JP2023043479A - 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 excellent in developability and pattern formability and capable of forming a cured film excellent in resistance (solvent resistance and heat cycle resistance) by curing at a low temperature (130°C or lower).SOLUTION: A photosensitive composition contains a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The polymerizable compound (C) contains a polymerizable compound (C1) having a structure selected from dendrimer structures and hyperbranched structures.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a photosensitive composition containing near-infrared absorbing dyes and uses thereof.

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 on the infrared cut filter by photolithography. However, the composition containing the near-infrared absorbing dye used for the infrared cut filter easily transmits light of active energy rays (i-line, etc.), so when exposed through a photomask, the unexposed portion of the mask periphery are also likely to be exposed to reflected light or scattered light from the substrate or the like, and the reaction in the portion covered with the mask tends to proceed. As a result, the solubility in the developing solution is lowered, the line width of the obtained pattern is increased, and there is a problem that a desired line width cannot be obtained and a problem that a development residue is generated. Conventionally, as a method for solving the above problems, adjustment of the amount of active radicals generated, that is, a method of adjusting the type and amount of the photopolymerization initiator, and adjustment of the amount of exposure have been studied. For example, in the case of thickening of the line width, it is possible to reduce the amount of active radicals by using a photopolymerization initiator with low sensitivity or reducing the amount used to reduce the amount of active radicals, or by reducing the amount of exposure. There was a method to reduce the reflected light and scattered light from the material and make the line width appropriate. However, this method has a problem that the resistance of the cured film is lowered, and the pattern shape and the resistance of the cured film are deteriorated.
When a pattern is formed by photolithography, heat treatment (hereinafter referred to as post-baking) is performed at 200° C. or higher to sufficiently harden the cured film. Since the near-infrared absorptivity tends to decrease during baking, heat treatment is performed at a low temperature. Therefore, the solvent resistance of the cured film is likely to deteriorate.

Therefore, Patent Document 1 discloses a photosensitive composition containing a phthalocyanine compound having a maximum absorption wavelength in the near-infrared region, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent. Further, Patent Document 2 includes an infrared absorbing dye and a resin having a glass transition temperature of 0 to 100 ° C., the resin having a cross-linking group, or a compound having a cross-linking group other than the resin, A near-infrared absorbing composition is disclosed.

Japanese Patent Application Laid-Open No. 2010-160380 WO2017/104735

However, the compositions described in Patent Documents 1 and 2 could not satisfy all of the developability, pattern formability, and cured film resistance at a certain level or higher. In addition, there is also a problem of heat cycle resistance in which peeling and cracking of the cured film occur due to changes in the temperature range in which it is used.

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 having excellent resistance (solvent resistance, heat cycle resistance) when cured at a low temperature (130° C. or less). .

The present invention is a photosensitive composition comprising a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The above-mentioned polymerizable compound (C) relates to a photosensitive composition containing a polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure.

According to the present invention, there is provided a photosensitive composition which is excellent in developability and pattern formability and can form a cured film having excellent resistance (solvent resistance, heat cycle resistance) when cured at low temperature (130° C. or less). can. Moreover, the present invention can provide a cured film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor.

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

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

In the present specification, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means, unless otherwise specified, respectively means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide" do. "C.I." means a color index (C.I.; published by The Society of Dyers and Colorists). The polymerizable group is an ethylenically unsaturated double bond.
Regarding the molecular weight of the compound in the present invention, the low molecular weight compound whose molecular weight can be specified is the value calculated by calculation (formula weight) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight distribution A compound with is a polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.
A monomer is a compound that forms a resin upon polymerization. A monomer is an unreacted state and a monomeric unit is a state in which a monomer forms a resin after polymerization.

<Photosensitive composition>
The photosensitive composition of the present invention is a photosensitive composition comprising a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The polymerizable compound (C) is characterized by including a polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure.

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

The polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure has a closer distance between polymerizable groups in the molecule and a higher density than general linear polymerizable compounds. . Therefore, it is less likely to be affected by oxygen inhibition and chain transfer of the solvent, and it is assumed that it reacts sufficiently even when the amount of photopolymerization initiator or exposure is small, or even at low temperature curing, and a highly resistant cured film can be obtained. In addition, it is speculated that the unique radial structure can effectively relieve external or internal stress, and is less susceptible to temperature differences.

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

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

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

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

The near-infrared absorbing dye (A) includes, for example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, oxonol compounds, pyrromethene compounds, azomethine compounds, triarylmethane compounds, dibenzofuranone compounds, and the like. Among these, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferred, and indigo compounds and naphthalocyanine compounds are more preferred, from the viewpoint of 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, WO 2017/002920, WO 2018/186490, etc.; 2013-230412, etc.; immonium compounds, JP-A-2005-336150, JP-A-2007-197492, JP-A-2008-88426, etc.; anthraquinone compounds, JP-A-62-903, Japanese Patent Laid-Open No. 1-172458, etc.; JP 2016-142891, WO 2017/135359, WO 2018/225837, WO 2019-001987, WO 2020/054718, etc.; 021767 and the like.

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

In general formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, and —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 , Represents —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 can be mentioned.
R ¹⁰⁰ to R ¹¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group. When R ¹⁰² of —COOR ¹⁰² is 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 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, a - 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 hydrogen Represents an atom, optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, and aralkyl group, where R ⁵² of —COOR ⁵² is hydrogen (i.e., carboxyl group) may have a dissociated hydrogen atom (i.e., carbonate group) or may be in the form of a salt.In addition, when R ⁶⁴ of —SO ₂ OR ⁶⁴ is a hydrogen atom (i.e., sulfo group), hydrogen Atoms may be dissociated (ie, a sulfonate group) or in a salt state, and R ⁵ and R ⁶ and R ⁷ and R ⁸ may be bonded together to form a ring. )

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

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

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

General formula (3)

(In general formula (3), R ^1x and R ^1y each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, 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 , R ^1x , R ^1y and R ³ , and each R ^4x R ^4y independently represents a substituent. It is described in JP-A-2009-263614, JP-A-2011-68731, and International Publication No. 2015/166873.

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

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

R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR ^4x R ^4y , and is represented by a hydrogen atom, an alkyl group, an aryl group, or -BR ^4x R ^4y is more preferred, and a group represented by —BR ^4x R ^4y is particularly preferred. The substituent represented by R ^4x R ^4y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. Two R ⁴ groups in general formula (3) may be the same or different.

Specific examples of the pyrrolopyrrole compound are shown below. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. Further, 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).

（一般式（４）中、Ｘ_１～Ｘ_８、Ｙ_ｌ～Ｙ_８は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいフタルイミドメチル基、または、置換基を有してもよいスルファモイル基を表す。また、Ｘ_１～Ｘ_８は、それぞれ独立に、互いに結合して置換基を有してもよい芳香環を形成しても良い。ただし、Ｘ_１とＸ_２、Ｘ_３とＸ_４、Ｘ_５とＸ_６、Ｘ_７とＸ_８のいずれか１つ以上は互いに結合して置換基を有してもよい芳香環を形成する。
Ｚは、下記一般式（５）で示す単量体単位を含む重合体部位、または下記一般式（６）で表すリン化合物部位であり、＊は、Ａｌとの結合手である。） general formula (4)

(In general formula (4), X ₁ to X ₈ and Y ₁ to Y ₈ are each independently a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an optionally substituted alkyl group, a substituent aryl group optionally having a substituent, a cycloalkyl group optionally having a substituent, a heterocyclic group optionally having a substituent, an alkoxyl group optionally having a substituent, having a substituent aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted phthalimidomethyl group, or optionally substituted represents a sulfamoyl group, and each of X ₁ to X ₈ may be independently bonded to each other to form an aromatic ring optionally having a substituent, provided that X ₁ and X ₂ and X ₃ Any one or more of 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 heterocyclic group optionally having a substituent includes a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group and the like. ” includes a 3-methylpyridyl group, an N-methylpiperidyl group, an 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.

（一般式（５）中、Ｘは、－ＣＯＮＨ－Ｒ^２５－、－ＣＯＯ－Ｒ^２６－、－ＣＯＮＨ－Ｒ^２７－Ｏ－、－ＣＯＯ－Ｒ^２８－Ｏ－、Ｒ^２５～Ｒ^２８は、炭素原子と炭素原子の間が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、または－ＮＨＣＯ－で連結されていても良いアルキレン基もしくはアリーレン基を表す。Ｒ^３１は水素または、メチル基を表す。） general formula (5)

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

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

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

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

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

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

（一般式（６）中、Ｒ^２９およびＲ^３０は、それぞれ独立に、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基または置換基を有してもよいアリールオキシ基を表し、Ｒ^２９とＲ^３０は、互いに結合して環を形成しても良い。） 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, an optionally substituted represents a good alkoxyl group or an optionally substituted aryloxy group, and R ²⁹ and R ³⁰ may combine with each other to form a ring.)

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

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

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

（一般式（７）中、Ｙ_９～Ｙ_１６、Ｒ_８～Ｒ_２１は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいフタルイミドメチル基、または、置換基を有してもよいスルファモイル基を表す。
Ｚは、一般式（５）で示す単量体単位を含む重合体部位、または一般式（６）で表すリン化合物部位であり、＊は、Ａｌとの結合手である。） general formula (7)

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

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

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

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

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

（一般式（８）、一般式（９）中、Ｘ_１～Ｘ_４０はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシル基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリールチオ基、アミノ基、置換基を有していてもよいアルキルアミノ基、置換基を有していてもよいアリールアミノ基、シアノ基、ハロゲン原子、ニトロ基、水酸基、－ＳＯ_３Ｈ；－ＣＯＯＨ；およびこれら酸性基の１価～３価の金属塩；アルキルアンモニウム塩を表す。Ｍは、金属原子を表す。）

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

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.

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

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

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

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

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

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

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

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

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

Resin (B) is not particularly limited, and known resins can be used. Examples thereof include (meth)acrylic resins, styrene resins, styrene-acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, and cyclic olefin resins. These can be used alone or in combination of two or more.

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

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

(Resin (B1))
The resin (B) contains an aromatic ring-containing monomer unit (b1) and a polymerizable group-containing monomer unit (b2) as a binder resin from the viewpoint of developability, pattern formability, and resistance of a cured film. and a resin (B1) in which a homopolymer of the aromatic ring-containing monomer unit (b1) has a glass transition temperature of 80° C. or higher. Resin (B1) is not particularly limited, and known resins can be used. For example, a monomer that forms an aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80 ° C. or higher and a monomer that forms a polymerizable group-containing monomer unit (b2) A copolymer or a copolymer of a monomer forming an aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80° C. or higher and another monomer copolymerizable therewith. To, a copolymer obtained by reacting a compound having a polymerizable group to introduce a polymerizable group-containing monomer unit (b2), a copolymer obtained by the method described in JP-A-2008-165059, etc. is mentioned. Incidentally, the polymerizable group-containing monomer unit (b2) is preferably imparted with a polymerizable group by modifying the precursor of the polymerizable group-containing monomer unit (b2) for copolymerization.

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

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

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

<Method (i)>
The carboxyl group of the carboxyl group-containing monomer is added to the epoxy group of the resin containing the aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80° C. or higher and the epoxy group-containing monomer unit. There is method (i).

Examples of monomers forming epoxy group-containing monomer units include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylates, and 3,4-epoxycyclohexyl (meth)acrylates. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

Carboxyl group-containing monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among these, acrylic acid and methacrylic acid are preferred.

From the viewpoint of developability, a polymerizable group-containing unit obtained by further reacting an acid anhydride with the site where the carboxyl group of the carboxyl group-containing monomer is added to the epoxy group of the epoxy group-containing monomer unit is also used. It is useful as a mer unit (b2).

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

<Method (ii)>
The epoxy group of the epoxy group-containing monomer is added to the carboxyl group of the resin containing the aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80° C. or higher and the carboxyl group-containing monomer unit. There is method (ii).

<Method (iii)>
A method of reacting the isocyanate group of the isocyanate group-containing monomer with the hydroxyl group of the resin containing the aromatic ring-containing monomer unit (b1) having a homopolymer glass transition temperature of 80 ° C. or higher and the hydroxyl group-containing monomer unit ( iii).

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) Examples include acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate.

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

Examples of the polymerizable group-containing monomer unit (b2) include the following units (b2-1) to (b2-8). In addition, this invention is not limited to these.

The content of the polymerizable group-containing monomer unit (b2) is preferably 5 to 95 mol%, more preferably 15 to 90 mol%, of the total structural units of the resin (B1) from the viewpoint of the resistance of the cured film. .

[Alicyclic hydrocarbon-containing monomer unit (b3)]
From the viewpoint of pattern formability, the resin (B1) preferably further contains an alicyclic hydrocarbon-containing monomer unit (b3). The alicyclic hydrocarbon-containing monomer unit (b3) includes, for example, units (b3-1) to (b3-6) below. In addition, this invention is not limited to these.

From the viewpoint of pattern formability, the content of the alicyclic hydrocarbon-containing monomer unit (b3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, of the total structural units of the resin (B1). preferable.

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

Other monomers forming the monomer unit (b4) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylates, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylates such as (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate;
2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) ) hydroxyl group-containing (meth)acrylates such as acrylates;
epoxy groups such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate; containing (meth)acrylates;
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid;
(Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine ;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Examples include fatty acid vinyls such as vinyl acetate and vinyl propionate.

Other monomer units (b4) include, for example, the following units (b4-1) to (b4-9). In addition, this invention is not limited to these.

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

The acid value of the resin (B1) is preferably 30 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, from the viewpoint of developability.

Resin (B1) can be used alone or in combination of two or more.

The content of the resin (B1) 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).

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

[Blocked isocyanate group-containing monomer unit (b5)]
The blocked isocyanate group-containing monomer unit (b5) is a structural unit derived from a blocked isocyanate group-containing monomer. The blocked isocyanate group-containing monomer includes, for example, a compound obtained by blocking the isocyanate group in an isocyanate compound having a polymerizable group with a blocking agent.

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

Blocking agents are lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam;
Alcohol compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol;
Phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. a phenolic compound of;
Active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone;
Mercaptan compounds such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan;
Amine compounds such as diphenylamine, phenylnaphthylamine, aniline and carbazole;
Acid amide compounds such as acetanilide, acetanisidide, acetic acid amide, and benzamide;
Acid imide compounds such as succinimide and maleic imide;
imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole;
Pyrazole compounds such as pyrazole and 3,5-dimethylpyrazole;
Oxime-based compounds such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime, cyclohexanone oxime, and the like are included. These blocking agents can be used alone or in combination of two or more.
Preferred blocking agents are diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, and 3,5-xylenol from the viewpoint of low-temperature curing.

Commercial products of blocked isocyanate group-containing monomers include Karenz MOI-DEM, MOI-BP and MOI-BM manufactured by Showa Denko.

The content of the blocked isocyanate group-containing monomer unit (b5) is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, of the total structural units of the resin (B2) from the viewpoint of low-temperature curing. is more preferable.

A monomer unit other than the blocked isocyanate group-containing monomer unit (b5) is not particularly limited as long as it is a unit formed from a monomer copolymerizable with the blocked isocyanate group-containing monomer. Monomers can be used. Examples thereof include monomer units (b1) to (b4) described for resin (B1).

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

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

The acid value of the resin (B2) is preferably 30 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, from the viewpoint of developability.

Resin (B2) can be used alone or in combination of two or more.

The content of the resin (B2) 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).

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

The resin (B3) is preferably a resin having an adsorptive group with 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 types of the resin (B3) 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 alkyl Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and amides formed by the reaction of polyesters having free carboxyl groups, Salts thereof, water-soluble resins such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters and the like can be mentioned.

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

Specifically, the resin (B3) is Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie Japan. ,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, 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等, 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, etc. Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by the company, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, international publication No. 2008/007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2012-255128, JP 2009- 251481, JP 2007-23195, JP 1996-143651, etc. and resins described in.

Resin (B3) can be used alone or in combination of two or more.

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

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

The polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure preferably has a weight average molecular weight (Mw) of 1,000 to 30,000 from the viewpoint of pattern formability and resistance of the cured film. 1,000 to 25,000 is more preferred.

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

In the polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure, the polymerizable group is an epoxy group, a vinyl group, a (meth)allyl group, from the viewpoint of pattern formability and resistance of the cured film. It is preferably at least one selected from the group consisting of (meth)acryloyl groups, more preferably (meth)acryloyl groups.

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

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

As the polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure, an appropriately synthesized one may be used, or a commercially available product may be used.

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

The polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure is, for example, "Viscoat #1000" manufactured by Osaka Organic Chemical Industry Co., Ltd. (dendrimer structure, weight average molecular weight 2,000, average acryloyl group number 14 ), "Miramer SP-1106" manufactured by Miwon Specialty Chemical (dendrimer structure, weight average molecular weight 1,630, average acryloyl group number 18), "Miramer SP-1108" (dendrimer structure, weight average molecular weight 3,000, average acryloyl Radix 13), "CN2301" manufactured by SARTOMER (hyperbranched structure, weight average molecular weight 7,500, average acryloyl group number 9), "CN2302" (hyperbranched structure, weight average molecular weight 1,500, average acryloyl group number 16), "CN2303" (hyperbranched structure, weight average molecular weight 1,400, average number of acryloyl groups 6), "CN2304" (hyperbranched structure, weight average molecular weight 2,900, average number of acryloyl groups 18) and the like.

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

Other polymerizable compounds (C2) are not particularly limited, and known compounds that can be polymerized by radicals, acids, or heat can be used. Examples thereof include compounds having a polymerizable group. Examples of polymerizable groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

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

Moreover, the other polymerizable compound (C2) may contain an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Examples of the polymerizable compound containing an acid group include, for example, polyhydric alcohols and (meth)acrylic acid, free hydroxyl group-containing poly(meth)acrylates, and esters of dicarboxylic acids; Esterified products with alkyl (meth)acrylates and the like can be mentioned. Specifically, monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

Moreover, the other polymerizable compound (C2) may contain a urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or a polyfunctional polyfunctional obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. urethane acrylate and the like.

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

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, DCPA-30, DCPA-60, Aronix M-303 manufactured by Toagosei Co., Ltd. , M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M -403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, M-510, M-520, M-521, Osaka organic company Viscote #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Gas Chemicals Co., Ltd. OGSOL EA-0200, EA-0300, GA-5060P, GA -2800, Miwon Specialty Chemical Co. , Ltd. Miramer HR6060, 6100, 6200, Shin Nakamura Chemical Co., Ltd. NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, A-9300, Daicel Allnex Co. EBECRYL40 , 130, 140, 145 and the like.

Other polymerizable compounds (C2) 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 nonvolatile content of the photosensitive composition, from the viewpoint of pattern formability and resistance of the cured film. preferable.

[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.
In addition, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, JP 2011-020998, WO 2015/036910, etc. Also included are the oxime compounds described.

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

Specific examples of the oxime compound include the following. In addition, this invention is not limited to these.

化学式（１５）

化学式（１６）

chemical formula (14)

chemical formula (15)

chemical formula (16)

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

The content of the photopolymerization initiator (D) is preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the near-infrared absorbing dye (A), from the viewpoint of pattern formability and resistance of the cured film, and 1 to 20 parts by mass. 15 parts by weight is more preferred, and 2 to 10 parts by weight is particularly preferred.

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

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 preferable, and the benzophenone-based compound (E2) is more preferable, from the viewpoint of developability and 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 50 to 400 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D) from the viewpoint of developability and pattern formability.

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

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

(pigment)
Pigments are preferably compounds classified as pigments in the Color Index.
Red pigments include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance, C.I. I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, the pigment described in Patent No. 6368844 is preferable, C. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more 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, JP 2012-226110, JP 2017-171912, JP 2017-171913, JP 2017-171914 Examples thereof include pigments described in JP-A-2017-171915 and the like. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A-2012-226110 are preferred.

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

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

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

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

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

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

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

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

Among the aspects of (5) above, C.I. I. Pigment Yellow 139 and blue pigment C.I. I. Pigment Blue 15:6 and purple pigment with C.I. I. Pigment Violet 23 is more preferred.

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

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

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

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

Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance and solvent resistance) and affinity with pigments. In salt-forming compounds of basic dyes, anion components that act as counter ions include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and halogenated carbonization compounds. A salt-forming compound obtained by salt-forming an anion compound having a conjugate base of an organic acid having a hydrogen group and an acid dye is preferred. It should be noted that the resistance of the salt-forming compound is further improved when it contains a polymerizable 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 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the non-volatile 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 cost. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, 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.

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

Examples of the dye derivative (H) include compounds having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (H) 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, phthalocyanine pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo, squarylium compounds, naphthalocyanine compounds, and the like.

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-based dye derivative, JP-A-2003-167112 as a quinophthalone-based dye derivative, JP 2006-291194, JP 2008-31281, JP 2012-226110, as a naphthol dye derivative, JP 2012-208329, JP 2014-5439, azo dye As derivatives, JP-A-2001-172520 and JP-A-2012-172092, as acidic substituents, JP-A-2004-307854, as basic substituents, JP-A-2002-201377 and 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.

[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.

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 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, trimercapto tris(2-hydroxyethyl) isocyanurate propionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

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

[Polymerization inhibitor (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 oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

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

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

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

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). Antioxidant (M) is the photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive coloring composition, which prevents yellowing caused by oxidation due to the thermal process during thermal curing and 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.

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 manufactured by ADEKA, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based (co)polymer Polyflow-No. 75, No. 90, No. 95 and the like.

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

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

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

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

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

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

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

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

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

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

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

Examples of the adhesion improver (P) include silane coupling agents and the like.

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]
To the photosensitive composition of the present invention, for example, a near-infrared absorbing dye (A), a dispersing resin, an organic solvent (Q), and the like are added and subjected to dispersion treatment to produce a dispersion. Thereafter, a binder resin (preferably an alkali-soluble resin), a polymerizable compound (C), a photopolymerization initiator (D), and the like are blended with the dispersion to produce the dispersion. 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, and 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 be a flat film.

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

The method for producing a cured film will be described in detail below.
(Step (1))
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 the necessary Dry (pre-bake) at a temperature of 50 to 100° C. for 10 to 120 seconds using an oven, hot plate, etc., depending on the conditions.
Examples of the substrate include a glass substrate and a silicon substrate. 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 film 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.

(Step (3))
The cured film obtained in step (2) is subjected to alkali development treatment, whereby the layer of the composition in the unexposed portions is eluted in an alkaline aqueous solution, leaving only the cured portions to obtain a patterned cured film.
Developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11-13, 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 130° C. or lower, more preferably 100° C. or lower. The heating time is preferably about 5 minutes to 1 hour, more preferably about 5 minutes to 30 minutes.

<Optical filter>
The optical filter of the present invention has a cured film. The use of the optical filter is preferably an infrared cut filter or an infrared transmission filter, more preferably an infrared cut filter. The optical filter of the present invention can be manufactured by the same method as the cured film described above.

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

An example of the image display device of the present invention will be described. An image display device comprises the cured film of the present invention and a light source. As a light source, a cold cathode fluorescent lamp (CCFL) and a white LED can be used. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view showing a configuration example of an image display device provided with the cured film of the present invention. The image display device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged facing each other with a gap between them, and a liquid crystal LC is enclosed between them.

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

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

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

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

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

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

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

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

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

Examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

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

<Solid-state image sensor>
The solid-state imaging device of the present invention has a cured film. When used for a solid-state imaging device, it is not particularly limited. and a light-receiving element made of polysilicon or the like, and the cured film of the present invention is provided on the light-receiving element formation surface side or the opposite side of the formation surface. FIG. 2 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device provided with the cured film of the present invention.

As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging device 201 and a transparent cover glass 203 that is held above the solid-state imaging device 201 and seals the solid-state imaging device 201. there is Further, a lens layer 211 is provided over the cover glass 203 with spacers 104 interposed therebetween. The lens layer 211 is composed of a support 213 and a lens material 212 . When stray light enters the peripheral region of the lens layer 211 , light diffusion weakens the light condensing effect of the lens material 212 , reducing the amount of light that reaches the imaging unit 202 . Also, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 211 is provided with the cured film 214 of the present invention to shield light.

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

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

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

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

<Infrared sensor>
The infrared sensor of the present invention has a cured film. FIG. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with the cured film of the present invention. The infrared sensor 300 shown in FIG.

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

Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 is arranged that allows transmission of the light of the wavelength that has passed through the infrared transmission filter 313. As shown in FIG.
The infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared rays of a specific wavelength, and is a cured film containing two or more kinds of chromatic colorants in the photosensitive composition of the present invention. can be used. The infrared transmission filter 313 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.

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

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

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

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

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

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

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

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

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40 ° C. , using a tetrahydrofuran (THF) solution as an eluent and measuring at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by weight 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 (17). 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 stainless steel gallon kneader (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 (17)

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

chemical formula (18)

(Near-infrared absorbing dye (A-3))
In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and three 34 parts of aluminum chloride was mixed and stirred, and after the temperature was raised, the mixture was refluxed at 136° C. for 5 hours. The reaction solution cooled to 30° C. while stirring was poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of ion-exchanged water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain compound a.
Next, 140 parts of compound a was added to 1,500 parts of concentrated sulfuric acid in a reaction vessel under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution is poured into 1,000 parts of cold water at 3°C, and the 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 b was obtained.
5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50°C. After adding 10 parts of compound b little by little to this solution, the mixture was stirred at 90° C. for 120 minutes. For confirmation of the end point of the reaction, for example, the reaction liquid was dropped onto a filter paper, and the end point was set at the point where the bleeding disappeared. Subsequently, this reaction solution is poured into 2,000 parts of ion-exchanged water, and the resulting precipitate is filtered, washed with water, and dried to obtain a mixture of compounds represented by the following chemical formula (19) ( A near-infrared absorbing dye (A-3) having a mixing ratio of n1:n2:n3:n4=7:19:59:15 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 (19)

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

chemical formula (20)

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

chemical formula (21)

<Production of resin (B)>
(Resin (B1-1) solution)
262.0 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a reaction vessel equipped with a separable four-necked flask, a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and 120 parts of nitrogen gas was introduced into the vessel. °C. Then, 0.1 mol of styrene, which is the monomer that forms the aromatic-containing monomer unit (b1), dicyclopenta, which is the monomer that forms the alicyclic hydrocarbon-containing monomer unit (b3) 0.3 mol of nil methacrylate, 0.6 mol of glycidyl methacrylate which is a monomer forming other monomer units (b4), t-butyl peroxy-2-ethylhexanoate which is a polymerization initiator, The PGMAc mixture was added dropwise from the drop tube over 2.5 hours.
After the dropwise addition was completed, the mixture was further stirred at 120°C for 2 hours. Then, the inside of the flask was replaced with air, 0.6 mol of acrylic acid, and triphenylphosphine and methylhydroquinone as catalysts were added, and the mixture was stirred at 110°C for 10 hours, and the epoxy group of glycidyl methacrylate and the carboxyl group of acrylic acid were added. was reacted, then 0.38 mol of tetrahydrophthalic anhydride was added and stirred at 110° C. for 4 hours. Thereby, a polymerizable group-containing monomer unit (b2) was formed.
Thereafter, PGMAc was added so that the non-volatile content was 40% by mass to prepare a resin (B1-1) solution. Resin (B1-1) had an acid value of 80 mgKOH/g and a weight average molecular weight of 9,000.

(Resin (B1-2) to (B1-13) solution)
Resins (B1-2) to (B1-13) were synthesized so that the molar ratios of the constituent components shown in Table 1 were obtained, and PGMAc was added to adjust the non-volatile content to 40% by mass.

Each of the monomeric units (b1) to (b4) of the constituents listed in Table 2 is the unit described above, and the corresponding monomers or their precursors were used for the synthesis.

(Resin (B2-1) solution)
After putting 257.3 g of PGMAc into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, the mixture was stirred while being replaced with nitrogen, and heated to 78°C. Next, 30 mol of dicyclopentanyl methacrylate, which is a monomer that forms the alicyclic hydrocarbon-containing monomer unit (b3), and glycidyl, which is a monomer that forms the other monomer unit (b4) 32 mol of methacrylate, 33 mol of methacrylic acid, which is a monomer that forms other monomer units (b4), and malonic acid-2, which is a monomer that forms a blocked isocyanate group-containing monomer unit (b5) A mixture of 5.0 moles of -[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester and 13.4 g of 2,2′-azobis ( 2,4-Dimethylvaleronitrile) (polymerization initiator) was added and dissolved in 78.7 g of PGMAc and dropped into the flask from the dropping funnel. After completion of dropping, the mixture was stirred at 78°C for 3 hours.
Thereafter, PGMAc was added so that the non-volatile content was 40% by mass to prepare a resin (B2-1) solution. Resin (B2-1) had an acid value of 111 mgKOH/g and a weight average molecular weight of 7,500.

(Resin (B3-1) 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 reactor 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 mass average molecular weight of 20,000, a molecular weight distribution Mw/Mn of 1.4, and a reaction conversion rate of 98.5%. Thus, a resin (B3-1) having an amine value per non-volatile content of 169.8 mgKOH/g was obtained. After cooling to room temperature, about 2 g of the sample was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added so that the non-volatile content was 30% by mass to obtain a resin (B3-1) solution. prepared.

(Resin (B3-2) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured. % or more, the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added to dilute the nonvolatile content to 30% by nonvolatile measurement to obtain a resin (B3-2) solution having an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn).

(Resin (B3-3) solution)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a temperature control, a condenser and a stirrer, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution of 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100° C. for 7 hours. . After confirming that 98% or more of the acid anhydride is half-esterified by acid value measurement, the reaction is terminated, and PGMAc is added to dilute so that the nonvolatile content is 30% by nonvolatile content measurement, and the acid value is 70 mgKOH / g. , to obtain a resin (B3-3) solution having a weight average molecular weight of 8,500.

<Production of polymerizable compound (C)>
(Other polymerizable compound (C2-3) solution)
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 and 66 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. 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. The non-volatile content was adjusted to 50% by mass to obtain another polymerizable compound (C2-3) solution.

<Production of colorant (F)>
(Micronized green pigment (F-1))
C. I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80° C. for a day and night. A fine green pigment (F-1) was obtained by drying and pulverizing.

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

(Micronized blue pigment (F-3))
C. I. Pigment Blue 15:6 (100 parts), sodium chloride (1,000 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50° C. for 12 hours. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. It was dried for 24 hours and pulverized to obtain a finely divided blue pigment (F-3).

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

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

<Production of dispersion>
(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 (P-1) is PGMAc.
Near-infrared absorbing dye (A-1): 15.0 parts Resin (B3-1) solution: 20.0 parts Organic solvent (P-1): 65.0 parts

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

<Production of photosensitive composition>
[Example 1]
(Photosensitive composition 1)
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive composition 1.
Dispersion 1: 15.0 parts Dispersion 3: 20.0 parts Resin (B1-1) solution: 15.0 parts Polymerizable compound (C1-1): 10.0 parts Photoinitiator (D-2) : 0.25 parts Photoinitiator (D-4): 0.25 parts Sensitizer (E2-1): 0.75 parts Leveling agent (N): 1.0 parts Organic solvent (P): 37. 75 copies

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

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

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

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

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

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

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

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

<Evaluation of photosensitive composition>
The resulting photosensitive compositions 1 to 41 (Examples 1 to 39, Comparative Examples 1 and 2) were evaluated for developability, pattern formability, and cured film resistance by the following methods. Table 5 shows the evaluation results.

[Evaluation of developability]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed through a photomask having a stripe pattern of 100 μm width using an ultra-high pressure mercury lamp under conditions of illuminance of 30 mW/cm ² and 40 mJ/cm ² . Further, after cooling the substrate to room temperature, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., washed with deionized water, and air-dried. The resulting substrate was post-baked in a clean oven at 130° C. for 20 minutes to form a stripe 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 3 or more is practical.
5: There was no development residue in the unexposed area, and there was no missing pattern.
4: A small amount of development residue occurred in the unexposed area, or a slight lack of pattern occurred.
3: A small amount of development residue occurred in the unexposed area, and a slight pattern missing occurred.
2: Many development residues occurred in the unexposed area, or many pattern defects occurred.
1: Many development residues occurred in the unexposed area, and many pattern defects occurred.

[Pattern Formability Evaluation (1): Linearity]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to light under the conditions of 30 mW/cm ² and 40 mJ/cm ² of illumination through a photomask having a stripe pattern with a width of 50 μm using an ultra-high pressure mercury lamp. After that, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., washed with deionized water, and air-dried. The obtained substrate was post-baked in a clean oven at 130° C. for 20 minutes to obtain a substrate for pattern shape evaluation.
The resulting substrate for pattern shape evaluation was evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using a Nikon ECLIPSE LV100POL Model optical microscope and averaging them. 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 formability evaluation (2): 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 (1) was confirmed. For the evaluation, a cross-sectional SEM image of a striped pattern with a width of 100 μm was captured, and the cross-sectional shape was evaluated by measuring the taper angle between the substrate and the end of the cross-section of the pattern. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Taper angle of 40 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of 30 degrees or more and less than 40 degrees, or 60 degrees or more and less than 70 degrees 2: Taper angle of 20 degrees or more and less than 30 degrees, or 70 degrees or more and less than 90 degrees 1: Taper angle less than 20 degrees or 90 degrees or more

[Evaluation of cured film resistance (1): solvent resistance]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling this substrate to room temperature, it was exposed to ultraviolet light through a photomask having a stripe pattern of 100 μm width using a high-pressure mercury lamp under conditions of illuminance of 30 mW/cm ² and 50 mJ/cm ² . Further, after cooling this substrate to room temperature, it was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., washed with deionized water, and air-dried. The resulting substrate was post-baked in a clean oven at 130° C. for 20 minutes to obtain a substrate for evaluation.
The resulting substrate was immersed in N-methylpyrrolidone at room temperature for 30 minutes, washed with deionized water, air-dried, and a stripe pattern portion with a width of 100 μm was observed with an optical microscope. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: No change in appearance and color.
4: Slight wrinkles, etc., but no change in color.
3: Some wrinkles or the like occur, but there is no change in color.
2: Wrinkles and the like are generated on the entire surface, and the color is slightly faded.
1: Peeling and discoloration occurred.

[Evaluation of cured film resistance (2): heat cycle]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed through a photomask with a stripe pattern of 100 μm using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . After that, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., washed with deionized water, and air-dried. The resulting substrate was post-baked in a clean oven at 130° C. for 20 minutes to obtain a heat cycle resistance evaluation substrate.
After that, the heat cycle resistance evaluation substrate was repeatedly subjected to 500 cycles of temperature rise/fall cycles of −20° C. for 10 minutes and 100° C. for 10 minutes. The evaluation criteria are as follows, and 3 or more is practical.
5: No abnormality in appearance at 500 cycles 4: Slight cracking and/or peeling at 500 cycles 3: Partial cracking and/or peeling at 500 cycles 2: Cracks and/or at 200 cycles or peeling occurs Cracking and/or peeling occurs at 1:100 cycles

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

Claims (13)

A photosensitive composition comprising a near-infrared absorbing dye (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
A photosensitive composition, wherein the polymerizable compound (C) comprises a polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure. 2. The photosensitive composition according to claim 1, wherein the polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure has a weight average molecular weight of 1,000 to 30,000. 3. The photosensitive composition according to claim 1, wherein the polymerizable compound (C1) having a structure selected from a dendrimer structure and a hyperbranched structure has an average of 6 or more polymerizable groups. Any one of claims 1 to 3, wherein the content of the polymerizable compound (C1) having a structure selected from a dendrimer structure or a hyperbranched structure is 50% by mass or more in 100% by mass of the polymerizable compound (C). 1. The photosensitive composition according to claim 1. The resin (B) has an aromatic ring-containing monomer unit (b1) and a polymerizable group-containing monomer unit (b2), and is a homopolymer glass of the aromatic ring-containing monomer unit (b1). 5. The photosensitive composition according to any one of claims 1 to 4, comprising a resin (B1) having a transition temperature of 80°C or higher. 6. The photosensitive composition according to any one of claims 1 to 5, wherein the near-infrared absorbing dye (A) has a π-conjugated plane containing a monocyclic or condensed aromatic ring. The photosensitive composition according to any one of claims 1 to 6, comprising a coloring agent (F). 8. The photosensitive composition according to claim 7, wherein the coloring agent (F) contains two or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments and violet pigments. A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 8. An optical filter comprising the cured film according to claim 9 . An image display device comprising the cured film according to claim 9 . A solid-state imaging device comprising the cured film according to claim 9 . An infrared sensor comprising the cured film according to claim 9 .

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