JP2023012949A - Photosensitive composition, optical filter, image display device, and solid state image sensor - Google Patents

Abstract

To provide a photosensitive composition that suppresses water stains on a coat after development, has excellent heat resistance, and can form an excellent pattern.SOLUTION: A photosensitive composition contains an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C), the photopolymerization initiator (C) containing a compound represented by the general formula (1) (C1), and an oxime-based photopolymerization initiator (C2). In the general formula (1), R1, R2 independently represent a hydrogen atom, or a C1 to 8 alkyl group. R3 is a hydrogen atom, or a monovalent substituent).SELECTED DRAWING: None

Description

The present invention relates to photosensitive compositions and uses thereof.

Color filters, which are one type of optical filters used in image display devices, solid-state imaging devices, etc., are produced by, for example, applying a photosensitive composition to a transparent substrate such as glass, and drying the coating to remove the solvent. , a step of irradiating and curing (hereinafter referred to as exposure) the coating film with radiation through a photomask having a desired pattern shape, and then washing and removing the unexposed portion of the coating film (hereinafter referred to as development) Then, if necessary, a heat treatment (hereinafter referred to as post-baking) is performed to sufficiently harden the cured film, thereby obtaining a filter segment pattern for the first color. By performing the same operation, filter segment patterns of other colors can be formed and manufactured.

In the developing step, an alkaline developer is used as the developer to wash and remove the unexposed portions. At that time, there is a problem that the exposed portion is chipped or peeled off, resulting in a defect in the pattern shape. In addition, when the coating film is exposed to an alkaline developer, there is also a problem that a phenomenon of discoloration of the coating film (hereinafter referred to as water staining) occurs. Therefore, there is a demand for a photosensitive composition that does not cause pattern shape defects and water stains in the development process. Furthermore, there was also a problem that the color changed during the post-baking process.

As an effort to improve water stains, Patent Document 1 discloses a colored photosensitive resin composition containing an alkali-soluble resin having a specific structure and an oxime ester fluorene derivative compound as a photopolymerization initiator. Further, Patent Document 2 discloses a resist composition containing a fluorine-based surfactant having a specific structure. As an approach to improve pattern defects during development, Patent Document 3 discloses a colored composition containing a polymerizable compound having an alkylene oxide structure.

JP 2017-173787 A JP 2016-102212 A JP 2014-142582 A

However, none of the compositions described in Patent Documents 1 to 3 were able to satisfy all of water stain, pattern shape, and heat resistance at a certain level or higher.

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive composition that suppresses water staining of a film after development, has good heat resistance, and is capable of forming an excellent pattern.

The present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),
The photopolymerization initiator (C) relates to a photosensitive composition containing a compound (C1) represented by the following general formula (1) and an oxime photopolymerization initiator (C2).
General formula (1)

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

ADVANTAGE OF THE INVENTION According to said invention, the photosensitive composition which suppresses the water stain of the film after image development, has favorable heat resistance, and can form an excellent pattern can be provided. Also, the present invention can provide an optical filter, an image display device, and a solid-state imaging device.

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

In the present invention, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" are each unless otherwise specified. , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide" . "C.I." means a color index (C.I.; published by The Society of Dyers and Colorists). A polymerizable unsaturated group is an ethylenically unsaturated double bond.
Further, with respect to the molecular weight of the compound in the present invention, for low molecular weight compounds whose molecular weight can be specified, it is a value calculated by calculation (formula weight), or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), For a compound having a molecular weight distribution, it is 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. A polymerizable compound is a compound that forms a film by polymerization.

<Photosensitive composition>
One embodiment of the invention relates to a photosensitive composition. The photosensitive composition of the present invention is a photosensitive composition containing an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),
The photopolymerization initiator (C) is characterized by containing a compound (C1) represented by the following general formula (1) and an oxime photopolymerization initiator (C2).
General formula (1)

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

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.
2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-(dimethylamino)-1-one photopolymerization initiators that have been widely used in the field of color filters. Compared to (4-morpholinophenyl)-2-benzyl-1-butanone, the compound (C1) represented by the general formula (1) has a rigid, hydrophobic, and heat-resistant fluorene skeleton. It is assumed that a cured film with high resistance can be obtained. In addition, due to the π-π interaction between the two benzene rings, the cured film has moderate cohesion. Therefore, it is presumed that while suppressing chipping of the pattern during development, it has a structure that is moderately softened against heat, and heat dripping occurs during host baking, and the cross-sectional shape of the pattern becomes good. Then, by using together with a specific oxime-based photopolymerization initiator (C2) that has a different absorption wavelength from the compound (C1) represented by the general formula (1) and has high sensitivity, the wavelength of light that can be used for photopolymerization The area is expanded and the reactivity is improved. Therefore, it is speculated that, for example, even a composition containing a coloring agent that does not allow light to pass deep into the film will undergo a reaction, suppress water staining of the film after development, and improve the pattern shape and heat resistance.

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

[Photoinitiator (C)]
The photosensitive composition of the present invention contains a compound (C1) represented by general formula (1) and an oxime-based photopolymerization initiator (C2) as the photopolymerization initiator (C).

(Compound (C1) represented by general formula (1))
The photosensitive composition of the present invention contains a compound (C1) represented by general formula (1) as a photopolymerization initiator (C).

（一般式（１）中、Ｒ_１、Ｒ_２は、それぞれ独立して、水素原子、または炭素原子数１～８のアルキル基を表す。Ｒ_３は、水素原子、または１価の置換基を表す。） General formula (1)

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

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

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

Examples of the method for producing the compound (C1) represented by the general formula (1) include the methods described in JP-A-2019-507108, JP-A-2019-528331, and the like.

Specific examples of the compound (C1) represented by formula (1) are shown below. In addition, this invention is not limited to these.

Among the compounds represented by the chemical formulas (2) to (4), the compound represented by the chemical formula (2) is preferable from the viewpoint of suppression of water stains, pattern shape and heat resistance.

Compound (C1) represented by formula (1) can be used alone or in combination of two or more.

(Oxime-based photopolymerization initiator (C2))
The oxime-based photopolymerization initiator (C2) includes a compound (C2a) containing one oxime group in one molecule and a compound (C2b) containing two oxime groups in one molecule. From the viewpoint of , a compound (C2b) containing two oxime groups in one molecule is more preferable.

[Compound (C2a) containing one oxime group in one molecule]
Commercial products of the compound (C2a) containing one oxime group in one molecule include, for example, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF, Adeka Arcles N-1919 manufactured by ADEKA, NCI- 730, 831, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Strong New Materials Co., Ltd., OMNIRAD 1312, 1314, 1316 manufactured by IGM Resins , SPI-02, 03, 04, 06, 07 manufactured by Samyang Corporation, and DFI-020, 036 and EOX-01 manufactured by Daito Chemix.

Specific examples of the compound (C2a) containing one oxime group in one molecule include the following. In addition, this invention is not limited to these.

chemical formula (5)

Methods for producing compounds of chemical formulas (5) to (8) include, for example, JP-A-2004-534797, JP-A-2008-80068, JP-A-2012-526185, International Publication No. 2015/036910, International Examples include methods described in Japanese Unexamined Patent Publication No. 2015/152153, Japanese Patent Publication No. 2016-504270, Japanese Patent Publication No. 2017-512886, and the like.

The compound (C2a) containing one oxime group in one molecule preferably contains one or more selected from the group consisting of compounds represented by chemical formulas (5) to (8) from the viewpoint of pattern shape and heat resistance. .

The compound (C2a) containing one oxime group in one molecule can be used alone or in combination of two or more.

[Compound (C2b) Containing Two Oxime Groups in One Molecule]
Compounds containing two oxime groups in one molecule (C2b) are, for example, JP-A-2005-215378, JP-A-2011-105713, JP-A-2017-523465, JP-A-2021-011486. and the like. Among them, a compound represented by the following general formula (9) is preferable.

一般式（９）中、Ｘ_１及びＸ_２は、それぞれ独立にカルボニル結合（－ＣＯ－）または単結合を表す。Ｘ_３は、単結合または硫黄原子を表す。Ｒ_１は、炭素数１～２０のアルキル基を表し、Ｒ_２及びＲ_３は、個々独立に水素原子、炭素数１～２０のアルキル基、炭素数２～３０の複素環、炭素数６～３０のアリール基、または炭素原子数７～３０のアリールアルキル基を表す。Ｒ_４及びＲ_５は、各々独立に炭素数１～２０のアルキル基、炭素原子数２～３０の複素環基、炭素数６～３０のアリール基、または炭素数７～３０のアリールアルキル基を表す。 general formula (9)

In general formula (9), X ₁ and X ₂ each independently represent a carbonyl bond (--CO--) or a single bond. _X3 represents a single bond or a sulfur atom. R ₁ represents an alkyl group having 1 to 20 carbon atoms, R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic ring having 2 to 30 carbon atoms, It represents an aryl group of 30 or an arylalkyl group of 7 to 30 carbon atoms. R ₄ and R ₅ each independently represents an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. show.

In general formula (9), X ₁ and X ₂ each independently represent a carbonyl bond (--CO--) or a single bond. Among them, from the viewpoint of solubility in organic solvents, at least one of X ₁ and X ₂ is preferably a carbonyl bond (-CO-), and X ₁ and X ₂ are a carbonyl bond (-CO-). It is more preferable to have

In general formula ( ₉ ), X3 is a single bond or a sulfur atom, preferably a single bond.

In general formula (9), R ₁ represents an alkyl group having 1 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof. may be a base. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group , nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group and the like. Among these, an ethyl group, a propyl group and an isopropyl group are preferred.

In general formula (9), R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic ring having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. represents an arylalkyl group of numbers 7 to 30;
The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof. may be a base. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group , nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group and the like. Among these, pentyl group, hexyl group, heptyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group and cyclohexylmethyl group are preferable.
Examples of the heterocyclic group having 2 to 30 carbon atoms include pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group and morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group and anthryl group. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, or the like.
Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group and the like. An arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, or the like.

Among these, from the viewpoint of solubility in organic solvents, at least one of R ₂ and R ₃ is preferably a linear alkyl group having 1 to 20 carbon atoms. And from the viewpoint of suppressing water staining, a linear alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms are more preferable.

In general formula (9), R ₄ and R ₅ each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms. represents an arylalkyl group of ∼30.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof. may be a base. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group and the like. . Among these, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable from the viewpoint of reactivity.
Examples of the heterocyclic group having 2 to 30 carbon atoms include pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group and morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group and anthryl group. Aryl groups may also be groups substituted with halogen atoms, amino groups, nitro groups, and the like. Among these, a phenyl group is preferable from the viewpoint of reactivity.
Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group and the like. An arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, or the like.

Among these, R ₄ and R ₅ are preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group or an ethyl group, from the viewpoint of reactivity.

The method for producing the compound represented by formula (9) is not particularly limited, and known methods can be used. For example, the methods described in JP-A-2017-523465, JP-A-2021-011486, etc. can be used.

Specific examples of the compound (C2b) containing two oxime groups in one molecule are shown below. In addition, this invention is not limited to these.

Among chemical formulas (10) to (13), the compound of chemical formula (10) is preferable from the viewpoint of suppressing water stains.

The compound (C2b) containing two oxime groups in one molecule can be used alone or in combination of two or more.

The mass ratio of the compound (C1) represented by the general formula (1) and the oxime-based photopolymerization initiator (C2) is 90:10 to 10:90 from the viewpoints of suppression of water stains, pattern shape, and heat resistance. is preferred, 80:20 to 20:80 is more preferred, and 70:30 to 30:70 is particularly preferred.

The total content of the compound (C1) represented by the general formula (1) and the oxime-based photopolymerization initiator (C2) is the photopolymerization initiator (C ) in 100% by mass, preferably 60 to 100% by mass, more preferably 80 to 100% by mass.

(Other photopolymerization initiators (C3))
The photosensitive composition of the present invention includes a compound (C1) represented by the general formula (1), and a photopolymerization initiator (C3) other than the oxime photopolymerization initiator (C2) (hereinafter, other photopolymerization initiators (also referred to as C3)).

Other photopolymerization initiators (C3) are not particularly limited as long as they are compounds capable of initiating polymerization of the polymerizable compound (B) by light, and known photopolymerization initiators can be used. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-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 acetophenone compounds such as 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-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;
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;

Other photopolymerization initiators (C3) can be used alone or in combination of two or more.

The content of the photopolymerization initiator (C) is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, based on 100 parts by mass of the polymerizable compound (B), from the viewpoint of photocurability. ~30 parts by weight is particularly preferred.

[Alkali-soluble resin (A)]
The photosensitive composition of the present invention contains an alkali-soluble resin (A). Alkali-soluble resin (A) is a binder resin.

The alkali-soluble resin (A) may be any resin that dissolves in an alkali developer, and known resins can be used. The alkali-soluble resin (A) preferably has alkali-soluble groups such as carboxyl groups, phosphoric acid groups, sulfonic acid groups, hydroxyl groups, and phenolic hydroxyl groups. Among these, a carboxyl group is preferred.
Specifically, an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/(anhydrous ) maleic acid copolymers and the like. Further, the alkali-soluble resin (A) can contain a vinyl group, a polymerizable unsaturated group such as (meth)allyl group or (meth)acryloyl group, or a thermosetting group such as epoxy group or oxetanyl group.

The weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, particularly preferably 4,000 to 25,000.

The acid value of the alkali-soluble resin (A) is preferably 30 to 200 mgKOH/g, more preferably 40 to 180 mgKOH/g, from the viewpoint of developability.

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

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

(Alkali-soluble resin (A1))
The alkali-soluble resin (A) contains an alicyclic hydrocarbon-containing monomer unit (a1) and a polymerizable unsaturated group-containing monomer unit (a2) from the viewpoint of water stain suppression and heat resistance. It preferably contains an alkali-soluble resin (A1). We presume that the alicyclic hydrocarbon structure, which is highly hydrophobic and has both flexibility and rigidity, has low affinity with the developer and can form a tough film. And it is presumed that by having a polymerizable unsaturated group, a stronger cured film can be formed by cross-linking the resins by exposure, water staining can be suppressed, and a pattern with good heat resistance can be obtained.

The alkali-soluble resin (A1) is not particularly limited as long as it contains an alicyclic hydrocarbon-containing monomer unit (a1) and a polymerizable unsaturated group-containing monomer unit (a2). Resin can be used. For example, a copolymer of a monomer forming the alicyclic hydrocarbon-containing monomer unit (a1) and a monomer forming the polymerizable unsaturated group-containing monomer unit (a2), reacting a compound having a polymerizable unsaturated group with a copolymer of a monomer forming the cyclic hydrocarbon-containing monomer unit (a1) and another monomer copolymerizable therewith; A copolymer into which a polymerizable unsaturated group-containing monomer unit (a2) is introduced, a copolymer obtained by the method described in JP-A-2008-165059, and the like can be mentioned. The polymerizable unsaturated group-containing monomer unit (a2) is a unit containing a polymerizable unsaturated group. Moreover, the alkali-soluble group may be present at any site of the resin (A1).

[Alicyclic hydrocarbon-containing monomer unit (a1)]
Monomers forming the alicyclic hydrocarbon-containing monomer unit (a1) include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth) Acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate and the like. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferable from the viewpoint of water stain suppression and pattern shape.

The content of the alicyclic hydrocarbon-containing monomer unit (a1) is preferably 1 to 60 mol% of the total structural units of the alkali-soluble resin (A1) from the viewpoint of water stain suppression and pattern shape. ~40 mol% is more preferred.

[Polymerizable unsaturated group-containing monomer unit (a2)]
Methods for incorporating the polymerizable unsaturated group-containing monomer unit (a2) into the alkali-soluble resin (A1) include, for example, the following methods (i) to (iii).

<Method (i)>
In method (i), for example, first, a polymer (precursor) of an epoxy group-containing monomer and other monomers is synthesized. Next, a carboxyl group-containing monomer (modified compound) is added to the epoxy group of the precursor.

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

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, the product obtained by adding the carboxyl group of the carboxyl group-containing monomer to the epoxy group of the epoxy group-containing monomer unit and the product obtained by further reacting the acid anhydride are also polymerizable non-polymerizable products. It is preferable as the saturated group-containing monomeric unit (a2).

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

<Method (ii)>
Method (ii), for example, first synthesizes a polymer (precursor) of a carboxyl group-containing monomer and other monomers. Then, by adding an epoxy group-containing monomer (modified compound) to part of the carboxyl groups of the precursor, it is possible to have carboxyl groups and polymerizable unsaturated groups.

<Method (iii)>
Method (iii), for example, first synthesizes a polymer (precursor) of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Next, the hydroxyl group of the precursor is reacted with the isocyanate group of the isocyanate group-containing monomer (modified compound).

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 or 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.

The content of the polymerizable unsaturated group-containing monomer unit (a2) is preferably 5 to 80 mol%, more preferably 10 to 80 mol% of the total constituent units of the alkali-soluble resin (A1) from the viewpoint of the pattern shape. more preferred.

[Monomer unit (a3) whose homopolymer has a glass transition temperature of 0° C. or lower]
From the viewpoint of the pattern shape, the alkali-soluble resin (A1) contains a monomer unit (a3) (excluding (a1) and (a2)) whose homopolymer glass transition temperature is 0° C. or lower. is preferred. More preferably, the monomeric unit (a3) is a homopolymer having a glass transition temperature of −10° C. or lower, and particularly preferably the monomeric unit (a3) is a homopolymer having a glass transition temperature of −30° C. or lower. ). The homopolymer means a homopolymer of each monomer, and the value of the glass transition temperature is according to Brandrup, J.; Immergut, E.; H. The values given in the ed. "Polymer Handbook, Third edition, John wiley & sons, 1989" are used.

Monomers forming the monomer unit (a3) whose homopolymer has a glass transition temperature of 0°C or lower include, for example, phenoxyethyl acrylate (-22°C), lauryl acrylate (-3°C), and 2-ethylhexyl acrylate. (-50°C), n-hexyl acrylate (-57°C), n-butyl acrylate (-48°C), isobutyl acrylate (-40°C), ethyl acrylate (-24°C), lauryl methacrylate (-65°C), n-hexyl methacrylate (-5°C), 2-ethylhexyl methacrylate (-10°C), 2-methoxyethyl acrylate (-50°C), tetrahydrofurfuryl acrylate (-12°C) and the like. Among these, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred.

The content of the monomer unit (a3) whose homopolymer has a glass transition temperature of 0° C. or lower is preferably 1 to 50 mol % of the total structural units of the alkali-soluble resin (A1) from the viewpoint of the pattern shape. 5 to 40 mol % is more preferred.

[Other monomer units (a4)]
The alkali-soluble resin (A1) can contain monomer units other than (a1) to (a3) (hereinafter also referred to as other monomer units (a4)).

Other monomers forming the monomer unit (a4) include, for example, methyl (meth)acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, benzyl (meth) (meth)acrylates such as acrylates;
hydroxy group-containing (meth)acrylates such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl methacrylate, glycerin monomethacrylate;
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;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4 '-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N -(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl -2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6- N-substituted maleimides such as maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(Meth)acryloyloxyethyl acid phosphate, a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid, etc. containing a phosphoric acid ester group (meth) acrylates and the like;
Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'- [oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene) )] and bis-2-propenoate. These monomers can be used alone or in combination of two or more.

Alkali-soluble resin (A1) can be used alone or in combination of two or more.

The content of the alkali-soluble resin (A1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on 100% by mass of the alkali-soluble resin (A) from the viewpoints of water stain suppression and pattern shape.

(Alkali-soluble resin (A2))
The photosensitive composition of the present invention can contain an alkali-soluble resin (hereinafter also referred to as alkali-soluble resin (A2)) other than the alkali-soluble resin (A1) as the alkali-soluble resin (A).

The photosensitive composition of the invention contains a polymerizable compound (B).

The polymerizable compound (B) includes monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group having an ethylenically unsaturated double bond, a (meth)allyl group, and a (meth)acryloyl group. The weight average molecular weight or formula weight of the polymerizable compound (B) is preferably less than 2000.

(Lactone-modified polymerizable compound (B1))
The polymerizable compound (B) preferably contains a lactone-modified polymerizable compound (B1) from the viewpoint of suppressing water stains.

The lactone-modified polymerizable compound (B1) is a compound having a lactone-modified structure in its molecule. The lactone-modified polymerizable compound (B1) is a polyvalent compound such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, or trimetrolmelamine. It is obtained by esterifying alcohol with (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound (B1) is preferably a compound represented by the following general formula (14).

general formula (14)

In general formula (14), all six R are groups represented by the following general formula (15), or 1 to 5 of the six R are groups represented by the following general formula (15) , and the rest are groups represented by the following general formula (16).

general formula (15)

In general formula (15), R ¹ represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond that bonds to the oxygen atom in general formula (14).

general formula (16)

In general formula (16), R ¹ represents a hydrogen atom or a methyl group, and * is a bond that bonds with the oxygen atom in general formula (14).

The lactone-modified polymerizable compound (B1) is commercially available, for example, as KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. For example, DPCA-20 (in the above general formulas (14) to (16), m = 1, the number of groups represented by general formula (15) = 2, R ¹ are all hydrogen atoms), DPCA- 30 (a compound in which m = 1, the number of groups represented by the general formula (15) = 3, and all R ¹ are hydrogen atoms in the above general formulas (14) to (16)), DPCA-60 (the above general In formulas (14) to (16), m = 1, the number of groups represented by general formula (15) = 6, and R ¹ are all hydrogen atoms), DPCA-120 (the above general formula (14) to (16), m=2, the number of groups represented by the general formula (15)=6, and all R ¹ are hydrogen atoms).

In the lactone-modified polymerizable compound (B1), in the general formulas (14) to (16), m = 1 and the number of groups represented by the general formula (15) = 2 from the viewpoint of suppressing water stains. ~ 6, compounds in which all R ¹ are hydrogen atoms are preferred, and in the above general formulas (14) to (16), m = 1, the number of groups represented by general formula (15) = 2 or 3, R ¹ are all hydrogen atoms are more preferred.

The lactone-modified polymerizable compound (B1) can be used alone or in combination of two or more.

The content of the lactone-modified polymerizable compound (B1) is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, based on 100% by mass of the polymerizable compound (B), from the viewpoint of suppressing water stains. .

(Polymerizable compound (B2) having an acid group)
From the viewpoint of pattern shape, the polymerizable compound (B) preferably contains a polymerizable compound (B2) having an acid group. Examples of the acid group of the polymerizable compound (B2) having an acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, a carboxyl group is preferred.

The polymerizable compound (B2) having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; Examples thereof include esterified products with hydroxyalkyl (meth)acrylates.
Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, and itaconic phthalate.
Examples of polyvalent carboxylic acids include trimellitic acid and pyromellitic acid.
Monohydroxyalkyl (meth)acrylates, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and the like.

Commercial products of the polymerizable compound (B2) having an acid group include Viscoat #2500P manufactured by Osaka Organic Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, M manufactured by Toagosei Co., Ltd. -521 and the like.

The polymerizable compound (B2) having an acid group can be used alone or in combination of two or more.

The content of the polymerizable compound (B2) having an acid group is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, based on 100% by mass of the polymerizable compound (B) from the viewpoint of pattern shape.

(Other polymerizable compounds (B3))
The photosensitive composition of the present invention includes, as the polymerizable compound (B), a lactone-modified polymerizable compound (B1), a polymerizable compound other than the polymerizable compound (B2) having an acid group (hereinafter referred to as other polymerizable compound (also referred to as B3)).

Other polymerizable compounds (B3) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxy Ethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, phenoxytetraethyleneglycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate Acrylates, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth) Acrylates, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth) Various acrylates and methacrylates such as acrylates, methylolated melamine (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta Erythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

Commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303 manufactured by Nippon Kayaku Co., Ltd. TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, Toagosei Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M- 452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Co., Ltd., Kyoeisha Chemical Co., Ltd. AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Shin-Nakamura Chemical Co., Ltd. NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, UA-160TM, Miwon Specialty Chemical Co. , Ltd. Miramer HR6060, 6100, 6200; Daicel Ornex EBECRYL40, 130, 140, 145; Osaka Gas Chemicals OGSOL EA-0200, 0300;

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

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

[Sensitizer (D)]
From the viewpoint of pattern shape, the photosensitive composition of the present invention preferably contains a sensitizer (D).

Sensitizers (D) 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, tetraphyllin-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 (D1) or the benzophenone-based compound (D2) is preferable, and the thioxanthone-based compound (D1) is more preferable, from the viewpoint of the pattern shape.

(Thioxanthone-based compound (D1))
Thioxanthone compounds (D1) 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 (D2))
Benzophenone compounds (D2) 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.

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

From the viewpoint of the pattern shape, the content of the sensitizer (D) is preferably 5 to 100 parts by mass, and 10 to 80 parts by mass with respect to 100 parts by mass of the compound (C1) represented by the general formula (1). is more preferred, and 15 to 60 parts by mass is particularly preferred.

The photosensitive composition of the invention can contain a colorant (E).

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

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

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

Yellow pigments include, for example, C.I. I. Pigment Yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in JP-A-2012-226110. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A-2012-226110 are preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

The salt milling process involves 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.

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

The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt, and is a solvent that 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 (F)]
The photosensitive composition of the present invention can contain a dye derivative (F).

A dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. The dye derivative (F) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxyl group, or a phosphoric acid group; and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

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

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

The content of the dye derivative (F) is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the colorant (E).

[Dispersion resin (G)]
The photosensitive composition of the present invention can contain a dispersing resin (G). The dispersing resin (G) is a resin used for dispersing the colorant (E).

The dispersing resin (G) is preferably a resin having an adsorptive group that has a high affinity for the colorant (E). The adsorptive group preferably has one or more of a basic group and an acidic group, and preferably has an acidic group from the viewpoint of developability.

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. Among these, a carboxyl group and a phosphoric acid group are preferable from the viewpoint of adsorption to pigments and developability.

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

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

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

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

From the viewpoint of dispersion stability, the content of the dispersing resin (G) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the colorant (E).

[Thermosetting compound (H)]
From the viewpoint of heat resistance, the photosensitive composition of the present invention preferably contains a thermosetting compound (H). As a result, the thermosetting compound (H) reacts in the heating step, increasing the crosslink density and improving the heat resistance.

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

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

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

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

(Oxetane compound (H2))
The oxetane compound (H2) is a known compound having an oxetane group. Oxetane compounds include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Monofunctional oxetane compounds include, for example, (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy silyl)propoxy]methyl}oxetane and the like.

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

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

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

Trifunctional or higher oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups ( For example, oxetane-modified phenolic novolak resins described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30 can be mentioned.

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

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

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

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

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

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

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

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).

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

The thiol-based chain transfer agent (I) 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.

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

The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of nonvolatile 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 (J)]
The photosensitive composition of the present invention can contain a polymerization inhibitor (J).

Polymerization inhibitor (J) 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 phosphine 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 (J) is preferably 0.01 to 0.4% by mass based on 100% by mass of non-volatile matter in the photosensitive composition.

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

The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

Benzotriazole compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H -benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1,1,3, 3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H- benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl -2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy- 5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl ) phenyl]propionate.

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

Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 2,4-bis'2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- and tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, Adekastab LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV- manufactured by Sun Chemical Co., Ltd. 1164 and the like.

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

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

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

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

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

The antioxidant (L) prevents the photopolymerization initiator (C) and the thermosetting compound (H) contained in the photosensitive composition from yellowing due to oxidation during the thermal process during thermal curing and ITO annealing. . In particular, when the colorant (E) concentration of the photosensitive composition is high, the content of the polymerizable compound (B) is relatively decreased, so the amount of the photopolymerization initiator (C) may be increased, or the thermosetting compound ( If H) is used, the cured film tends to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

Antioxidants (L) include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound containing no halogen atom.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

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

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

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

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

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

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

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

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

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

The content of antioxidant (L) 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 (M)]
The photosensitive composition of the invention can contain a leveling agent (M). This further improves the wettability and dryability of the substrate during coating.

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

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition. Within this range, the balance between the applicability and adhesion of the photosensitive composition is further improved.

[Storage stabilizer (N)]
The photosensitive composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive composition over time.

Storage stabilizers (N) 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.

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

The content of the storage stabilizer (N) is preferably 0.1 to 10% by mass based on 100% by mass of non-volatile matter in the photosensitive composition.

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

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

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

The content of the adhesion improver (O) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of non-volatile matter in the photosensitive composition.

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

Organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-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 (P) can be used alone or in combination of two or more.

[Method for producing photosensitive composition]
For the photosensitive composition of the present invention, for example, a coloring agent (E), a dispersing resin (G), a dye derivative (F), an organic solvent (P), etc. are blended and subjected to dispersion treatment to produce a dispersion. do. After that, the dispersion can be produced by blending and mixing the alkali-soluble resin (A), the polymerizable compound (B), the photopolymerization initiator (C), and the like. The materials to be blended and the timing of blending them are arbitrary. Moreover, a dispersion|distribution process can also be performed in multiple times.

Examples of the dispersing machine for the dispersion 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 colorant 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.

<Optical filter>
The optical filter of the present invention comprises a substrate and filter segments formed from the photosensitive composition of the present invention. Optical filters can be used in a variety of applications. The optical filters used herein are preferably color filters.
In the case of a color filter, the filter segment has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of coloring agent (E) used. Instead of or in addition to the filter segments, it is also possible to have a magenta filter segment, a cyan filter segment, a yellow filter segment, a white filter segment, a gray filter segment, and a black filter segment. It can also have a clear filter.
Examples of the substrate include a transparent substrate and a reflective substrate. As for the said transparent substrate, a glass substrate is mentioned, for example. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[Method for producing an optical filter]
The method for producing an optical filter includes, for example, a step (1) of applying a photosensitive composition on a substrate to form a layer (coating) of the composition, and a step (2) of patternwise exposing the layer through a mask. ), the step (3) of alkali-developing the unexposed portion to form a patterned cured film, and the step (4) of heat-treating (post-baking) the pattern.

A method for manufacturing an optical filter 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 120° 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 layer thickness 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 developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11-13, more preferably 11.5-12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed, and the residual film rate after development can be improved.

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

(Step (4))
In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature for post-baking is preferably 100 to 300.degree. C., more preferably 150 to 250.degree. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

<Image display device>
An image display device of the present invention includes the optical filter of the present invention. Examples of image display devices include liquid crystal displays and organic EL displays.
The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, there is a configuration described in "Next Generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Industrial Research Institute, 1994).
For the definition of the image display device and the details of each image display device, see, for example, "Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

<Solid-state image sensor>
A solid-state imaging device of the present invention includes the optical filter of the present invention.
The form used for the solid-state imaging device is not particularly limited. It has an electrode, has a light-shielding film on the photodiode and the transfer electrode with only the light-receiving portion of the photodiode opened, and is made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. It has a device protective film and a filter on the device protective film. Furthermore, there is a configuration in which a condensing means (for example, a microlens, etc.; the same shall apply hereinafter) is provided on the device protective film and below the filter (on the side close to the substrate), or a configuration in which the condensing means is provided on the filter. may Further, the filter may have a structure in which a cured film forming each color pixel is embedded in spaces partitioned, for example, in a grid pattern by partition walls. The partition wall in this case preferably has a low refractive index for each color pixel.
Imaging devices equipped with the solid-state imaging device of the present invention can be used in various applications such as, for example, digital cameras, electronic devices having imaging functions (mobile phones, smart phones, etc.), vehicle-mounted cameras, surveillance cameras, and the like.

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

Prior to Examples, each measuring method will be described.
The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g) and amine value (mgKOH/g) of the resin are 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. The average molecular weight is a polystyrene equivalent 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 colorant (E)>
(Refined red pigment (E-1))
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 finely divided red pigment (E-1).

(Refined red pigment (E-2))
C. I. Pigment Red 177 (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 finely divided red pigment (E-2).

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

(Micronized purple pigment (E-4))
C. I. Pigment Violet 23 (100 parts), sodium chloride (1,200 parts) and diethylene glycol (100 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product was put into 8,000 parts of hot water, stirred for 2 hours with a high-speed mixer while heating to 80° C. to form a slurry, and repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After that, it was dried at 85° C. for 24 hours and pulverized to obtain a finely divided purple pigment (E-4).

(Micronized green pigment (E-5))
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 finely divided green pigment (E-5) was obtained by drying and pulverizing.

(Micronized green pigment (E-6)
A green pigment (E-6) of the following chemical formula (17) was obtained according to the example of JP-A-2017-111398. 100 parts of green pigment (E-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 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 finely divided green pigment (E-6) was obtained by drying and pulverizing.
chemical formula (17)

(Micronized yellow pigment (E-7))
C. I. Pigment Yellow 150 (100 parts), sodium chloride (700 parts) and diethylene glycol (180 parts) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. This mixture is poured into 2,000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 80°C to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80°C for a day and night. A finely divided yellow pigment (E-7) was obtained by drying and pulverizing.

(Micronized yellow pigment (E-8))
C. I. Pigment Yellow 139 (“Novoperm Yellow P-M3R” manufactured by Clariant) 100 parts, pulverized 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 yellow pigment (E-8) was obtained by drying and pulverizing.

(Micronized yellow pigment (E-9))
C. I. 100 parts of Pigment Yellow 185 (“Palitol Yellow D1155” manufactured by BASF Japan), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, this kneaded product is put into 8 liters of hot water, stirred with a high-speed mixer for 2 hours while heating to 80°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then heated to 85°C. The mixture was dried overnight at room temperature and pulverized to obtain a finely divided yellow pigment (E-9).

(Micronized yellow pigment (E-10)
A yellow pigment (E-10) of the following chemical formula (18) was obtained according to the example of JP-A-2012-226110. 100 parts of yellow pigment (E-10), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product is put into 8 liters of hot water, stirred with a high-speed mixer for 2 hours while heating to 80°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then heated to 85°C. The mixture was dried overnight and pulverized to obtain a finely divided yellow pigment (E-10).
chemical formula (18)

The average primary particle size of the finely divided pigment was in the range of 5 to 120 nm.

(Dye (E-11))
The C.I. I. A dye (E-11), which is a salt forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile ) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the non-volatile matter and the weight average molecular weight (Mw) was 6,830, and the mixture was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in a side chain containing 47% by mass of ammonium group as a resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.
Next, to 2,000 parts of water, 30 parts of Resin 1 having a cationic group on a side chain was added in terms of non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 52, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer. I. A dye (E-11), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. I. The content of components derived from Acid Red 52 was 25% by mass.

<Production of alkali-soluble resin (A)>
(Alkali-soluble resin (A1-1) 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. ℃, and at the same temperature from the dropping tube 49.7 parts of 2-ethylhexyl acrylate (hereinafter, 2-EHA), glycidyl methacrylate (hereinafter, GMA) 99.4 parts, dicyclopentanyl methacrylate (hereinafter, DCPMA) A mixture of 6.6 parts, 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise over 2.5 hours.
After the dropwise addition was completed, the mixture was further stirred at 120° C. for 2 hours to obtain a precursor. Then, the inside of the flask was replaced with air, and 50.4 parts of acrylic acid (hereinafter referred to as AA) as a modified compound, and 0.6 parts of triphenylphosphine and 0.2 parts of methylhydroquinone as catalysts were added. It was made to react for 10 hours. As a result, a monomer unit (hereinafter referred to as GMA+AA) was obtained by reacting the epoxy group of GMA with the carboxyl group of AA, and a polymerizable unsaturated group-containing monomer unit (a2) was introduced.
Then, 21.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) was added as a modifying compound and reacted at 110° C. for 4 hours. This caused a portion of the hydroxyl groups of GMA+AA to react with THPA. After that, PGMAc is added so that the nonvolatile content is 20% by mass, and the alicyclic hydrocarbon-containing monomer unit (a1), the polymerizable unsaturated group-containing monomer unit (a2), and the homopolymer An alkali-soluble resin (A1-1) solution containing monomer units (a3) having a glass transition temperature of 0° C. or less was prepared. The alkali-soluble resin (A1-1) had an acid value of 38 mgKOH/g and a weight average molecular weight of 12,000.

(Alkali-soluble resin (A1-2) to (A1-6) solution)
Alkali-soluble resins (A1-2) to (A1-6) were synthesized in the same manner as the alkali-soluble resin (A1-1) by changing the compounding type and amount so that the composition ratio shown in Table 1 was obtained. , and PGMAc were added to adjust the non-volatile content to 20% by mass.

MAA+GMA described in Table 1 represents a polymerizable unsaturated group-containing monomer unit (a2) obtained by adding the epoxy group of GMA to the carboxyl group of methacrylic acid (hereinafter referred to as MAA) in the precursor. GMA+AA+SHA represents a polymerizable unsaturated group-containing monomer unit (a2) obtained by reacting part of the hydroxyl groups of GMA+AA with succinic anhydride (hereinafter referred to as SHA).

(Alkali-soluble resin (A2-1) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 25.1 parts of benzyl methacrylate, 23.0 parts of n-butyl methacrylate, 14.3 parts of 2-hydroxyethyl methacrylate, 13.4 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110") 24.1 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content, and PGMAc is added to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Then, an alkali-soluble resin (A2-1) solution was prepared. It had an acid value of 87 mgKOH/g and a weight average molecular weight of 25,000.

(Alkali-soluble resin (A2-2) and (A2-3) solution)
Alkali-soluble resins (A2-2) and (A2-3) were synthesized by changing the compounding type and amount so that the composition ratio shown in Table 2 was obtained, and PGMAc was added to make the non-volatile content 20% by mass. .

<Production of polymerizable compound (B)>
(Polymerizable compound having an acid group (B2-2))
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 a polymerizable compound (B2-2) having an acid group.

<Production of dispersion resin (G)>
(Dispersion resin (G-1) 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. , and a dispersion resin (G-1) solution having a weight average molecular weight of 8,500 was obtained.

(Dispersion resin (G-2) solution)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer. After substitution, reaction was carried out at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Parts, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80° C., 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a diluted PGMAc solution with a non-volatile content of 50% of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the isocyanate was measured by IR. The reaction was carried out until the disappearance of the 2270 cm ^-1 peak based on the group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (G-2) solution with a non-volatile content of 30%. The resulting dispersion resin (G-2) had an acid value of 68 mgKOH/g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Dispersion resin (G-3) 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 dispersion resin (G-3) solution having an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn). .

(Dispersion resin (G-4) solution)
250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketenemethyltrimethylsilyl acetal as an initiator were placed in a 500 mL four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a stirrer, and a digital thermometer. was added through the addition funnel, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate as a block monomer having solvent affinity. , 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added for 60 minutes using an addition funnel. dripped over. The temperature was kept below 40° C. by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to terminate the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered and vacuum dried for purification.
Subsequently, 15.0 parts by mass of the resulting block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottomed flask, and 1.1 parts by mass of phenylphosphinic acid (dimethylaminopropyl methacrylamide), which is a salt-forming component, was dissolved. 0.5 molar equivalent) was added, stirred at a reaction temperature of 30° C. for 20 hours, and adjusted by adding PGMAc to obtain a dispersion resin (G-4) solution having a nonvolatile content of 30%.

<Production of dispersion>
(Dispersion 1)
Using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), it was filtered through a filter with a pore size of 1.0 μm. Dispersion 1 was produced. Organic solvent (P-1) is PGMAc.
Micronized blue pigment (E-3): 9.05 parts by mass Micronized purple pigment (E-4): 0.31 parts by mass Dye (E-11): 4.16 parts by mass Dye derivative (F-1 ): 1.04 parts by mass Dispersion resin (G-1) solution: 3.47 parts by mass Alkali-soluble resin (A2-1) solution: 10.0 parts by mass Organic solvent (P-1): 71.97 parts by mass

ｐｃは、フタロシアニン骨格を表す。 Dye derivative (F-1): the following structure

pc represents a phthalocyanine skeleton.

Dispersions 2 to 9 were prepared in the same manner as Dispersion 1 except that the raw materials and amounts shown in Table 3 were changed.

Dye derivative (F-2) in Table 3: the following structure

Dye derivative (F-3) in Table 3: the following structure

<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: 28.85 parts by mass Alkali-soluble resin (A1-2) solution: 9.0 parts by mass Polymerizable compound (B1-1): 5.0 parts by mass Polymerizable compound (B2-1): 1.2 Parts by weight Compound represented by general formula (1) (C1-1): 0.70 parts by weight Oxime-based photopolymerization initiator (C2b-1): 0.50 parts by weight Sensitizer (D1-1): 0 .30 parts by mass Thermosetting compound (H1-1): 0.30 parts by mass Polymerization inhibitor (J): 0.01 parts by mass Leveling agent (M): 1.00 parts by mass Organic solvent (P): 53. 14 parts by mass

[Examples 2 to 35, Comparative Examples 1 to 3]
(Photosensitive compositions 2 to 38)
Photosensitive compositions 2 to 38 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 (B)]
(Lactone-modified polymerizable compound (B1))
B1-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)
B1-2: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)

(Polymerizable compound (B2) having an acid group)
B2-1: Aronix M-520 (manufactured by Toagosei Co., Ltd.)

(Other polymerizable compound (B3))
B3-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[Photoinitiator (C)]
(Compound (C1) represented by general formula (1))
C1-1: compound of chemical formula (2) above C1-2: compound of chemical formula (3) above C1-3: compound of chemical formula (4) above

(Oxime-based photopolymerization initiator (C2))
C2a-1: TRONLY TR-PBG-3057 (manufactured by Changzhou Tenryu New Materials Co., Ltd., a compound containing one oxime group in one molecule)
C2a-2: compound of chemical formula (5) above C2a-3: compound of chemical formula (6) above C2a-4: compound of chemical formula (7) above C2a-5: compound of chemical formula (8) above C2b- 1: the compound of the above chemical formula (10) C2b-2: the compound of the above chemical formula (13)

(Other photopolymerization initiators (C3))
C3-1: Omnirad 907 (manufactured by IGM Resins, acetophenone-based compound)
C3-2: Omnirad 369 (manufactured by IGM Resins, acetophenone-based compound)

[Sensitizer (D)]
(Thioxanthone-based compound (D1))
D1-1: 2,4-diethylthioxanthone (benzophenone compound (D2))
D2-1: 4,4'-bis(diethylamino)benzophenone

[Thermosetting compound (H)]
(Epoxy compound (H1))
H1-1: EHPE-3150 (manufactured by Daicel)

[Polymerization inhibitor (J)]
J-1: 4-methylcatechol J-2: methylhydroquinone J-3: t-butylhydroquinone Above, (J-1) to (J-3) are mixed in the same amount, respectively, polymerization inhibitor (J) and

[Leveling agent (M)]
M-1: BYK-330 (manufactured by BYK-Chemie)
M-2: Megafac F-551 (manufactured by DIC)
1 part each of (M-1) and (M-2) were 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 obtained photosensitive compositions 1 to 38 (Examples 1 to 35, Comparative Examples 1 to 3) were evaluated for water spots, pattern shape (adhesion, cross-sectional shape), and heat resistance by the following methods. . Table 5 shows the evaluation results.

[Water stain evaluation]
The obtained photosensitive composition was coated on a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning) by spin coating so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, it was exposed to ultraviolet light under the conditions of illuminance of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp through a mask having a stripe pattern of 100 μm width. Then, it was developed by being immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 40 seconds, and then washed with pure water. The surface of the obtained pattern was observed using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon, and the degree of discoloration was evaluated. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: There was no water stain.
4: Water stains were less than 10% of the whole.
3: Water stains were 10% or more and less than 20% of the whole.
2: Water stains were 20% or more and less than 30% of the whole.
1: Water stains were 30% or more of the whole.

[Pattern shape evaluation (1): adhesion]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to light at an intensity of 30 mW/cm ² and 50 mJ/cm ² using a high-pressure mercury lamp through a photomask having a stripe pattern with a width of 5 to 25 μm in increments of 5 μm. Thereafter, the substrate was developed by spraying with an aqueous developer containing 0.12% by mass of nonionic surfactant and 0.04% by mass of potassium hydroxide at 23° C., washed with deionized water, and air-dried. , in a clean oven at 230° C. for 30 minutes. Spray development was carried out for the shortest possible time for pattern formation without development residue for each photosensitive composition film.
The obtained patterns with widths of 5, 10, 15, 20 and 25 μm on the substrate were observed with an optical microscope to confirm the minimum line width of the remaining patterns. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Fine lines of 10 μm or less remain.
4: Fine lines of 15 μm or more remain.
3: Fine lines of 20 μm or more remain.
2: Fine lines of 25 μm remain.
1: Fine lines do not remain.

[Pattern shape evaluation (2): cross-sectional shape]
The resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long, 100 mm wide and 0.7 mm thick by a spin coating method so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to light at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² through a photomask having a stripe pattern of 100 μm width using a high-pressure mercury lamp. Thereafter, the substrate was developed by spraying with an aqueous developer containing 0.12% by mass of nonionic surfactant and 0.04% by mass of potassium hydroxide at 23° C., washed with deionized water, and air-dried. , in a clean oven at 230° C. for 30 minutes. Spray development was carried out for the shortest possible time for pattern formation without development residue for each photosensitive composition film.
The cross-sectional shape of the pattern was confirmed using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Tech Co., Ltd.). For the evaluation, a cross-sectional SEM image of a striped pattern with a width of 100 μm was captured, and the cross-sectional shape was evaluated by measuring the taper angle between the substrate and the end of the cross-section of the pattern. The evaluation criteria are as follows, and 3 or more is regarded as practical.
5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle of 70 degrees or more and less than 90 degrees 1: Taper angle of 90 degrees that's all

[Heat resistance evaluation]
The obtained photosensitive composition was coated on a 0.7 mm glass substrate (Eagle 2000 manufactured by Corning) by spin coating so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, it was exposed using a high-pressure mercury lamp at an illumination intensity of 30 mW/cm ² and 50 mJ/cm ² . After that, it was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C for 40 seconds, then washed with deionized water, air-dried, and cleaned. Heated in an oven at 230° C. for 30 minutes.
Chromaticity ([L * (1), a * (1), b * (1)]) of the resulting coating film at C light source is measured with a microscopic spectrophotometer (manufactured by Olympus Optical Co., Ltd. "OSP-SP100"). was measured using After that, heat resistance was evaluated by heating at 230 ° C. for 1 hour, measuring chromaticity ([L * (2), a * (2), b * (2)]) with C light source, and using the following formula , the color difference ΔEab* was determined. The evaluation criteria are as follows, and 3 or more is regarded as practical.
ΔEab*=((L*(2)-L*(1)) ² +(a*(2)-a*(1)) ² +(b*(2)-b*(1)) ² ) ^{1 /2}
5: ΔEab* is less than 1 4: ΔEab* is 1 to 2
3: ΔEab* is 2 to 3
2: ΔEab* is 3 to 5
1: ΔEab* is 5 or more

Claims (8)

A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C),
A photosensitive composition, wherein the photopolymerization initiator (C) comprises a compound (C1) represented by the following general formula (1) and an oxime photopolymerization initiator (C2).
General formula (1)

(In general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom or a monovalent substituent. show.) 2. The photosensitive composition according to claim 1, wherein the oxime-based photopolymerization initiator (C2) contains a compound (C2b) containing two oxime groups in one molecule. The alkali-soluble resin (A) comprises an alkali-soluble resin (A1) containing an alicyclic hydrocarbon-containing monomer unit (a1) and a polymerizable unsaturated group-containing monomer unit (a2). Item 3. The photosensitive composition according to Item 1 or 2. The photosensitive resin composition according to claim 3, wherein the alkali-soluble resin (A1) is a resin containing a monomer unit (a3) whose homopolymer glass transition temperature is 0°C or lower. The photosensitive composition according to any one of claims 1 to 4, further comprising a sensitizer (D). An optical filter comprising a substrate and a filter segment formed from the photosensitive composition according to any one of claims 1 to 5. An image display device comprising the optical filter according to claim 6 . A solid-state imaging device comprising the optical filter according to claim 6 .