adjusting the amount of generated active radicals, that is, a method of adjusting the kind and amount of the photopolymerization initiator, has been investigated. For example, in the case of thickening of the line width, there has been a method of using a photopolymerization initiator with low sensitivity or reducing the amount thereof to reduce the amount of active radicals and obtain an appropriate line width. However, this method has a problem that the pattern is chipped or peeled off in the developing process. In addition to this, there is also a problem that the near-infrared absorbing dye agglomerates during the heating process to generate foreign substances.

Various efforts have been made to solve the above problems. For example, in Patent Document 1, a photosensitive composition capable of forming a cured film having a pattern with good rectangularity and suppressed heat shrinkage includes a near-infrared absorber, a curable compound, a photoinitiator, Photosensitive compositions containing certain UV absorbers are disclosed. Further, in Patent Document 2, an infrared absorbing dye and a resin having a glass transition temperature of 150 to 300° C. are used as a pattern forming composition which is excellent in suppressing development residue and in the shape and heat resistance of the resulting pattern. A patterning composition comprising: Further, Patent Document 3 describes a curable composition having good water-resistant adhesion and less aggregates derived from a near-infrared absorbing dye, a near-infrared absorbing dye, a compound having a cyclic ether group, and a radically polymerizable compound. and a thermal radical polymerization initiator.

WO2018/043218 WO2019/058882 WO2019/021790

However, none of the compositions described in Patent Documents 1 to 3 satisfy all of developability, pattern formability, and suppression of agglomerated foreign matter.

An object of the present invention is to provide a photosensitive composition which is excellent in developability and pattern formability and which can form a cured film with less agglomerated foreign matter.

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

ADVANTAGE OF THE INVENTION According to said invention, the photosensitive composition which is excellent in developability and pattern formability and can form the cured film with few aggregated foreign substances 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 shows a schematic cross-sectional view of an infrared sensor provided with the cured film of the present invention.

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

In the present invention, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" are each unless otherwise specified. , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide” . "C.I." means a color index (C.I.; published by The Society of Dyers and Colorists). A polymerizable unsaturated group is an ethylenically unsaturated double bond.
Regarding the molecular weight of the compound in the present invention, for a low molecular weight compound whose molecular weight can be specified, it is a value calculated by calculation or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and a compound having a molecular weight distribution. is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.

<Photosensitive composition>
One embodiment of the invention relates to a photosensitive composition. The photosensitive composition of the present invention is a photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The polymerizable compound (C) is characterized by containing a polymerizable compound (C1) having a urethane bond.

The components that are or can be included in the photosensitive composition of one embodiment are described in detail below.

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

The near-infrared absorbing dye (A) is a compound that absorbs light with a wavelength of 700 to 2,000 nm, and may be a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye). may Also, a near-infrared absorbing pigment and a near-infrared absorbing dye may be used in combination. Near-infrared absorbing pigments are preferred from the viewpoint of heat resistance.
In the present invention, the solubility of the near-infrared absorbing pigment in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less. .

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

Cyanine compounds, WO 2006/006573, WO 2010/073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; JP-A-4-23868, JP-A-06-192584, JP-A-2000-63691, International Publication No. 2014/208514, etc.; JP, JP 2009-29955 A, International Publication No. 2018/186490, etc.; Indigo compounds, JP 2013-230412, etc.; 197492, JP 2008-88426, etc.; anthraquinone compounds, JP 62-903, JP 1-172458, etc.; pyrrolopyrrole compounds, JP 2009-263614, JP 2010-90313, JP-A-2011-068731; the squarylium compound is disclosed in JP-A-2011-132361, JP-A-2016-142891, WO 2017/135359, WO 2018/225837, Japanese Patent Application Laid-Open No. 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 hydrogen (ie, carboxyl group), the hydrogen atom may be dissociated (ie, carbonate group), or may be in the form of a salt. In addition, 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 .
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 hydrogen (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. In addition, 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 compound represented by formula (2) 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. Details of the general formula (3) can be referred to the descriptions of JP-A-2009-263614, JP-A-2011-68731, and WO 2015/166873, the contents of which are incorporated herein.

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 and 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 compound represented by formula (3) are shown below. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. Further, as the pyrrolopyrrole compound, 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 No. 2015/166873, paragraphs 0010-0033. In addition, this invention is not limited to these.

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

general formula (4)

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

The "alkyl group" of the alkyl group optionally having a substituent is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, and an n-hexyl group. , n-octyl group, stearyl group, 2-ethylhexyl group, and other linear or branched alkyl groups. "Alkyl group having a substituent" includes, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoro propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

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

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

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

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

The "aryloxy group" of the aryloxy group optionally having a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, etc.
"Aryloxy group having a substituent" includes, for example, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4- A chlorophenoxy group and the like can be mentioned.

The "alkylthio group" of the alkylthio group optionally having a substituent is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc. 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 optionally having a substituent includes, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like.
"Arylthio group having a substituent" includes, for example, a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like. .

The substituents of the aromatic ring which may have a substituent include a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, and a substituent which may have aryl group, optionally substituted cycloalkyl group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group, substituted An arylthio group optionally having a group is exemplified.

general formula (5)

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

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

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

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

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

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

general formula (6)

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

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

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

Specific examples of the compound represented by formula (4) are shown below. In addition, this invention is not limited to these.

From the viewpoint of light resistance and heat resistance, the compound represented by the general formula (4) is any two of X ₁ and X ₂ , X ₃ and X ₄ , X ₅ and X ₆ , X ₇ and X ₈ It is preferable to include a compound that forms an aromatic ring where the above are bonded to each other to form an optionally substituted aromatic ring, and three or more are bonded to each other to form an aromatic ring that may have a substituent. is more preferable.

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

Specific examples of the compound represented by the general formula (7) or the compound represented by the general formula (8) are shown below. In addition, this invention is not limited to these.

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

From the viewpoint of near-infrared absorption, the content of the near-infrared absorbing dye (A) is preferably 0.5 to 70% by mass, more preferably 3 to 50% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition.

[Alkali-soluble resin (B)]
The photosensitive composition of the present invention contains an alkali-soluble resin (B). As a result, resistance such as heat resistance and chemical resistance of the cured film is improved.

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

The alkali-soluble resin (B) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. From the standpoint of developability, the alkali-soluble resin (B) preferably has an alkali-soluble group. The alkali-soluble group includes, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a phenolic hydroxyl group, etc. Among these, a carboxyl group is preferred.
Also, the alkali-soluble resin (B) 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 chemical 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, which can be used singly or in combination of two or more.

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, which can be used singly or in combination of two or more.

Polybasic acid anhydrides include, for example, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and can be used alone or in combination of two or more. In addition, if necessary, a tricarboxylic dianhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic anhydride can be used to hydrolyze the 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. These can be used alone or in combination of two or more. 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, or 1,1-bis[methacryloyloxy]ethyl isocyanate, which may be used alone or in combination of two or more. Can be used together.

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

Alkali-soluble resin (B) can be synthesized by using the above monomers alone or in combination of two or more.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, from the viewpoint of developability. Also, the value of Mw/Mn is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to substrates and solubility in alkali development.

The acid value of the alkali-soluble resin (B) is preferably 50-200 mgKOH/g, more preferably 70-180 mgKOH/g. Adhesion to substrates and solubility in alkali development are improved by an appropriate acid value.

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

The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, per 100 parts by mass of the near-infrared absorbing dye (A).

[Polymerizable compound (C)]
(Polymerizable compound (C1) having a urethane bond)
The photosensitive composition of the present invention contains a polymerizable compound (C1) having a urethane bond as the polymerizable compound (C). Thereby, it is possible to form a cured film which is excellent in developability and pattern formability and which contains less agglomerated foreign matters.
Although the mechanism by which the effects of the present invention are obtained is not clear, it is speculated as follows.

The polymerizable compound (C1) having a urethane bond forms a physical crosslinked structure due to the intermolecular hydrogen bond of the urethane bond together with the chemical crosslinked structure due to the reaction of the polymerizable portion in the coating film. The molecular cohesive energy of the intermolecular hydrogen bonds of this urethane bond is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the coating film obtained by curing the composition containing the polymerizable compound (C1) having a urethane bond is strengthened by the interaction between the urethane bonds. In addition, the interaction between urethane bonds is weaker than that of chemical bonds and has moderate flexibility. Therefore, it is presumed that the developability was excellent and the damage to the coating film was suppressed. In addition, it is speculated that the intermolecular hydrogen bond portion of the urethane bond inhibited the movement of the near-infrared absorbing dye in the coating film, thereby suppressing aggregation.

The polymerizable compound (C1) having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, a polyhydric alcohol reacted with a polyfunctional isocyanate, and Examples include urethane (meth)acrylates obtained by reacting (meth)acrylates having a hydroxyl group.

(Meth)acrylates having a hydroxyl group 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-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, Examples include glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

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

The number of polymerizable unsaturated groups in the polymerizable compound (C1) having a urethane bond is preferably 5 to 12 from the viewpoint of developability and pattern formability.

The molecular weight of the polymerizable compound (C1) having a urethane bond is preferably 500 to 5,000, more preferably 500 to 3,000, from the viewpoints of developability, pattern formation, and suppression of agglomerated foreign matter. More preferably, it is particularly preferably 500 to 2,000.

The polymerizable compound (C1) having a urethane bond can be used alone or in combination of two or more.

The content of the polymerizable compound (C1) having a urethane bond is preferably 20 to 100% by mass based on 100% by mass of the polymerizable compound (C) from the viewpoint of developability, pattern formability, and suppression of aggregated foreign matter. 20 to 80% by mass is more preferable.

The polymerizable compound (C1) having a urethane bond is at least one selected from the group consisting of alicyclic urethane (meth)acrylates and aromatic urethane (meth)acrylates, from the viewpoint of pattern formability and suppression of aggregated foreign matter. It preferably contains a seed, and more preferably contains an aromatic urethane (meth)acrylate.
By having a rigid alicyclic structure or aromatic ring structure, a tougher coating film can be obtained, and pattern formability and suppression of agglomerated foreign matter are improved. In addition, the effects are further improved by the π-π interaction due to the aromatic ring structure.

[Alicyclic urethane (meth)acrylate]
The alicyclic urethane (meth)acrylate is not particularly limited, and known ones can be used. For example, it can be obtained by using a polyfunctional isocyanate having an alicyclic structure as the polyfunctional isocyanate of the polymerizable compound (C) having a urethane bond.

Examples of polyfunctional isocyanates having an alicyclic structure include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane and the like. Moreover, these buret bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies, etc. are mentioned.

[Aromatic urethane (meth)acrylate]
Aromatic urethane (meth)acrylates are not particularly limited, and known ones can be used. For example, it can be obtained by changing the polyfunctional isocyanate having an alicyclic structure of the alicyclic urethane (meth)acrylate described above to a polyfunctional isocyanate having an aromatic ring structure.

Polyfunctional isocyanates having an aromatic ring structure include, for example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane Diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4 -diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene and the like. Moreover, these buret bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies, etc. are mentioned.

In the photosensitive composition of the present invention, the polymerizable compound (C1) having a urethane bond preferably further has an acid group from the viewpoint of developability.

A compound obtained by introducing an acid group into the polymerizable compound (C1) having a urethane bond, for example, first reacts the (meth)acrylate having a hydroxyl group with the polyfunctional isocyanate, and then the product has a carboxyl group. a compound to which a mercapto compound is added,
After reacting the polyhydric alcohol with the polyfunctional isocyanate, the (meth)acrylate having a hydroxyl group is reacted, and then a compound obtained by adding a mercapto compound having a carboxyl group to the product, a polyhydric alcohol having a carboxyl group Compounds obtained by reacting the above-mentioned polyfunctional isocyanate and then reacting the above-mentioned (meth)acrylate having a hydroxyl group, and the like can be mentioned.

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.

The polyhydric alcohol having a carboxyl group is, for example, the polyhydric alcohol and polybasic acid or its anhydride (e.g., succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, tetrahydrophthalic anhydride, etc.) and dimethylol Examples thereof include compounds obtained by reacting propionic acid.

(Polymerizable compound (C2) other than polymerizable compound (C1) having urethane bond)
From the standpoint of developability and pattern formability, the photosensitive composition of the present invention includes a polymerizable compound (C2) other than the polymerizable compound (C1) having a urethane bond (hereinafter, also referred to as other polymerizable compound (C2)). is preferably included.

Other polymerizable compounds (C2) 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, tricyclodecanedimethanol di (Meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth) Acrylates, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate ) 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 melamine ( Various acrylic and methacrylic esters such as meth)acrylate, epoxy (meth)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. Among these, those having 5 or more polymerizable unsaturated groups are preferable from the viewpoint of pattern formability.

Other commercial products of the polymerizable compound (C2) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, and R-604 manufactured by Nippon Kayaku Co., Ltd. , R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, manufactured by Toagosei Co., Ltd. Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M -402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, M-5300, M-5400, M-5700 , M-510, M-520, M-521, 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, Osaka Organic Chemical Industry Co., Ltd. Viscoat #2500P, Shin Nakamura Chemical Co., Ltd. NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, EBECRYL40, 130, 140, 145 manufactured by Daicel Allnex Co., Ltd., and the like.

The mass ratio of the polymerizable compound (C1) having a urethane bond and the other polymerizable compound (C2) is 80:20 to 20:80 from the viewpoint of developability, pattern formability, and suppression of agglomerated foreign matter. is preferred.

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

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

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

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

Commercially available products include Omnirad 907, 369E and 379EG manufactured by IGM Resins as acetophenone compounds, Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds, and IRGACURE OXE-01 and 02 manufactured by BASF as oxime compounds. , 03, 04, N-1919 manufactured by ADEKA, NCI-730, 831, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365 manufactured by Changzhou New Material Co., Ltd. , 610, 3054, 3057, Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306 manufactured by Daito Chemix, EOX-01 etc.
Further, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, JP 2011-020998, International Publication WO2015/036910, International Oxime-based compounds described in Publication No. 2021/175855 and the like are also included. Among these, acetophenone-based compounds and oxime-based compounds are preferable, and oxime-based compounds are more preferable, from the viewpoint of developability and pattern formability.

The oxime-based compound is preferably a compound represented by the following chemical formula (9) from the viewpoint of pattern formability.

chemical formula (9)

The method for producing the compound of chemical formula (9) is not particularly limited, and known methods can be used. For example, the method described in International Publication No. 2015/036910 can be used.

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

The content of the photopolymerization initiator (D) is preferably 1 to 50 parts by mass, based on 100 parts by mass of the near-infrared absorbing dye (A), from the viewpoint of photocurability and developability, and 2 to 30 parts by mass. Parts by mass are more preferable.

[Sensitizer (E)]
The photosensitive composition of the present invention preferably contains a sensitizer (E) from the viewpoint of developability and pattern formability.

Sensitizers (E) 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, the thioxanthone-based compound (E1) or the benzophenone-based compound (E2) is preferred, and the benzophenone-based compound (E2) is more preferred, from the viewpoint of pattern formability.

(Thioxanthone-based compound (E1))
Thioxanthone compounds (E1) include, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. be done. Among these, 2,4-diethylthioxanthone is preferred.

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

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

The content of the sensitizer (E) is preferably 150 to 400 parts by mass, more preferably 150 to 300 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D), from the viewpoint of pattern formability.

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

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

(pigment)
A pigment is a compound classified as a pigment 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 preferred.

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, and pigments described in JP-A-2012-226110. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A-2012-226110 are preferred.

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like. Among these, C.I. I. Pigment Green 36, 58, 59, 62, 63 are preferred.

Blue pigments include, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

Purple pigments include, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, C.I. I. Pigment Violet 19, 23 are preferred.

Black pigments include, for example, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. At least two pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and violet pigments may be used as the black colorant.

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

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

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

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

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

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

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

The content of the coloring agent (F) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less, based on 100% by mass of the nonvolatile matter of the photosensitive composition.

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

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferred from the viewpoint of price. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

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

[Dispersion resin (G)]
The photosensitive composition of the present invention can contain a dispersing resin (G). When calculating the content of the alkali-soluble resin (B) when the alkali-soluble dispersing resin (G) is included, the alkali-soluble dispersing resin (G) is calculated as the alkali-soluble resin (B).

The dispersing resin (G) is preferably a resin having an adsorptive group that has a high affinity for the near-infrared absorbing dye (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 dispersion stability.

Commercial products of the dispersing resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by BYK-Chemie Japan. 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Nippon Lubrizol Co., Ltd. ，１６０００，１７０００，１８０００，２００００，２１０００，２４０００，２６０００，２７０００，２８０００，３１８４５，３２０００，３２５００，３２５５０，３３５００，３２６００，３４７５０，３５１００，３６６００，３８５００，４１０００，４１０９０，５３０９５，５５０００，５６０００，７６５００ Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan Ajinomoto Fine Techno's Ajisuper PA111, PB711, PB821, PB822, PB824, etc., JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, International Publication 2008/007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007- 23195, JP-A-1996-143651, and the like.

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

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

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

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

Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520, WO 2009/081930, WO 2011/052617, WO 2012/102399, JP 2017 -156397, as phthalocyanine dye derivatives, JP 2007-226161, WO 2016/163351, JP 2017-165820, JP 5753266, as anthraquinone dye derivatives, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009/025325, quinacridone system As dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, as dioxazine-based dye derivatives, JP-A-2011-162662, thiazine indigo dyes As a derivative, JP-A-2007-314785, as a triazine dye derivative, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208 Publications, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole dye derivative, JP-A-2003-167112 as a quinophthalone dye derivative, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, naphthol dye derivatives, JP-A-2012-208329, JP-A-2014-5439, azo dyes Derivatives include JP-A-2001-172520 and JP-A-2012-172092; acidic substituents include JP-A-2004-307854; Examples thereof include known dye derivatives described in JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

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

[Thermosetting compound (I)]
The photosensitive composition of the present invention can contain thermosetting compound (I). As a result, the thermosetting compound (I) reacts in the heating step, increasing the crosslink density and improving the heat resistance.

Thermosetting compound (I) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Thermosetting compounds (I) include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (I1))
Epoxy compounds (I1) 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 dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymerization of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) 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.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine type epoxy resins, glycidyl ester type 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 (H1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

(Oxetane compound (I2))
Oxetane compound (I2) is a known compound 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.

Examples of commercially available products include 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 (I2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol-type or ether-type compound, and more preferably a melamine compound having an average number of methylol groups and/or ether groups of 5.0 or more per melamine ring. Having an appropriate number of methylol groups and ether groups makes it easy to obtain just the right amount of heat resistance.

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

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

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

[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 (I). 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 (I).

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

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

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

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

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

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

The polymerization inhibitor (K) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol , 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol , 4-t-butylcatechol, 3,5-di-t-butylcatechol and other alkylcatechol compounds, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 alkylresorcinol compounds such as -propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc. phosphine compounds, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and phloroglucine.

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

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

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

Benzotriazole compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of 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.

Commercially available products are, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, and 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, KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, Adekastab LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV manufactured by Sun Chemical. -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'-dihydroxy-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, KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Chemicals, SEESORB101, 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

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

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

[Antioxidant (M)]
The photosensitive composition of the invention can contain an antioxidant (M). The antioxidant (M) prevents the photopolymerization initiator (D) and the thermosetting compound (I) in the photosensitive composition from yellowing due to oxidation due to thermal curing and thermal processes during ITO annealing. In particular, when the concentration of the near-infrared absorbing dye (A) of the photosensitive composition is high, the content of the polymerizable compound (C) is relatively decreased, so that the amount of the photopolymerization initiator (D) is increased, and the thermosetting The cured film tends to turn yellow if it is handled by compounding the compound. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. Antioxidant (M) is preferably a compound containing no halogen atom.

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

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

Commercially available 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 esters, 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 etc.

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

Phosphorus antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4' -Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-t-butyl-6-methylphenyl) and the like.

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

Sulfur antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′- ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.

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

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

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

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

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

Commercially available products are, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 manufactured by BYK Chemie, 378, 3455, UV3510, 3570, Toray Dow Corning FZ-7002, 2110, 2122, 2123, 2191, 5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22-4272, X- 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

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

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

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

Commercially available products are, for example, Kao Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Rhodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31, 44 manufactured by ADEKA, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and (meth)acrylic acid-based (co)polymer polyflow No. manufactured by Kyoeisha Chemical Co., Ltd.; 75, No. 90, No. 95 and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the dispersing machine for performing the dispersing treatment include a two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor.

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

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

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

<Cured film>
The cured film of the present invention can be obtained by curing the film formed using the photosensitive composition of the present invention by treatment such as exposure. The cured film may have a pattern or may be a film without a pattern (flat film).

[Method for producing cured film]
The method for producing the cured film is not particularly limited. step (2) of developing the unexposed portion with alkali to form a patterned cured film (3); and step (4) of heat-treating (post-baking) the pattern.

The method for producing a cured film will be described in detail below.
(Step (1))
In the step (1) of forming a layer of the composition, the photosensitive composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and if necessary It is dried (pre-baked) at a temperature of 50 to 120° C. for 10 to 120 seconds using an oven, a hot plate, or the like.
Examples of the substrate include a glass substrate, a resin substrate, a silicon substrate, and the like. 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 thickness of the layer after drying is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 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.
Radiation used for exposure includes, for example, ultraviolet rays such as g-line, h-line and i-line. 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.
Further, 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 photosensitive composition in the unexposed portion is eluted in an alkaline aqueous solution, leaving only the cured portion 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 100 to 300.degree. C., more preferably 150 to 250.degree. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

<Optical filter>
The cured film of the present invention can be used for optical filters. An infrared cut filter, an infrared transmission filter, etc. are mentioned as an optical filter. 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.

The cured film of the present invention can be used on the edge and/or side of the surface of the infrared cut filter 111, and if it is used on the inner wall of the infrared sensor, it prevents internal reflection and/or unintended incidence of light on the light receiving part. and improve sensitivity.

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.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these. In addition, "part" is "mass part" and "%" is "mass%".
In addition, in the present invention, non-volatile matter or non-volatile matter concentration refers to the mass residue after standing in an oven at 280° C. for 30 minutes.

Prior to Examples, each measuring method will be described.

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

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

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

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

<Production of near-infrared absorbing dye (A)>
(Near-infrared absorbing dye (A-1))
40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed with 400 parts of toluene and mixed in a nitrogen gas atmosphere. The mixture was heated with stirring and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the resulting reaction mixture. After filtering the resulting black-brown precipitate, it was washed with hexane, ethanol and acetone in turn and dried under reduced pressure to obtain a near-infrared absorbing dye (A-1) represented by the following chemical formula (10). rice field. 50 parts of the near-infrared absorbing dye (A-1) thus obtained, 500 parts of sodium chloride and 60 parts of diethylene glycol were placed in a gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 12 hours. Next, the kneaded mixture is poured into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, dried at 80°C for a day and night, and pulverized. Thus, a fine near-infrared absorbing dye (A-1) was obtained.

chemical formula (10)

(Near-infrared absorbing dye (A-2))
40.0 parts of 1,8-diaminonaphthalene, 50.1 parts of 2-hydroxy-9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed with 400 parts of toluene and mixed in a nitrogen gas atmosphere. The mixture was heated and stirred at , and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the resulting reaction mixture. After filtering the resulting black-brown precipitate, it was washed with hexane, ethanol and acetone in turn and dried under reduced pressure to obtain a near-infrared absorbing dye (A-2) represented by the following chemical formula (11). rice field.
A micronized near-infrared absorbing dye (A-2) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (11)

(Near-infrared absorbing dye (A-3))
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 aluminum chloride anhydride were 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 being stirred was poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain compound a.
Next, 10 parts of compound a was added to 100 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 that order, and dried to obtain a compound. obtained b.
5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50°C. After adding 10 parts of compound b little by little to this solution, the mixture was stirred at 90° C. for 120 minutes. For confirmation of the end point of the reaction, for example, the reaction liquid was dropped onto a filter paper, and the end point was set at the point where the bleeding disappeared. Subsequently, this reaction solution is poured into 2,000 parts of ion-exchanged water, and the resulting precipitate is filtered, washed with water, and dried to obtain a near-infrared absorbing dye represented by the following chemical formula (12). (A-3) was obtained.
A micronized near-infrared absorbing dye (A-3) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (12)

(Near-infrared absorbing dye (A-4))
A near-infrared absorbing dye (A-4) represented by the following chemical formula (13) was obtained according to the description of International Publication No. 2019/058882.
A fine near-infrared absorbing dye (A-4) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (13)

(Near-infrared absorbing dye (A-5))
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 of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain compound c.
Next, 140 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 formed precipitate is filtered, washed with water, washed with a 2.5% sodium hydroxide aqueous solution, washed with water in this order, dried, and dried. Compound d 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 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 in this order, and dried to obtain a mixture of compounds represented by the following chemical formula (14) ( A near-infrared absorbing dye (A-5) having a mixing ratio of n1:n2:n3:n4=7:19:59:15 was obtained.
A fine near-infrared absorbing dye (A-5) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (14)

(Near-infrared absorbing dye (A-6))
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/1 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 water, dried, and mixed with a compound represented by the following chemical formula (15) (mixing ratio: dimer: trimer: 4 A near-infrared absorbing dye (A-6) having a monomer ratio of 81:17:2 was obtained.
A fine near-infrared absorbing dye (A-6) was obtained in the same manner as the near-infrared absorbing dye (A-1).

chemical formula (15)

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B-1) solution)
100 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) , 2,2'-azobisisobutyronitrile 1.1 parts was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. Acetate (hereinafter also referred to as PGMAc) was added to prepare an alkali-soluble resin (B-1) solution. The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (B-2) solution)
100 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare an alkali-soluble resin (B-2) solution. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (B-3) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirring device was charged with 200 parts of cyclohexanone, heated to 80 ° C., and after replacing the inside of the flask with nitrogen, parachlorate was added from the dropping tube. Milphenol ethylene oxide-modified acrylate (Toagosei Aronix M110) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 20 parts of cyclohexanone was added, and the reaction was further continued at 100° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl groups). The reaction was continued for a period of time, and the reaction was terminated when the acid value of the non-volatile matter reached 0.5. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of hydroxyl groups produced) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare an alkali-soluble resin (B-3) solution. The weight average molecular weight (Mw) was 19,000.

(Alkali-soluble resin (B-4) solution)
A separable flask equipped with a cooling pipe was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate 40 parts, methacrylic acid 40 parts, methacrylic acid 120 parts of methyl, 4 parts of t-butylperoxy 2-ethylhexanoate (NOF "Perbutyl O"), and 40 parts of PGMAc are prepared by stirring well, and n-dodecanethiol is used as a chain transfer agent dropping tank. 8 parts and 32 parts of PGMAc were thoroughly stirred and mixed to prepare a mixture.
After 200 parts of PGMAc was charged in a reaction vessel and purged with nitrogen, the temperature of the reaction vessel was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropping was performed over 135 minutes while maintaining the temperature at 90°C. After 60 minutes from the end of the dropwise addition, the temperature of the reactor was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen=5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2′-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel and allowed to react at 110° C. for 12 hours. rice field. Then, add 150 parts of PGMAc and cool to room temperature, sample about 2 g of the resin solution, heat and dry at 180 ° C. for 20 minutes, measure the non-volatile content, and the non-volatile content of the previously synthesized resin solution becomes 40% by mass. An alkali-soluble resin (B-4) solution was obtained by adding PGMAc as described above. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (B-5) solution)
150 parts of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100° C., followed by benzyl methacrylate. Azobisiso was added to a mixture of 70.5 parts (0.40 mol), 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc. A solution containing 3.6 parts of butyronitrile was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 43.0 parts of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of the glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0 9 parts and 0.145 parts of hydroquinone were charged into the flask, and the reaction was continued at 110° C. for 6 hours until the acid value of the non-volatile matter reached 1 mgKOH/g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a resin solution with an acid value of 80 mgKOH/g. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and PGMAc is added to the previously synthesized resin solution so that the nonvolatile content is 40% by mass. to prepare an alkali-soluble resin (B-5) solution. The weight average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (B-6) solution)
150 parts of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100° C., followed by benzyl methacrylate. Azobisisobutyl was added to a mixture of 70.5 parts (0.40 mol), 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate and 136 parts of PGMAc. A solution containing 3.6 parts of lonitrile was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0 .9 parts and 0.145 parts of hydroquinone were put into the flask and the reaction was continued at 110° C. for 6 hours to obtain a resin solution with an acid value of 79 mgKOH/g. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and PGMAc is added to the previously synthesized resin solution so that the nonvolatile content is 40% by mass. Then, an alkali-soluble resin (B-6) solution was prepared. The weight average molecular weight (Mw) was 13,000.

<Production of polymerizable compound (C1) having urethane bond>
(Polymerizable compound (C1-1) having a urethane bond)
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, and the temperature was maintained at 70°C. , and a mixture of 112 parts of hexamethylene diisocyanate and 112 parts of PGMAc was dropped from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aliphatic urethane acrylate solution having 6 polymerizable unsaturated groups.

(Polymerizable compound having a urethane bond (C1-2))
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, and the temperature was maintained at 70°C. and a mixture of 148 parts of isophorone diisocyanate and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. PGMAc was added so that the non-volatile content was 50% by mass to obtain an alicyclic urethane acrylate solution having 6 polymerizable unsaturated groups.

(Polymerizable compound (C1-3) having a urethane bond)
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, and the temperature was maintained at 70°C. and a mixture of 107 parts of 1,3-phenylene diisocyanate and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aromatic urethane acrylate solution having 6 polymerizable unsaturated groups.

(Polymerizable compound (C1-4) having a urethane bond)
400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube. C., and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aliphatic urethane acrylate solution having 10 polymerizable unsaturated groups.

(Polymerizable compound having a urethane bond (C1-5))
400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube. C., and a mixture of 84 parts of isophorone diisocyanate and 84 parts of PGMAc was dropped from the dropping pipe over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. An alicyclic urethane acrylate solution having 10 polymerizable unsaturated groups was obtained by adjusting the non-volatile content to 50% by mass.

(Polymerizable compound (C1-6) having a urethane bond)
400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube. C., and a mixture of 66 parts of toluene diisocyanate (mixture of 2,4 and 2,6) and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aromatic urethane acrylate solution having 10 polymerizable unsaturated groups.

(Polymerizable compound having a urethane bond (C1-7))
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, and the temperature was maintained at 70°C. and a mixture of 116 parts of toluene diisocyanate (mixture of 2,4 and 2,6) and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. Then, 66 parts of mercaptoacetic acid and 0.4 parts of 4-methoxyphenol were charged and reacted at a temperature of 50-60° C. for 6 hours. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aromatic urethane acrylate solution having an average number of polymerizable unsaturated groups of 5 and having an acid group.

(Polymerizable compound having a urethane bond (C1-8))
400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube. ℃, and a mixture of 61 parts of 1,3-phenylene diisocyanate and 61 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After dropping, reaction was carried out at a temperature of 50 to 70° C. for 8 hours, and disappearance of absorption of isocyanate at 2180 cm ⁻¹ was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50-60° C. for 6 hours. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aromatic urethane acrylate solution having an average number of polymerizable unsaturated groups of 9 and having an acid group.

<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, and the mixture was heated at 50°C while flowing nitrogen. 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. After 2 hours from the addition, the polymerization solution was sampled and nonvolatile content was measured to confirm that the polymerization conversion rate of the second block (A block) was 98% or more in terms of 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 weight 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 nonvolatile content, and PGMAc was added so that the nonvolatile 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 It was filtered through a 1.0 μm filter to prepare Dispersion 1. Organic solvent (Q-1) is PGMAc.
Near infrared absorbing dye (A-1): 15.0 parts Dispersion resin (G-1) solution: 20.0 parts Organic solvent (Q-1): 65.0 parts

(Dispersions 2 to 6)
Dispersions 2 to 6 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)
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive composition 1.
Dispersion 1: 35.0 parts Alkali-soluble resin (B): 25.0 parts Polymerizable compound having a urethane bond (C1-1): 12.0 parts Photopolymerization initiator (D-3): 0.5 parts Benzophenone compound (E2-1): 1.0 parts Leveling agent (N): 1.0 parts Organic solvent (Q): 25.5 parts

[Examples 2 to 31, Comparative Examples 1 to 3]
(Photosensitive compositions 2 to 34)
Photosensitive compositions 2 to 34 were prepared in the same manner as in Example 1 except that the photosensitive composition 1 of Example 1 was changed to the components and amounts shown in Tables 2-1 to 2-4.

The respective components listed in Tables 2-1 to 2-4 are as follows.

[Alkali-soluble resin (B)]
Alkali-soluble resin (B-1) to (B-6) solutions were mixed in equal amounts to obtain an alkali-soluble resin (B).

[Polymerizable compound (C)]
(Polymerizable compound (C1) having a urethane bond)
C1-9: EBECRYL4666 (manufactured by Daicel Allnex, aliphatic urethane acrylate having 4 polymerizable unsaturated groups)
C1-10: NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., aliphatic urethane acrylate having 15 polymerizable unsaturated groups)

(Other polymerizable compounds (C2))
C2-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)
C2-2: Aronix M-521 (manufactured by Toagosei Co., Ltd.)
C2-3: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[Photoinitiator (D)]
D-1: Omnirad 369 (manufactured by IGM Resins)
D-2: Omnirad 907 (manufactured by IGM Resins)
D-3: Compound represented by the above chemical formula (9) D-4: IRGACURE OXE-02 (manufactured by BASF)
D-5: Omnirad 184 (manufactured by IGM Resins)

[Sensitizer (E)]
(Thioxanthone-based compound (E1))
E1-1: 2,4-diethylthioxanthone (benzophenone compound (E2))
E2-1: 4,4'-bis(diethylamino)benzophenone

[Thermosetting compound (I)]
(Epoxy compound (I1))
I1-1: EHPE-3150 (manufactured by Daicel)

[Leveling agent (N)]
N-1: BYK-330 (manufactured by BYK-Chemie)
N-2: Megafac F-551 (manufactured by DIC)
1 part of each of (N-1) and (N-2) above was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution as a leveling agent (N).

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

<Evaluation of photosensitive composition>
The photosensitive compositions 1 to 34 (Examples 1 to 31 and Comparative Examples 1 to 3) obtained were evaluated for developability, pattern formability, and agglomerated foreign matter by the following methods. Table 3 shows the evaluation results.

[Evaluation of developability]
The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) of 100 mm length×100 mm width and 0.7 mm thickness using a spin coater 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, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . Furthermore, after cooling this substrate to room temperature, using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., two levels of development time (40 seconds, 70 seconds), washed with deionized water, and air-dried. The resulting substrate was post-baked in a clean oven at 230° C. for 30 minutes to form a striped pattern on the substrate.
The pattern was observed with an optical microscope, and the presence or absence of development residues in unexposed areas and chipping was evaluated. The evaluation criteria are as follows, and 2 or more is practical.
3: At the development time of 70 seconds, there was no development residue in the unexposed area, and there was no missing pattern.
2: At the development time of 70 seconds, development residue occurred or pattern missing occurred in the unexposed area.
1: Development residue or pattern missing occurred in the unexposed area at the development time of 40 seconds.

[Pattern Formability 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 this substrate to room temperature, it was exposed at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp through a photomask having a stripe pattern with a width of 5 μm. Thereafter, the substrate was developed by spraying with an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., washed with deionized water, air-dried, and cleaned. A substrate for evaluation was obtained by heating in an oven at 230° C. for 30 minutes. Spray development was carried out for the shortest time for pattern formation without development residue for each photosensitive composition film, and this was taken as the proper development time.
Among the patterns of the substrate for evaluation, fine line patterns with a width of 5 to 25 μm were observed with an optical microscope to confirm residual fine line patterns. The evaluation criteria are as follows, and 3 or more is practical.
5: Fine lines of 10 μm or less remain.
4: Fine lines of 15 μm or more remain.
3: Fine lines of 20 μm or more remain.
2: Fine lines of 25 μm remain.
1: Fine lines do not remain.

[Pattern Formability Evaluation (2): Linearity]
The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) of 100 mm length×100 mm width and 0.7 mm thickness using a spin coater 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, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . Thereafter, the substrate was developed by spraying with an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., washed with deionized water, air-dried, and cleaned. A substrate for evaluation was obtained by heating in an oven at 230° C. for 30 minutes. Spray development was carried out for the shortest time for pattern formation without development residue for each photosensitive composition film, and this was taken as the proper development time.
Evaluation substrates were evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon, and averaging the values. The evaluation criteria are as follows, and 3 or more is practical.
5: The difference between the maximum value and the minimum value of the line width is less than 0.5 μm 4: The difference between the maximum value and the minimum value of the line width is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum value and the minimum value of the line width The difference is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum value and the minimum value of the line width is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum value and the minimum value of the line width is 2.0 μm or more

[Pattern formation evaluation (3): cross-sectional shape]
Using a scanning electron microscope (“S-3000H” manufactured by Hitachi High-Tech Co., Ltd.), the cross-sectional shape of the pattern on the substrate prepared in pattern formability evaluation (2) was confirmed. For the evaluation, an SEM image of the cross section of the pattern was captured, and the cross-sectional shape was evaluated by measuring the taper angle between the substrate and the end of the cross section of the pattern. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle of 70 degrees or more and less than 90 degrees 1: Taper angle of 90 degrees that's all

[Evaluation of aggregated foreign matter]
Using a scanning electron microscope (“S-3000H” manufactured by Hitachi High-Tech Co., Ltd.), the surface of the pattern was observed on the substrate prepared in pattern formability evaluation (2). The particle size of 50 aggregates was measured, the average value was calculated, and the average particle size was obtained. The evaluation criteria are as follows, and 3 or more is practical.
5: Average particle size of aggregates is less than 100 nm 4: Average particle size of aggregates is 100 nm or more and less than 300 nm 3: Average particle size of aggregates is 300 nm or more and less than 500 nm 2: Average particle size of aggregates is 500 nm or more 1, Less than 000 nm 1: Average particle size of aggregates is 1,000 nm or more

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 (11)

A photosensitive composition comprising a near-infrared absorbing dye (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The photosensitive composition, wherein the polymerizable compound (C) contains a polymerizable compound (C1) having a urethane bond. The photosensitive composition according to claim 1, wherein the polymerizable compound (C) further contains a polymerizable compound (C2) other than the polymerizable compound (C1) having a urethane bond. The mass ratio of the polymerizable compound (C1) having a urethane bond and the polymerizable compound (C2) other than the polymerizable compound (C1) having a urethane bond is 80:20 to 20:80. The photosensitive composition according to . 3. The photosensitive composition according to claim 1, wherein the polymerizable compound (C1) having a urethane bond has 5 to 12 polymerizable unsaturated groups. 3. The photosensitizer according to claim 1 or 2, wherein the polymerizable compound (C1) having a urethane bond contains at least one selected from the group consisting of alicyclic urethane (meth)acrylates and aromatic urethane (meth)acrylates. sex composition. 3. The photosensitive composition according to claim 1, wherein the polymerizable compound (C1) having a urethane bond has an acid group. A cured film obtained by curing the photosensitive composition according to claim 1 . An optical filter comprising the cured film according to claim 7 . An image display device comprising the cured film according to claim 7 . A solid-state imaging device comprising the cured film according to claim 7 . An infrared sensor comprising the cured film according to claim 7.

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