CN115700411A

CN115700411A - Photosensitive composition, optical filter, image display device, and solid-state imaging element

Info

Publication number: CN115700411A
Application number: CN202210796311.8A
Authority: CN
Inventors: 新戸翔; 小野寺由宇; 吉田寛之
Original assignee: Dongyang Yihuan Co ltd; Toyo Ink SC Holdings Co Ltd
Current assignee: Dongyang Yihuan Co ltd; Artience Co Ltd
Priority date: 2021-07-14
Filing date: 2022-07-07
Publication date: 2023-02-07
Also published as: JP2023012949A; TW202302659A

Abstract

The invention aims to provide a photosensitive composition, an optical filter, an image display device and a solid-state imaging element, which can inhibit water stain of a coating film after development, have good heat resistance and can form excellent patterns. The problem can be solved by a photosensitive composition containing an alkali-soluble resinThe photosensitive composition comprises (A) a polymerizable compound (B) and a photopolymerization initiator (C), wherein the photopolymerization initiator (C) comprises a compound (C1) represented by the following general formula (1) and an oxime photopolymerization initiator (C2). (in the general formula (1), R ₁ 、R ₂ Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₃ Represents a hydrogen atom or a monovalent substituent. ) General formula (1) [ formula 1]]

Description

Photosensitive composition, optical filter, image display device, and solid-state imaging element

Technical Field

The invention relates to a photosensitive composition, an optical filter, an image display device and a solid-state imaging element.

Background

A color filter, which is one of filters used in an image display device, a solid-state imaging element, or the like, obtains a filter pattern of a first color by, for example, the following steps: a step of applying a photosensitive composition to a transparent substrate such as glass and drying the composition to remove a solvent from the coating film; a step of irradiating the coating film with radiation through a photomask having a desired pattern shape to cure the coating film (hereinafter, referred to as exposure); subsequently, a step of cleaning and removing (hereinafter referred to as development) an unexposed portion of the coating film; thereafter, a heat treatment (hereinafter, referred to as a post-baking) step is performed as necessary to sufficiently cure the cured film. Further, by performing the same operation, filter patterns of other colors can be formed and manufactured.

In the developing step, an alkaline developer is used as the developer, and the unexposed portion is cleaned and removed. At this time, there is a problem that the exposed portion is missing or peeled off, so that a pattern shape is defective. In addition, there is a problem that when the coating film is exposed to an alkaline developer, a phenomenon of discoloration of the coating film (hereinafter referred to as water stain) occurs. Therefore, a photosensitive composition which does not cause defects in pattern shape and water stains in a developing process is required. Further, there is a problem that the color changes in the post-baking step.

In addition, as a measure for improving water stain, 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 a measure for improving the pattern defect at the time of development, patent document 3 discloses a coloring composition containing a polymerizable compound having an alkylene oxide structure.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2017-173787

[ patent document 2] Japanese patent laid-open No. 2016-102212

[ patent document 3] Japanese patent laid-open No. 2014-142582

Disclosure of Invention

[ problems to be solved by the invention ]

However, any of the compositions described in patent documents 1 to 3 cannot satisfy all of water stains, pattern shapes, and heat resistance at a certain level or more.

The invention aims to provide a photosensitive composition which can inhibit water stain of a film after development, has good heat resistance and can form an excellent pattern.

[ means for solving problems ]

The invention relates to a photosensitive composition, which comprises an alkali-soluble resin (A), a polymerizable compound (B) and a photopolymerization initiator (C), wherein in the photosensitive composition,

the photopolymerization initiator (C) includes a compound (C1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (C2).

General formula (1)

[ solution 1]

(in the general formula (1), R ₁ 、R ₂ Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₃ Represents a hydrogen atom or a monovalent substituent. )

[ Effect of the invention ]

The present invention provides a photosensitive composition which suppresses water staining of a film after development, has good heat resistance, and can form an excellent pattern. The invention also provides an optical filter, an image display device, and a solid-state imaging element.

Detailed Description

The form of the photosensitive composition used for carrying out the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be modified and implemented within a range in which the problem can be solved.

In the present invention, "(meth) acryloyl group", "(meth) acrylic acid", "(meth) acrylate" or "(meth) acrylamide" means "acryloyl group and/or methacryloyl group", "acrylic group and/or methacrylic group", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively. Additionally, "c.i." means The color Index (color Index) (c.i.; issued by The Society of Dyers and colorrists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.

The molecular weight of the compound of the present invention is a value (formula weight) calculated by calculation or a molecular weight measured by electrospray ionization-mass spectrometry (ESI-MS) with respect to a low-molecular compound whose molecular weight can be determined, and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography with tetrahydrofuran as a solvent with respect to a compound having a molecular weight distribution.

The monomer is a compound that forms a resin by polymerization. The monomer is in an unreacted state, and the monomer unit is in a state in which the monomer is polymerized to form a resin. The polymerizable compound is a compound that forms a coating film by polymerization.

< photosensitive composition >

One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the invention comprises an alkali-soluble resin (A), a polymerizable compound (B) and a photopolymerization initiator (C),

General formula (1)

[ solution 2]

The mechanism by which the problem of the present invention can be solved in the photosensitive composition having the above-described structure is not clear, but is presumed to be as follows.

The compound (C1) represented by the general formula (1) has a fluorene skeleton which is hard and straight, and has high hydrophobicity and heat resistance, compared with 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one or 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, which is a photopolymerization initiator widely used in the field of color filters since now, it is presumed that a cured film having high resistance can be obtained. In addition, the hardened film has a moderate cohesive force by pi-pi interaction of two benzene rings. Therefore, it is presumed that the structure is likely to be softened appropriately to heat while suppressing pattern chipping and the like at the time of development, and that heat sagging occurs at the time of post-baking, and the cross-sectional shape of the pattern becomes good. Further, by using a specific oxime-based photopolymerization initiator (C2) having a different absorption wavelength from that of the compound (C1) represented by the general formula (1) and a high sensitivity in combination, the wavelength region of light used for photopolymerization is expanded, and the reactivity is improved. Therefore, it is presumed that, for example, in a composition containing a colorant which is difficult to transmit light to the deep portion of the film, the reaction proceeds, and water staining of the film after development is suppressed, thereby improving the pattern shape and heat resistance.

Hereinafter, components contained or capable of being contained in the photosensitive composition of one embodiment will be described in detail.

[ photopolymerization initiator (C) ]

The photosensitive composition of the present invention comprises a compound (C1) represented by general formula (1) and an oxime photopolymerization initiator (C2) as a photopolymerization initiator (C).

(Compound (C1) represented by the general formula (1))

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

General formula (1)

[ solution 3]

R ₁ 、R ₂ Each independently represents 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, or cyclic, or a group in which these groups are bonded, and examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl and the like. Among them, from the viewpoint of suppressing water staining and pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferable, and a linear alkyl group having 4 to 6 carbon atoms is more preferable.

R ₃ Represents a hydrogen atom or an arbitrary monovalent substituent.

As monovalent substituents, mention may be made of: alkyl groups having 1 to 20 carbon atoms such as methyl and ethyl; alkoxy groups having 1 to 20 carbon atoms such as methoxy and ethoxy; F. halogen atoms such as Cl, br, I, etc.; 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, an aromatic ring group having 4 to 20 carbon atoms; an amino group; an aminoalkyl group having 1 to 20 carbon atoms; a hydroxyl group; a nitro group; a cyano group; a benzoyl group which may have a substituent; a thenoyl group which may have a substituent, and the like. Examples of the substituent which a benzoyl group or a thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxycarbonyl group having 1 to 10 carbon atoms. Among them, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferable, and a hydrogen atom is more preferable.

Examples of the method for producing the compound (C1) represented by the general formula (1) include the methods described in, for example, japanese patent application laid-open No. 2019-507108 and Japanese patent application laid-open No. 2019-528331.

Specific examples of the compound (C1) represented by the general formula (1) are shown below. The present invention is not limited to these examples.

[ solution 4]

Chemical formula (4)

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

The compound (C1) represented by the general formula (1) may be used alone or in combination of two or more.

(Oxime photopolymerization initiator (C2))

The oxime-based photopolymerization initiator (C2) includes a compound (C2 a) having one oxime group in one molecule and a compound (C2 b) having two oxime groups in one molecule, and from the viewpoint of inhibiting water staining, a compound (C2 b) having two oxime groups in one molecule is more preferable.

[ Compound (C2 a) having an oxime group in one molecule ]

Examples of commercially available products of the compound (C2 a) having one oxime group in one molecule include: gorgeous good solid (IRGACURE) OXE-01, gorgeous good solid (IRGACURE) OXE-02, gorgeous good solid (IRGACURE) OXE-03, gorgeous good solid (IRGACURE) OXE-04, adeka Z (ADEKA arkks) N-1919, adeka Z (ADEKA arkks) NCI-730, adeka Z (ADEKA arkks) NCI-831, and Adeka Z (ADEKA arkks) NCI-930, all manufactured by BASF Corporation, strong (TRONLY) TR-PBG-301, strong (TRONLY) TR-PBG-304, strong (TRONLY) TR-PBG-305, strong (TRONLY) TR-PBG-309, strong (TRONLY) TR-PBG-314, strong (TRONLY) TR-PBG-358, strong (TRONLY) TR-PBG-380, strong (TRONLY) TR-PBG-365, strong (TRONLY) TR-PBG-610, strong (TRONLY) TR-PBG-3054, strong (TRONLY) TR-PBG-3057, ohmic Ni rad (OMNIRAD) 1312, ohmic Ni rad (OMNI) 1314, and ohmic Ni rad (OMNI) 1316 manufactured by IGM resins (IGMRins) Inc., SPI-02, SPI-03, SPI-04, SPI-06, SPI-07, manufactured by Sanyo Corporation, DFI-020, manufactured by Daito Chemix Corporation, manufactured by Daito Corporation, DFI-036, EOX-01, and the like.

Specific examples of the compound (C2 a) having one oxime group in one molecule include the following compounds. The present invention is not limited to these examples.

[ solution 5]

Chemical formula (5)

[ solution 6]

Chemical formula (8)

Examples of the method for producing the compounds of chemical formulae (5) to (8) include the methods described in, for example, japanese patent application laid-open No. 2004-534797, japanese patent application laid-open No. 2008-80068, japanese patent application laid-open No. 2012-526185, international publication No. 2015/036910, international publication No. 2015/152153, japanese patent application laid-open No. 2016-504270, and Japanese patent application laid-open No. 2017-512886.

From the viewpoint of pattern shape and heat resistance, the compound (C2 a) containing one oxime group in one molecule preferably contains one or more selected from the group consisting of compounds of chemical formulas (5) to (8).

The compound (C2 a) having one oxime group in one molecule may be used alone or in combination of two or more.

[ Compound (C2 b) having two oxime groups in one molecule ]

Examples of the compound (C2 b) having two oxime groups in one molecule include compounds described in, for example, japanese patent laid-open No. 2005-215378, japanese patent laid-open No. 2011-105713, japanese patent laid-open No. 2017-523465, and Japanese patent laid-open No. 2021-011486. Among them, a compound represented by the following general formula (9) is preferable.

General formula (9)

[ solution 7]

In the general formula (9), X ₁ And X ₂ Each independently represents a carbonyl bond (-CO-) or a single bond. X ₃ 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 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. R is 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, or an aryl group having 6 to 30 carbon atomsOr an arylalkyl group having 7 to 30 carbon atoms.

In the general formula (9), X ₁ And X ₂ Each independently represents a carbonyl bond (-CO-) or a single bond. Among them, X is preferable from the viewpoint of solubility in an organic solvent ₁ And X ₂ At least one of which is a carbonyl bond (-CO-), more preferably X ₁ And X ₂ Is a carbonyl bond (-CO-).

In the general formula (9), X ₃ Is a single bond or a sulfur atom, preferably a single bond.

In the 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 any of linear, branched, cyclic, or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. Examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl (amyl), isopentyl, pentyl (amyl), hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, and the like. Among these, ethyl, propyl and isopropyl are preferable.

In the general formula (9), R ₂ And R ₃ Each independently represents a hydrogen atom, 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.

The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, cyclic, or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl and the like. Among these, preferred are pentyl, hexyl, heptyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl groups.

Examples of the heterocyclic group having 2 to 30 carbon atoms include: pyridyl, pyrimidinyl, furanyl, tetrahydrofuryl, dioxolanyl, imidazolidinyl, oxazolidinyl, piperidinyl, morpholinyl, and the like.

Examples of the aryl group having 6 to 30 carbon atoms include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, and the like. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group or the like.

Examples of the arylalkyl group having 7 to 30 carbon atoms include: benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and the like. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, or the like.

Among these, R is R from the viewpoint of solubility in an organic solvent ₂ And R ₃ Preferably at least one linear alkyl group having 1 to 20 carbon atoms, and R is a group having a high solubility in an organic solvent and a low water stain ₂ And R ₃ More preferably, the alkyl group is a linear alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group having 1 to 20 carbon atoms.

In the general formula (9), 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.

The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, cyclic, or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. Examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, pentyl, hexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl and the like. Among these, methyl, ethyl, propyl, and isopropyl are preferable from the viewpoint of reactivity.

Examples of the heterocyclic group having 2 to 30 carbon atoms include: pyridyl, pyrimidinyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidinyl, oxazolidinyl, piperidyl, morpholinyl, and the like.

Examples of the aryl group having 6 to 30 carbon atoms include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, and the like. The aryl 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 reactivity, a phenyl group is preferable.

Among these, R is R from the viewpoint of reactivity ₄ And R ₅ Preferably methyl, ethyl or phenyl, more preferably methyl or ethyl.

The method for producing the compound represented by the general formula (9) is not particularly limited, and a known method can be used. For example, the methods described in Japanese patent application laid-open No. 2017-523465 and Japanese patent application laid-open No. 2021-011486 can be used.

Specific examples of the compound (C2 b) having two oxime groups in one molecule are shown below. The present invention is not limited to these examples.

[ solution 8]

Chemical formula (10)

Chemical formula (11)

[ solution 9]

Chemical formula (12)

Chemical formula (13)

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

The compound (C2 b) having two oxime groups in one molecule may be used alone or in combination of two or more.

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

from the viewpoints of water stain inhibition, pattern shape, and heat resistance, the total content of the compound (C1) represented by the general formula (1) and the oxime-based photopolymerization initiator (C2) is preferably 60 to 100% by mass, and more preferably 80 to 100% by mass, based on 100% by mass of the photopolymerization initiator (C).

(other photopolymerization initiator (C3))

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

The other photopolymerization initiator (C3) is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable compound (B) by light, and a known photopolymerization initiator can be used. Examples thereof include: acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-tert-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- (benzyl) -1-butanone, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone;

triazine compounds such as 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 (trichloromethyl) -6-styryl s-triazine, 2- (naphtho-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxy-naphtho-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine, or 2, 4-trichloromethyl- (4' -methoxystyryl) -6-triazine;

acylphosphine-based compounds such as bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide) and diphenyl-2, 4, 6-trimethylbenzoyl phosphine oxide;

quinone compounds such as 9, 10-phenanthrenequinone, camphorquinone and ethylanthraquinone; a borate ester compound; a carbazole-based compound; an imidazole-based compound; or titanocene-based compounds.

The other photopolymerization initiators (C3) may 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, and particularly preferably 5 to 30 parts by mass, with respect to 100 parts by mass of the polymerizable compound (B), from the viewpoint of photocurability.

[ alkali-soluble resin (A) ]

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

The alkali-soluble resin (a) may be a resin that is soluble in an alkali developing solution, and a known resin may be used. The alkali-soluble resin (a) preferably has an alkali-soluble group such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Of these, a carboxyl group is preferable.

Specifically, there may be mentioned: acrylic resins having an acidic group, α -olefin/maleic acid (anhydride) copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth) acrylic acid copolymers, isobutylene/maleic acid (anhydride) copolymers, and the like. The alkali-soluble resin (A) may contain a polymerizable unsaturated group such as a vinyl group, (meth) allyl group or (meth) acryloyl group, and a thermosetting group such as an 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, and particularly preferably 4,000 to 25,000.

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

The content of the alkali-soluble resin (a) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, in 100% by mass of the nonvolatile component of the photosensitive composition.

The alkali-soluble resin (a) may be used alone or in combination of two or more.

(alkali-soluble resin (A1))

From the viewpoints of inhibition of water staining and heat resistance, the alkali-soluble resin (a) preferably contains an alkali-soluble resin (A1), and the alkali-soluble resin (A1) preferably contains a monomer unit (A1) containing an alicyclic hydrocarbon and a monomer unit (a 2) containing a polymerizable unsaturated group. It is presumed that an alicyclic hydrocarbon structure having high hydrophobicity and both flexibility and rigidity has low affinity with a developer, and can form a strong film. It is also presumed that by having a polymerizable unsaturated group and crosslinking the resins by exposure, a stronger cured film can be formed, and a pattern with suppressed water stain and good heat resistance can be obtained.

The alkali-soluble resin (A1) is not particularly limited as long as it contains a monomer unit (A1) containing an alicyclic hydrocarbon and a monomer unit (a 2) containing a polymerizable unsaturated group, and known resins can be used. Examples thereof include: a copolymer in which a monomer having an alicyclic hydrocarbon-containing monomer unit (a 1) and a monomer having a polymerizable unsaturated group-containing monomer unit (a 2) are formed, a copolymer in which a monomer having an alicyclic hydrocarbon-containing monomer unit (a 1) and another monomer copolymerizable with the above-mentioned monomer are reacted with a compound having a polymerizable unsaturated group, and a polymerizable unsaturated group-containing monomer unit (a 2) is introduced, a copolymer obtained by the method described in japanese patent laid-open No. 2008-165059, and the like. The polymerizable unsaturated group-containing monomer unit (a 2) is a unit containing a polymerizable unsaturated group in the unit. The alkali-soluble group may be present at any position of the resin (A1).

[ alicyclic hydrocarbon-containing monomer unit (a 1) ]

Examples of the monomer forming the alicyclic hydrocarbon-containing monomer unit (a 1) include: isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, and the like. Of these, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate are preferable from the viewpoint of suppression of water stain and pattern shape.

From the viewpoint of water stain inhibition and pattern shape, the content of the alicyclic hydrocarbon-containing monomer unit (A1) in the entire constituent units of the alkali-soluble resin (A1) is preferably 1 to 60 mol%, more preferably 1 to 40 mol%.

[ polymerizable unsaturated group-containing monomer Unit (a 2) ]

Examples of the method for incorporating the polymerizable unsaturated group-containing monomer unit (a 2) into the alkali-soluble resin (A1) include the following methods (i) to (iii).

< method (i) >)

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

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

Examples of the carboxyl group-containing monomer include: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. Of these, acrylic acid and methacrylic acid are preferable.

From the viewpoint of developability, a product obtained by adding an epoxy group of an epoxy group-containing monomer unit to a carboxyl group of a carboxyl group-containing monomer, and further a product obtained by reaction with an acid anhydride are also preferably the polymerizable unsaturated group-containing monomer unit (a 2).

Examples of the acid anhydride include: tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride; succinic anhydride, maleic anhydride, and the like.

< method (ii) >)

Method (ii) is, for example, to first synthesize a polymer (precursor) of a carboxyl group-containing monomer and other monomers. Then, an epoxy group-containing monomer (modified compound) is added to a part of the carboxyl group of the precursor, whereby the precursor can have a carboxyl group and a polymerizable unsaturated group.

< method (iii) >

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

Examples of the hydroxyl group-containing monomer include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate.

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

From the viewpoint of the pattern shape, the content of the polymerizable unsaturated group-containing monomer unit (a 2) in all the constituent units of the alkali-soluble resin (A1) is preferably 5 to 80 mol%, more preferably 10 to 80 mol%.

[ monomer unit (a 3) having a homopolymer glass transition temperature of 0 ℃ or lower ]

From the viewpoint of the pattern shape, the alkali-soluble resin (A1) preferably contains a monomer unit (a 3) (except (A1) and (a 2)) having a glass transition temperature of a homopolymer of 0 ℃ or lower. The monomer unit (a 3) having a glass transition temperature of a homopolymer of-10 ℃ or lower is more preferable, and the monomer unit (a 3) having a glass transition temperature of a homopolymer of-30 ℃ or lower is particularly preferable. The homopolymer is a homopolymer of each monomer, and the glass transition temperature is a value shown in "Handbook of polymers" (Polymer Handbook), third edition (Third edition), john Wiley and Sons, 1989 "edited by Brandrup, e.h. elmugit, e.h.

Examples of the monomer forming the monomer unit (a 3) having a glass transition temperature of 0 ℃ or lower of a homopolymer include: phenoxyethyl acrylate (-22 ℃), lauryl acrylate (-3 ℃), 2-ethylhexyl acrylate (-50 ℃), n-hexyl acrylate (-57 ℃), n-butyl acrylate (-48 ℃), isobutyl acrylate (-40 ℃), ethyl acrylate (-24 ℃), lauryl methacrylate (-65 ℃), n-hexyl methacrylate (-5 ℃), 2-ethylhexyl methacrylate (-10 ℃), 2-methoxyethyl acrylate (-50 ℃), tetrahydrofurfuryl acrylate (-12 ℃), and the like. Of these, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferable.

From the viewpoint of the pattern shape, the content of the monomer unit (a 3) having a glass transition temperature of a homopolymer of 0 ℃ or lower in all the constituent units of the alkali-soluble resin (A1) is preferably 1 mol% to 50 mol%, more preferably 5 mol% to 40 mol%.

[ other monomer unit (a 4) ]

The alkali-soluble resin (A1) may contain a monomer unit other than the monomer units (A1) to (a 3) (hereinafter, also referred to as another monomer unit (a 4)).

Examples of the monomer forming the other monomer unit (a 4) include: (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and glycerol monomethacrylate;

epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 3, 4-epoxycyclohexyl (meth) acrylate;

unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid;

(meth) acrylamides such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine;

vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;

vinyl esters of fatty acids such as vinyl acetate and vinyl propionate;

phenylmaleimide, methylmaleimide, ethylmaleimide, 1, 2-bismaleimidoethane, 1, 6-bismaleimidohexane, 3-maleimidopropionic acid, 6, 7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4' -bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N ' -1, 3-phenylenedimaleimide, 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-succinimido-3-maleimidobenzoate, N-succinimido-3-maleimido-3-maleimidopropionate, N-succinimido-4-succinimidobutyrate, N-6-succinimido-6-phenylmaleimide, N- [2- (4-benzimidazolyl) maleimide ] maleimide, N- [ 9- (2-benzimidazolyl) maleimide ] maleimide, N-substituted with 9-benzimidazolyl maleimide;

2- (meth) acryloyloxyethyl acid phosphate, or a phosphate group-containing (meth) acrylate such as a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth) acrylate with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid;

dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, diethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, di (n-propyl) -2,2' - [ oxybis (methylene) ] bis-2-acrylate, di (isopropyl) -2,2' - [ oxybis (methylene) ] bis-2-acrylate, di (2-ethylhexyl) -2,2' - [ oxybis (methylene) ] bis-2-acrylate, and the like. These monomers may be used alone or in combination of two or more.

The alkali-soluble resin (A1) may be used alone or in combination of two or more.

From the viewpoint of suppressing water staining and the shape of the pattern, the content of the alkali-soluble resin (A1) is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, in 100 mass% of the alkali-soluble resin (a).

(alkali-soluble resin (A2))

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

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

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

(lactone-modified polymerizable Compound (B1))

From the viewpoint of suppressing water damage, the polymerizable compound (B) preferably contains a lactone-modified polymerizable compound (B1).

The lactone-modified polymerizable compound (B1) is a compound having a structure modified with a lactone in a molecule. The lactone-modified polymerizable compound (B1) can be obtained by: polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerol, diglycerol, or trimethylolmelamine are esterified with (meth) acrylic acid, epsilon-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)

[ solution 10]

In the general formula (14), all of six R are groups represented by the following general formula (15), or one to five of six R are groups represented by the following general formula (15), and the remainder are groups represented by the following general formula (16).

General formula (15)

[ solution 11]

In the 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 to the oxygen atom of the general formula (14).

General formula (16)

[ solution 12]

In the general formula (16), R ¹ Represents a hydrogen atom or a methyl group, and is a bond to the oxygen atom of the general formula (14).

The lactone-modified polymerizable compound (B1) is commercially available as, for example, the Karyalard (KAYARAD) DPCA series manufactured by japan chemical company. Examples thereof include: DPCA-20 (in the general formulae (14) to (16), m =1, the number of groups represented by the general formula (15) =2, and R ¹ All hydrogen atoms), DPCA-30 (in the general formulae (14) to (16), m =1, the number of groups represented by the general formula (15) =3, R ¹ All hydrogen atoms), DPCA-60 (in the general formulae (14) to (16), m =1, the number of groups represented by the general formula (15) =6, R ¹ All hydrogen atom compounds), DPCA-120 (in the general formula (14)) In general formula (16), m =2, the number of groups represented by general formula (15) =6, and R ¹ Compounds all of which are hydrogen atoms), and the like.

In the lactone-modified polymerizable compound (B1), in the general formulae (14) to (16), m =1, the number of groups represented by the general formula (15) is preferably from 2 to 6, and R is preferably selected from ¹ The compound having all hydrogen atoms is more preferably a compound in which m =1 and the number of groups represented by general formula (15 =2 or 3, and R in general formulae (14) to (16) ¹ All are hydrogen atoms.

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

From the viewpoint of water stain inhibition, the content of the lactone-modified polymerizable compound (B1) in 100% by mass of the polymerizable compound (B) is preferably 5% by mass to 90% by mass, and more preferably 10% by mass to 85% by mass.

(polymerizable Compound (B2) having acid group)

From the viewpoint of the 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. Of these, a carboxyl group is preferable.

Examples of the polymerizable compound (B2) having an acid group include: esters of poly (meth) acrylates containing free hydroxyl groups of polyols and (meth) acrylic acid with dicarboxylic acids; and esters of polycarboxylic acids with monohydroxyalkyl (meth) acrylates.

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

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

Examples of the polycarboxylic acid include trimellitic acid and pyromellitic acid.

Examples of monohydroxyalkyl (meth) acrylates include: 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.

Commercially available products of the polymerizable compound (B2) having an acid group include Biscoat #2500P manufactured by Osaka organic Co., ltd, aronix M-5300 manufactured by Toyo Synthesis Co., ltd, aronix M-5400, aronix M-5700, aronix M-510, aronix M-520, and Aronix M-521.

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

From the viewpoint of pattern formation, the content of the polymerizable compound (B2) having an acid group in 100% by mass of the polymerizable compound (B) is preferably 5% by mass to 90% by mass, and more preferably 10% by mass to 85% by mass.

(other polymerizable Compound (B3))

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

Examples of the other polymerizable compound (B3) include: methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethyleneglycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, isocyanurate-modified di (meth) acrylate, isocyanurate EO-modified tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tricyclodecyl (meth) acrylate, pentaerythritol tri (meth) acrylate, tridecyl (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and mixtures thereof, various acrylates and methacrylates such as (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, and urethane (meth) acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

Examples of commercially available products include: kayarad (KAYARAD) R-128H, kayaRAD (KAYARAD) R526, kayaRAD (KAYARAD) PEG400DA, kayaRAD (KAYARAD) MAND, kayaRAD (KAYARAD) NPGDA, kayaRAD (KAYARAD) R-167, kayaRAD (KAYARAD) HX-220, kayaRAD (KAYARAD) R-551, kayarad (KARAD) R712, kayarad (YARAD) R-604, kayarad (KARAD) R-684, kayarad (KAYARAD) GPO-303, kayarad (KAYARAD) TMPTA, kayaraD (YAKAYAKARAD) DPHA, kayara DPEA-12, kayarad (KAYARAD) KAYAD-12, KAYARAD-KAYAD (KAYARAD) KAYARAD 310, KAYARAD-C-330, aronius (Aronix) M-303, aronix (Aronix) M-305, aronix (Aronix) M-306, aronix (Aronix) M-309, aronix (Aronix) M-310, aronix (Aronix) M-321, aronix (Aronix) M-325, aronix (Aronix) M-350, aronix (Aronix) M-360, aronix (Aronix) M-313, aronix (Aronix) M-315, aronix (Aronix) M-400, aronix (Aronix) M-402, manufactured by Toya Synthesis Inc, aronix M-403, aronix M-404, aronix M-405, aronix M-406, aronix M-450, aronix M-452, aronix M-408, aronix M-211B, aronix M-101A, viscok (Viscoat) 310HP, viscoat (Viscoat) 335HP, viscok (Viscoat) 700, viscok (Viscoat) 295, viscok (Viscoat) 330, viscok (Viscoat) 360, viscok (Viscoat) T, viscoat (Viscoat) 400, viscoat (GPoat) 400, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, NK ester A-9300, NK ester ABE-300, NK ester A-DOG, NK ester A-DCP, NK ester A-BPE-4, NK ester UA-160TM, manufactured by Xinzhongcun Chemical company, milamor (Miramer) 6060, milamor (Miramer) HR6100, milamor (Miramer) HR6200, everyl (EBECRYL) 40, everg (EBECRYL) 130, everg (EBECRYL) 140, everg (EBRYL) 130, and, ebergco (EBECRYL) 145, OGSOL (OGSOL) EA-0200, OGSOL (OGSOL) EA-0300 manufactured by Otsuka gas Chemicals, and the like.

The polymerizable compound (B) may 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, in 100% by mass of the nonvolatile component of the photosensitive composition.

[ sensitizer (D) ]

The photosensitive composition of the present invention preferably contains a sensitizer (D) from the viewpoint of the pattern shape.

Examples of the sensitizer (D) include: chalcone compounds, unsaturated ketones such as dibenzylideneacetone (dibenzylidene acetonone), 1, 2-dione compounds such as benzil or camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthene compounds, thioxanthone compounds, coumarin compounds, cyanine compounds, merocyanine compounds, oxonol compounds, polymethine pigments such as oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene (azulene) compounds, squarylium compounds, porphyrin compounds, porphyrinoline compounds, triarylporphyrine compounds, triarylmethane compounds, tetraphenylporphyrin compounds, tetrapyrazine (tetrapyrazinonoporphyrin) compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraazaoxazine compounds, phenanthroline compounds, phenanthreneazine compounds, phenanthreneyne (tetrapylenone) compounds, thiopyrenoyl spiro (pyrane) compounds, thiopyreneimine compounds, thiopyrenequinone compounds, thiopyrenespirone compounds, thiopyrenosine compounds, and thiopyrenespirone compounds. 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))

Examples of the thioxanthone-based compound (D1) include: 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Of these, 2, 4-diethylthioxanthone is preferable.

(benzophenone-series Compound (D2))

Examples of the benzophenone-based compound (D2) include: 4,4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 2-aminobenzophenone, and the like. Of these, 4' -bis (diethylamino) benzophenone is preferable.

The sensitizer (D) may be used alone or in combination of two or more.

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

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

The colorant (E) may be any of a pigment and a dye, and may be used in combination.

(pigment)

Pigments are compounds that are classified as pigments in the color index.

Examples of red pigments include: c.i. pigment red (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: 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 and 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 101, 101: 1. 104, 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, 296, 63296, 63295, 134712, pigments disclosed in japanese patent publication No. 688-68844, pigments disclosed in japanese patent publication No. 295-6344, and the like. Among these, c.i. pigment red 48: 1. 122, 177, 224, 242, 269, 254, 291, 295, 296, pigments described in japanese patent laid-open publication No. 2014-134712, pigments described in japanese patent No. 6368844, and more preferably c.i. pigment red 177, 254, 291, 295, 296, pigments described in japanese patent laid-open publication No. 2014-134712, and pigments described in japanese patent No. 6368844.

Examples of orange pigments include: c.i. pigment orange 36, 38, 43, 64, 71, 73, etc.

Examples of the yellow pigment include: c.i. pigment yellow 1,2,3,4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 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, 233, 231 of japanese patent laid-open No. 2012-226110, and the like. Among these, c.i. pigment yellow 138, 139, 150, 185, 231, 233 and the pigments described in japanese patent laid-open publication No. 2012-226110 are preferred.

Examples of the green pigment include: c.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, etc. Of these, c.i. pigment green 36, 58, 59, 62, 63 is preferable.

Examples of blue pigments include: c.i. pigment blue (pigment blue) 1, 1: 2.9, 14, 15: 1. 15: 2. 15: 3. 15: 4. 15:6. 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56: 1. 60, 61: 1. 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Of these, c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15:6.

examples of violet pigments include: c.i. pigment violet (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, etc. Among these, c.i. pigment violet 19 and 23 are preferable.

Examples of the black pigment include: c.i. pigment black 1,6, 7, 12, 20, 31, etc. In addition, at least two pigments selected from the group consisting of a red pigment, a yellow pigment, a blue pigment, a green pigment and a violet pigment may be used as the black colorant.

Among the pigments, examples of the inorganic pigments include: titanium oxide, barium sulfate, silicon oxide, zinc white, lead sulfate, chrome yellow, zinc yellow, red iron oxide (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, umber (umber), synthetic iron black, and the like.

(dyes)

Examples of dyes include: acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like. Further, there may be mentioned derivatives thereof and lake pigments obtained by laking dyes.

The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid [ sulfonic acid group or carboxylic acid group ]. Further, a salt compound, which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, is preferable. Also, salt compounds, which are salts of the resin component having these functional groups and the acid dye, are also preferable. In addition, the salt-forming compound is modified to a sulfonamide compound by performing sulfonylation, and thus a photosensitive composition having excellent resistance (light resistance and solvent resistance) can be easily obtained.

Also, a salt former compound of an acid dye and a compound having an onium salt group is preferable because it is excellent in resistance (light resistance and solvent resistance). Further, the compound having an onium salt group is preferably a resin having a cationic group.

The basic dye can be used as it is, but is preferably a salt-forming compound which forms a salt with an organic acid or perchloric acid or a metal salt thereof. The salt-forming compound of the basic dye is preferable because it is excellent in resistance (light resistance, solvent resistance) and affinity with the pigment. Among the salt-forming compounds of basic dyes, the anionic component that functions as a counter ion is preferably a salt-forming compound obtained by forming a salt with an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anionic compound, a fluorine-containing boron anionic compound, a cyano-containing nitrogen anionic compound, an anionic compound containing a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. In addition, if the salt-forming compound contains a polymerizable unsaturated group in the molecule, the resistance is further improved.

Examples of the chemical structure of the dye include dyes derived from a dye selected from azo dyes, bisazo dyes, azomethine dyes (indoaniline) dyes, indophenol (indophenol) dyes, and the like), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, and the like), carbonium (carbonium) dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, and the like), quinonimine dyes (oxazine dyes, thiazine dyes, and the like), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylene (arylidene) dyes, styryl dyes, cyanine dyes, squarylium dyes, perinone (croconium) dyes, and the like), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine (subphthalocyanine) dyes, cyclocyanine dyes, perinone dyes, quinophthalone dyes, nitrone dyes, and rhodamine dyes, and complex dyes thereof.

Among these, from the viewpoint of color characteristics such as hue, color separability, color unevenness, etc., a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes is preferable, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine dyes, etc. is more preferable.

The colorant (E) may be used alone or in combination of two or more.

The content of the colorant (E) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the nonvolatile component of the photosensitive composition.

(micronization of pigment)

The pigment is preferably used for the purpose of micronization. The micronizing method is not particularly limited, and any of wet grinding, dry grinding and dissolution precipitation methods can be used, for example. Among these, salt milling (salt milling) treatment by a kneader method which is one of wet milling is preferable. The average primary particle diameter of the fine pigment is preferably 5nm to 90nm as determined by a Transmission Electron Microscope (TEM). In addition, the average primary particle diameter is more preferably 10nm to 70nm from the viewpoint of dispersibility and contrast ratio.

The salt milling treatment means the following treatment: the mixture of the pigment, the water-soluble inorganic salt and the water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader (kneader), a two-roll mill (two-roll mill), a three-roll mill (three-roll mill), a ball mill (ball mill), an attritor (attritor) or a sand mill (sandmill), and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution can be obtained.

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

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is a solvent that dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is easily evaporated, a high boiling point solvent having a boiling point of 120 ℃ or higher is preferable in terms of safety. For example, the following may be used: 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. 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, per 100 parts by mass of the pigment.

In the salt milling treatment, a resin may be added as necessary. The kind of the resin is not limited, and examples thereof include: natural resins, modified natural resins, synthetic resins modified with natural resins, and the like. Of these, it is preferable that the organic solvent is solid and water-insoluble at room temperature, and a part of the organic solvent is soluble. The amount of the resin added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[ pigment derivative (F) ]

The photosensitive composition of the present invention may contain a pigment derivative (F).

The dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the pigment derivative (F) include: compounds having an acidic substituent such as a sulfo group, a carboxyl group, or a phosphoric acid group; and amine salts thereof or compounds having a sulfonamide group or a basic substituent such as a tertiary amino group at the terminal; and compounds having a neutral substituent such as phenyl or phthalimidoalkyl.

Examples of the organic pigment include: indole pigments such as diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzindole pigments; isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, reduction pigments, metal complex pigments, azo pigments such as azo, bisazo, and polyazo pigments, and the like.

Specifically, known dye derivatives described in the following publications and the like can be mentioned, and examples of the diketopyrrolopyrrole-based dye derivatives include: japanese patent laid-open publication No. 2001-220520, international publication No. 2009/081930, international publication No. 2011/052617, international publication No. 2012/102399, japanese patent laid-open publication No. 2017-156397; examples of the phthalocyanine-based coloring matter derivative include: japanese patent laid-open No. 2007-226161, international publication No. 2016/163351, japanese patent laid-open No. 2017-165820, japanese patent No. 5753266; examples of the anthraquinone-based pigment derivative include: japanese patent laid-open publication Nos. Sho 63-264674, hei 09-272812, hei 10-24501, hei 10-265697, hei 2007-079094, and International publication No. 2009/025325; as quinacridone pigment derivatives, there can be mentioned: japanese patent laid-open Nos. Sho 48-54128, hei 03-9961, and 2000-273383; examples of the dioxazine dye derivative include Japanese patent laid-open publication No. 2011-162662; examples of thiazine indigo-based pigment derivatives include those described in Japanese patent laid-open No. 2007-314785; examples of the triazine-based dye derivative include: japanese patent laid-open publication No. Sho 61-246261, japanese patent laid-open publication No. Hei 11-199796, japanese patent laid-open publication No. 2003-165922, japanese patent laid-open publication No. 2003-168208, japanese patent laid-open publication No. 2004-217842, and Japanese patent laid-open publication No. 2007-314681; examples of the benzisoindole dye derivatives include Japanese patent laid-open No. 2009-57478; examples of the quinophthalone-based pigment derivative include: japanese patent laid-open No. 2003-167112, japanese patent laid-open No. 2006-291194, japanese patent laid-open No. 2008-31281, japanese patent laid-open No. 2012-226110; examples of the naphthol-based pigment derivative include: japanese patent laid-open Nos. 2012-208329 and 2014-5439; examples of the azo dye derivative include: japanese patent laid-open Nos. 2001-172520 and 2012-172092; examples of the acidic substituent include those described in Japanese patent laid-open publication No. 2004-307854; examples of the basic substituent include: japanese patent laid-open Nos. 2002-201377, 2003-171594, 2005-181383 and 2005-213404. In these documents, the pigment derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic pigment residue has the same meaning as the pigment derivative.

The pigment derivatives (F) may be used alone or in combination of two or more.

The content of the pigment 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 may contain a dispersion resin (G). The dispersion resin (G) is a resin used for dispersion of the colorant (E).

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

Examples of the basic group include: and nitrogen atom-containing groups such as primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium salt groups, and nitrogen-containing heterocycles.

Examples of the acidic group include: carboxyl group, phosphoric group, sulfonic group, and the like. Of these, carboxyl groups and phosphoric groups are preferable from the viewpoint of adsorption to the pigment and developability.

Examples of the resin species of the dispersion resin (G) include: a urethane resin; 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 phosphate salts, hydroxyl group-containing polycarboxylic acid esters, or modified products thereof; amides formed by the reaction of poly (lower alkylene imine) with polyester having free carboxyl group or salts thereof, and the like; water-soluble resins or water-soluble high molecular compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; polyester, modified polyacrylate, ethylene oxide/propylene oxide adduct, phosphate ester, and the like.

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

Examples of commercially available products of the dispersion resin (G) include: dipaki (Disperbyk) -101, dipaki (Disperbyk) -103, dipaki (Disperbyk) -107, dipaki (Disperbyk) -108, dipaki (Disperbyk) -110, dipaki (Disperbyk) -111, dipaki (Disperbyk) -116, dipaki (Disperbyk) -130, dipaki (Disperbyk) -140, dipaki (Disperbyk) -154, dipaki (Disperbyk) -161, dipaki (Disperbyk) -162, dspybyk (Disperbyk) -163, dsbyk-164, dspybyk) -164, dsbyk (Disperbyk) -107, dsbyk (Disperbyk) -162, dsbyk-163, dsbbyk-108, dsbyk (Disperbyk) -108, bybyk-103, bybyk (Bybk) -108, manufactured by Bybk, japan, bybyk Disperbyk (Disperbyk) -166, disperbyk (Disperbyk) -167, disperbyk (Disperbyk) -168, disperbyk (Disperbyk) -170, disperbyk (Disperbyk) -171, disperbyk (Disperbyk) -174, disperbyk (Disperbyk) -180, disperbyk (Disperbyk) -181, disperbyk (Disperbyk) -182, disperbyk (Disperbyk) -183, disperbyk (Disperbyk) -184, disperbyk (Disperbyk) -185, disperbyk (Disperbyk) -2001, disperbyk (Disperbyk) -2009, disperbyk (Disperbyk) -2000, disperbyk (Disperbyk) -2009, dikepbyk (Disperbyk) -2010, dikepbyk (Disperbyk) -2020, dikepbyk (Disperbyk) -2025, dikepbyk (Disperbyk) -2050, dikepbyk (Disperbyk) -2070, dikepbyk (Disperbyk) -2095, dikepbyk (Disperbyk) -2150, dikepbyk (Disperbyk) -2155, dikepbyk (Disperbyk) -2163, dikepbyk (Disperbyk) -2164, or Titlera (Antiu-Terra) -U203, antietala (Antiu-Terra) -U204, or dik-P104, BYK-P104S, BYK-220S, or Lakenby (Lamon), lamon (Bkun) -or Munich (Munich), etc., sonopause (SOLSPERSE) -3000, sonopause (SOLSPERSE) -9000, sonopause (SOLSPERSE) -13000, sonopause (SOLSPERSE) -13240, sonopause (SOLSPERSE) -13650, sonopause (SOLSPERSE) -13940, sonopause (SOLSPERSE) -16000, sonopause (SOLSPERSE) -17000, manufactured by LUBRIZOL, japan Sonopas (SOLSPERSE) -18000, sonopas (SOLSPERSE) -20000, sonopas (SOLSPERSE) -21000, sonopas (SOLSPERSE) -24000, sonopas (SOLSPERSE) -26000, sonopas (SOLSPERSE) -27000, sonopas (SOLSPERSE) -28000, sonopas (SOLSPERSE) -31845, sonopas (SOLSPERSE) -20000, sonopause (SOLSPERSE) -32000, sonopause (SOLSPERSE) -32500, sonopause (SOLSPERSE) -32550, sonopause (SOLSPERSE) -33500, sonopause (SOLSPERSE) -32600, sonopause (SOLSPERSE) -34750, sonopause (SOLSPERSE) -35100, sonopause (SOLSPERSE) -36600, sonopause (SOLSPERSE) -38500, sonopause (SOLSPERSE) -41000, sonopause (SOLSPERSE) -41090, sonopause (SOLSPERSE) -53095, sonopause (SOLSPERSE) -55000, sonopause (SOLSPERSE) -56000, SOLSSPERSE (SOLSPERSE) -00, etc., afv card (EFKA) -46, afv card (EFKA) -47, afv card (EFKA) -48, afv card (EFKA) -452, afv card (EFKA) -4008, afv card (EFKA) -4009, afv card (EFKA) -4010, afv card (EFKA) -4015, afv card (EFKA) -4020, afv card (EFKA) -4047, afv card (EFKA) -4050, afv card (EFKA) -4055, afv card (EFKA) -4060, afv card (EFKA) -4080, afv card (EFKA) -4400, afv card (EFKA) -4401, afv card (EFKA) -4402, afv card (EFKA) -3, afv card (EFKA) -4406, afv card (EFKA) -4408, EFKA-4408, manufactured by BASF corporation, japan, afka (EFKA) -4300, afka (EFKA) -4310, afka (EFKA) -4320, afka (EFKA) -4330, afka (EFKA) -4340, afka (EFKA) -450, afka (EFKA) -451, afka (EFKA) -453, EFKA (EFKA) -4540, EFKA (EFKA) -4550, EFKA (EFKA) -4560, EFKA (EFKA) -4800, EFKA (EFKA) -5010, EFKA (EFKA) -5065, EFKA (EFKA) -5066, EFKA (EFKA) -5070, EFKA (EFKA) -7500, EFKA (EFKA) -7554, EFKA (EFKA) -1101, EFKA) -120, EFKA (EFka) -150, EFKA (EFKA) -1501, EFKA) -1502, EFKA) -1503, ajispar (Ajisper) PA111, ajisper (Ajisper) PB711, ajisper (Ajisper) PB821, ajisper (Ajisper) PB822, and Ajisper (Ajisper) PB824 manufactured by ajinomoto fine technology (ajinomoto fine-Techno) corporation, and japanese patent laid-open publication nos. 2008-029901, 2009-155406, 2010-185934, 2011-157416, international publication nos. 2008/007776, 2008-029901, and the like, resins described in Japanese patent laid-open Nos. 2009-155406, 2010-185934, 2011-157416, 2009-251481, 2007-23195, 1996-143651 and the like.

The dispersion resin (G) may be used alone or in combination of two or more.

From the viewpoint of dispersion stability, the content of the dispersion resin (G) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, with respect 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). This causes the thermosetting compound (H) to react in the heating step, thereby increasing the crosslinking 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. Examples of the thermosetting compound (H) include: an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferable.

(epoxy Compound (H1))

Examples of the epoxy compound (H1) include: polycondensates of bisphenols (bisphenol a, bisphenol F, bisphenol S, 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, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polymers of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); polycondensates of phenols with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of phenols with aromatic dimethanol (benzene dimethanol, α, α, α ', α' -benzene dimethanol, biphenyl dimethanol, α, α, α ', α' -biphenyl dimethanol, etc.); polycondensates of phenols with aromatic dichloromethyl groups (α, α' -dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of bisphenols with various aldehydes; glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidylester epoxy resins obtained by glycidylating alcohols and the like.

Examples of commercially available products include: ipecot (EPICOAT) 807, ipecot (EPICOAT) 815, ipecot (EPICOAT) 825, ipecot (EPICOAT) 827, ipecot (EPICOAT) 828, ipecot (EPICOAT) 190P, ipecot (EPICOAT) 191P, teckomo (TECHNORE) VG3101L, made by Mitsui Chemicals, EPPN-201, EPPN-501H, EPPN-502H, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, ipecot (EPICOAT) 1004, made by Nippon epoxy resins, ipecot (EPOAT) 1256, ipeco 1032R 60, JER157S65, JER157S70, JER152, JER154, celluloid (CELLOXIDE) 2021 and EHPE-3150 manufactured by Daicel chemical industries, inc., sericol (DENACOL) EX-211, desacol (DENACOL) EX-212, desacol (DENACOL) EX-252, desacol (DENACOL) EX-313, desacol (DENACOL) EX-314, desacol (DENACOL) EX-321, desacol (DENACOL) EX-411, desacol (DENACOL) EX-421, desacol (DENACOL) EX-512, desacol (DENACOL) EX-521, desacol (DENACOL) EX-611, desacol (DENACOL) EX-612, desacol (DENACOL) EX-614B, desacol (DENACOL) EX-622, desacol (DENACOL) EX-614, and Desacol (DENACOL) EX-252, danacol (DENACOL) EX-711, danacol (DENACOL) EX-721, TEPIC (TEPIC) -L, TEPIC (TEPIC) -H, TEPIC (TEPIC) -S, etc., manufactured by nippon chemical industries, inc.

The content of the epoxy compound (H1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the nonvolatile component of the photosensitive composition.

(Oxetane Compound (H2))

The oxetane compound (H2) is a known compound having an oxetanyl group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and oxetane compounds having three or more functions.

Examples of monofunctional oxetane compounds are: (3-Ethyloxetan-3-yl) methyl acrylate, (3-ethyloxetan-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloyloxymethyl) oxetane, 3-ethyl-3- { [3- (triethoxysilyl) propoxy ] methyl } oxetane, and the like.

Examples of commercially available products include OXE-10 and OXE-30 manufactured by Osaka organic chemical industries, and OXT-101 and OXT-212 manufactured by east Asia Synthesis.

Examples of difunctional oxetane compounds include: 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, bis [ 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-oxanonane, 1, 2-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ethane, ethylene glycol bis (3-ethyl-3-oxetanylmethoxy) methyl ] propane, ethylene glycol bis (3-oxetanyl) methoxy) ether, dicycloethyl (3-ethylt-ylether, ethylene glycol bis (3-ethylt-3-oxetanyl) methyl ] ether, ethylene glycol bis (3-ethylt-3-oxetanyl) ether, ethylene glycol bis (3-ethylt-3-ethylcyclobutyloxy) methyl ether, ethylene glycol bis (3-ethylt-oxetanyl) ether, ethylene glycol bis (3-ethylcyclobutyloxy) methyl ether, ethylene glycol bis (3-ethylcyclobutyloxy) methyl) ether, ethylene glycol bis (3-ethylt, 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-oxetanylmethyl) ether and the like.

Examples of commercially available products include: OXBP and OXTP manufactured by Uygur corporation, and OXT-121 and OXT-221 manufactured by east Asia Synthesis corporation.

Examples of the trifunctional or higher oxetane compound include: pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetra (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetra (3-ethyl-3-oxetanylmethyl) ether, oxetanyl group-containing resins (for example, oxetane-modified phenol novolac resin described in japanese patent No. 3783462), or (meth) acrylic monomers such as OXE-30 are subjected to radical polymerization.

The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the nonvolatile component of the photosensitive composition.

The 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 per melamine ring of 5.0 or more. If the number of methylol groups or ether groups is appropriately large, adequate heat resistance can be easily obtained.

Examples of commercially available products include: and Nicacharaks (NIKALAC) MW-30HM, NICARACK (NIKALAC) MW-390, NICARACK (NIKALAC) MW-100LM, NICARACK (NIKALAC) MX-750LM, NICARACK (NIKALAC) MW-30M, NICARACK (NIKALAC) MW-30, NICARACK (NIKALAC) MW-22, NICARACK (NIKALAC) MS-21, NICARACK (NIKALAC) MS-11, NICARACK (NIKALAC) MW-24X, NICARACK (NIKALAC) MS-001, NICARACK (NIKALAC) MW-002, NICARACK (NIKALAMX) MX-730, NICARACK (NIKALAC) NIKALAMX-750, NICARACK (NIKALAC) LAC-417, NICARACK (NIKALAC) LAC) NIKAMX-500, NICARACK (NIKALAC) MW-520, NICARACK-500, NIC (NIKALAC) MX-500 KALAC, NIC-500 KALAC (NIKALAC) MX-500 KALAC), seimel (CYMEL) 232, seimel (CYMEL) 235, seimel (CYMEL) 236, seimel (CYMEL) 238, seimel (CYMEL) 285, seimel (CYMEL) 300, seimel (CYMEL) 301, seimel (CYMEL) 303, and Seimel (CYMEL) 32, manufactured by Japan cyanote Industries, inc, seimell (CYMEL) 350, seimell (CYMEL) 370, and the like.

Of these, nicarback (NIKALAC) MW-30HM, nicarback (NIKALAC) MW-390, nicarback (NIKALAC) MW-100LM, nicarback (NIKALAC) MX-750LM, nicarback (NIKALAC) MW-30M, nicarback (NIKALAC) MW-30, nicarback (NIKALAC) MW-22, nicarback (NIKALAC) MS-21, nicarback (NIKALAC) MS-11, nicarback (NIKALAC) MW-24X, nicarback (NIKALAC) MW-45, seimel (CYMEL) 232, seimel (CYMEL) 235, seimel (CYMEL) 236, seimel (CYMEL) 238, seimel (CYMEL) 300, seimel (CYMEL) 301, seimel (CYMEL) 303, seimel (CYMEL) 350, and the like, which are manufactured by Japan Cytec Industries, are preferable in terms of increasing the crosslinking density.

The thermosetting compound (H) may be used alone or in combination of two or more.

[ hardening agent (hardening accelerator) ]

In order to assist in curing the thermosetting compound (H), a curing agent (curing accelerator) may be used in combination with the photosensitive composition of the present invention. Examples of the curing agent include: amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. Examples of the curing agent include: examples of the amine compound include dicyandiamide, benzyldimethylamine (benzyldimethylamine), 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine and the like), quaternary ammonium salt compounds (triethylbenzylammonium chloride and the like), blocked isocyanate compounds (dimethylamine and the like), imidazole derivative bicyclic amidine compounds and salts thereof (imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and the like), phosphorus compounds (triphenylphosphine and the like), S-triazine derivatives (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-methylacryloyloxyethyl-S-triazine and the like.

The curing agent may 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 chain transfer agent (I) ]

The photosensitive composition of the present invention may contain a thiol chain transfer agent (I). When the thiol chain transfer agent (I) is used in combination with the photopolymerization initiator (C), a sulfur radical (thiylradial) which is less likely to be inhibited by polymerization by oxygen is generated during radical polymerization after light irradiation, and the photosensitivity of the photosensitive composition is improved.

The thiol chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more thiol groups (SH groups). When the number of functional groups increases, the film is easily photo-cured from the surface to the deepest part of the film.

Examples of polyfunctional thiols include: hexane dithiol, decane dithiol, 1, 4-butanediol bisthiopropionate, 1, 4-butanediol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1, 4-dimethylmercaptobenzene, 2,4, 6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4, 6-dimercapto-s-triazine, etc., and preferable examples thereof include: ethylene glycol bisthiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate.

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

The content of the thiol chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, in 100% by mass of the nonvolatile component of the photosensitive composition. When the amount is contained in a proper amount, the light sensitivity 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 may contain a polymerization inhibitor (J).

Examples of the polymerization inhibitor (J) include: alkyl catechol-based compounds such as 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-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3, 5-di-tert-butylcatechol; alkyl resorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, t-butyl hydroquinone, and 2, 5-di-t-butyl hydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, and the like; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol, phloroglucin, 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 the nonvolatile component of the photosensitive composition.

[ ultraviolet absorber (K) ]

The photosensitive composition of the present invention may contain an ultraviolet absorber (K).

The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and examples thereof include: benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

Examples of the benzotriazole-based compound include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [ 2-hydroxy-3, 5-bis (. Alpha., alpha-dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% phenylpropionic acid and mixtures of 3- (2H-benzotriazol-2-yl) - (1, 1-dimethylethyl) -4-hydroxy and 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, 3-tetramethylbutyl) phenol, a reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate/polyethylene glycol 300, and 2- (2H-benzotriazol-2-yl) -4- (1, 3 -tetramethylbutyl) phenol, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ], 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2- (3, 5-di-tert-pentyl-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.

Examples of commercially available products include: bin (TINUVIN) P, dinun (TINUVIN) PS, dinun (TINUVIN) 234, dinun (TINUVIN) 326, dinun (TINUVIN) 329, dinun (TINUVIN) 384-2, dinun (TINUVIN) 900, dinun (TINUVIN) 928, dinun (TINUVIN) 99-2, dinun (TINUVIN) 1130, adekata (Adekab) LA-29, dekostob (Adekab) LA-31, adekata (Adekab) LA-32, adekab (Adekab) LA-36, kamikava (MIS) 93, kamikami, kamikumi B71, kamikumi) 93, and so on.

Examples of the triazine compound include: 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, a reaction product of 2- (2, 4-dihydroxyphenyl) -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-ethylhexyloxy) ethoxy ] phenol, 2,4, 6-tris (2-hydroxy-4-methylhexyloxy) -3-triazin-2-yl, 5-triazine, and the like.

Examples of commercially available products include: camisole (KEMISORB) 102 manufactured by Chemipro Kasei, innovin (TINUVIN) 400 manufactured by BASF, innoxin (TINUVIN) 405, innovin (TINUVIN) 460, innovin (TINUVIN) 477, innovin (TINUVIN) 479, innovin (TINUVIN) 1577ED, addisotab (Adekab) LA-46 manufactured by ADEKA, addisotab LA-F70, addisotab (Adekab) UV-1164 manufactured by Sun chemical, and the like.

Examples of the benzophenone-based compound include: 2, 4-bis-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2 '-bis-hydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 2',4,4 '-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and the like.

Examples of commercially available products include: kemike cloth (KEMISORB) 10, kemike cloth (KEMISORB) 11S, kemike cloth (KEMISORB) 12, kemike cloth (KEMISORB) 111, kemike cloth (semisorb) 101, semike cloth (SEESORB) 107, idecolat (ADEKA) 1413, UV-12, and the like, manufactured by sumiproni (Sun Chemical).

Examples of the salicylate-based compound include: phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

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

[ antioxidant (L) ]

The photosensitive composition of the present invention may contain an antioxidant (L).

The antioxidant (L) prevents yellowing due to oxidation of the photopolymerization initiator (C) and the thermosetting compound (H) contained in the photosensitive composition, which may occur in a thermal step during thermal curing or annealing of Indium Tin Oxide (ITO). In particular, when the concentration of the colorant (E) in the photosensitive composition is high, the content of the polymerizable compound (B) is relatively reduced, and therefore, if the amount of the photopolymerization initiator (C) is increased or the thermosetting compound (H) is blended, the cured film tends to be yellowed. Therefore, the inclusion of the antioxidant prevents yellowing of the cured film due to oxidation in the heating step.

Examples of the antioxidant (L) include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds and hydroxylamine compounds. Further, the antioxidant in the present specification 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 preferable.

Examples of the hindered phenol antioxidant include: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,1, 3-tris- (2 '-methyl-4' -hydroxy-5 '-tert-butylphenyl) -butane, 4,4' -butylidene-bis- (2-tert-butyl-5-methylphenol), stearyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis (tert-butyl-5-methyl-phenyl) propionate, bis (2-tert-butyl-5-methyl-ethyl-propyl-methyl-ethyl-methyl-4-butyl-hydroxy-phenyl) -butane, bis (2, 4-butyl-5-methyl-phenyl) -propionate, and mixtures thereof 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4, 6-trimethylbenzene, 1,3, 5-tris (3-hydroxy-4-tert-butyl-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2 '-methylenebis (6-tert-butyl-4-ethylphenol), 2' -thiodiethylbis- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylene bis (3, 5-di-tert-butyl-4-hydroxy-hydroxycinnamamide), isooctyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 4, 6-bis (dodecylthiomethyl) -o-cresol, the calcium salt of monoethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 4, 6-bis (octylthiomethyl) -o-cresol, bis [3- (3- (methyl-4-hydroxy-5-tert-butylphenyl) propanoic acid ] ethylenedioxydiethylene ester, 1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 4-bis- (n-octylthio) -6- (4-hydroxy-3, 5-di-tert-butylaniline) -1,3, 5-triazine, 2' -thio-bis- (6-tert-butyl-4-methylphenol), 2, 5-di-tert-pentyl-hydroquinone, 2, 6-di-tert-butyl-4-nonylphenol, 2' -isobutylidene-bis- (4, 6-dimethyl-phenol), 2' -methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol, 2-dimethyl-cyclohexylene) -phenol, and the like.

Examples of commercially available products include: adekastab (Adekastab) AO-20, adekastab (Adekastab) AO-30, adekastab (Adekastab) AO-40, adekastab (Adekastab) AO-50, adekastab (Adekastab) AO-60, adekastab (Adekastab) AO-80, adekastab (Adekastab) AO-330, caminox (KEMINOX) 101, keminox (KEMINOX) 179, keminox (KEMINOX) 76, keminox (KEMINOX) 9425, louisin (IRGANOX) 1010, louisin (IRGANOX) 1035, louisin (IRGANOX) 1076, louisin (IRGANOX) 1098, louisin (IRGANOX) 1135, louisin (IRGANOX) 1330, louisin (IRGANOX) 1726, louisin (IRGANOX) 1425WL, louisin (IRGANOX) 1520L, louisin (IRGANOX) 245, louisin (IRGANOX) 259, louisin (IRGANOX) 3114, louisin (IRGANOX) 5057, louisin (IRGANOX) 565, louisin (CYANOX) CY 1790, etc. manufactured by Sun Chemical corporation.

Examples of the hindered amine antioxidant include: 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-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, a polycondensate of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, dimethyl succinate with 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, a polycondensate of poly [. 6- [ (1,1,3,3-tetramethylbutyl) amino ] -s-triazine-2,4-yl ] - [ (2-tetramethyl-4-hydroxy-2,6,6-piperidyl) piperidine, a polycondensate of poly [. 6- [ (1,1,3,3,3-tetramethylbutyl) amino ] -s-4-piperidyl ] -1,7,6-bis (1,6-N-4-piperidyl) N-6-aminohexan-1,7,4-piperidine, 4-piperidyl } -1,6,6,6,6, <xnotran> (2,2,6,6- -1- ( ) -4- ) 1,1- , (1,2,2,6,6- -4- ) [ [3,5- (1,1- ) -4- ] ] , 1,2,2,6,6- -4- , [ [6- - -2,4- ] - [ (2,2,6,6- -4- ) ] - - [ (2,2,6,6- -4- ) ] ], 2,2,6,6- -4- -C12-21 C18 , N, N' - (2,2,6,6- -4- ) -1,6- ,2- -2- (2,2,6,6- -4- ) -N- (2,2,6,6- -4- ) . </xnotran>

Examples of commercially available products include: addicostat (Adekastab) LA-52, addicustat (Adekastab) LA-57, addicustat (Adekastab) LA-63P, addicustat (Adekastab) LA-68, addicustat (Adekastab) LA-72, addicustat (Adekastab) LA-77Y, addicustat (Adekastab) LA-77G, adekastab LA-81, addicustat (Adekastab) LA-82, adekastab (Adekastab) LA-87, adekastab (Adekastab) LA-402F, and Adekastab (Adekastab) LA-502, kamitaba wave (KAMISTAB) 29, kamitaba wave (KAMISTAB) 62, kamitaba wave (KAMISTAB) 77, kamitaba wave (KAMISTAB) 94, dennu Bin (TINUVIN) 111FDL, dennun Bin (TINUVIN) 123, dennun Bin (TINUVIN) 144, dennun Bin (TINUVIN) 249, dennun Bin (TINUVIN) 292, dennun Bin (TINUVIN) 5100, seayou cloth (ASCYORB) UV-3346, seayou cloth (ASCYORB) UV-3529, seayou Cloth (CYORB) UV-3853, etc., manufactured by Chemiprozo Kasei (Chemiki).

Examples of the phosphorus-containing antioxidant include: bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2 '-methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (C12-C15 alkyl) -4,4' -isopropylidenediphenyl diphosphite, a salt of a phosphonic acid with a metal halide diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris (isodecyl) phosphite, triphenyl phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4-biphenylyl diphosphonite, tris (tridecyl) phosphite, phenyl isooctyl phosphite phenyl isodecyl phosphite, phenyl ditridecyl phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4 '-isopropylidenediphenol alkyl phosphite, trinonylphenyl phosphite, tris-dinonylphenyl phosphite, tris (biphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra-tridecyl 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, hexa-tridecyl 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite Diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphite, sodium bis (4-tert-butylphenyl) phosphite, sodium 2, 2-methylene-bis (4, 6-di-tert-butylphenyl) -phosphite, 1, 3-bis (diphenoxyphosphonooxy) -benzene, ethylbis (2, 4-di-tert-butyl-6-methylphenyl) phosphite, and the like.

Examples of commercially available products include: addicotabo (Adekastab) PEP-36, addicotabo (Adekastab) PEP-8, addicotabo (Adekastab) HP-10, addicotabo (Adekastab) 2112, addicotabo (Adekastab) 1178, addicotabo (Adekastab) 1500, addicotabo (Adekastab) C, addicotabo (Adekastab) 135A, addicotabo (Adekastab) 3010, adekastab (Adekastab) TPP, idiscotabo (Adekastab) TPP, yinlufos (IRGAFOS) 168, manufactured by Nippon Bauss Kario (BASF), hohaystans (EPQ, etc., manufactured by Clien Chemicals (Antikerias).

Examples of the sulfur-based antioxidant include: 2, 2-bis { [3- (dodecylthio) -1-oxopropoxy ] methyl } propane-1, 3-diylbis [3- (dodecylthio) propionate ], ditridecyl 3,3' -thiodipropionate, 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.

Examples of commercially available products include Adekastab AO-412S manufactured by Adekata corporation, adekastab AO-503, and Keminox PLS manufactured by Chemipro Kasei corporation.

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

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass in 100% by mass of the nonvolatile component of the photosensitive composition. When contained in an appropriate amount, the transmittance, spectroscopic characteristics and sensitivity are improved.

[ leveling agent (M) ]

The photosensitive composition of the invention may contain a leveling agent (M). This further improves the wettability and drying property with respect to the substrate during coating.

Examples of the leveling agent (M) include: silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and the like.

Examples of the silicone surfactant include: a linear polymer containing a siloxane bond, or a modified siloxane polymer having an organic group introduced into a side chain or a terminal thereof.

Examples of commercially available products include: BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-UV3570, FZ-7002, FZ-2110, FZ-2122, FZ-2123, FZ-2191 and FZ-5609 manufactured by Toray Corning (Toray Dow Corning) 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 and KP-341 manufactured by shin-Etsu chemical Co., ltd.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain and a leveling agent.

Examples of commercially available products include: shafu long (Surflon) S-242, shafu long (Surflon) S-243, shafu long (Surflon) S-420, shafu long (Surflon) S-611, shafu long (Surflon) S-651, shafu long (Surflon) S-386, meijia method (Megafac) F-253, meijia method (Megafac) F-477, meijia method (Megafac) F-551, meijia method (Megafac) F-552, meijia method (Megafac) F-555, meijia method (Megafac) F-558, meijia method (Megafac) F-560, meijia method (Megafac) F-570, meijiafac (Megafac) F-575, meijiafac method (Megafac) F-576, meijiafac method (Megafac) R-40-LM, meijiafac (Megafac) R-41, meijiafac method (Megafac) RS-72-K, meijiafac method (Megafac) DS-21 manufactured by Dielson (DIC), FC-4430 and FC-4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi electro Chemical Co., ltd., fojite (Ftergent) 602A manufactured by Nios (NEOS), and the like.

Examples of the nonionic surfactant include: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , . </xnotran>

Examples of commercially available products include: the Aimu root (Emulgen) 103, aimu root (Emulgen) 104P, aimu root (Emulgen) 106, aimu root (Emulgen) 108, aimu root (Emulgen) 109P, aimu root (Emulgen) 120, aimu root (Emulgen) 123P, aimu root (Emulgen) 130K, aimu root (Emulgen) 147, aimu root (Emulgen) 150, aimu root (Emulgen) 210P, aimu root (Emulgen) 220, aimu root (Emulgen) 306P, aimu root (Emulgen) 320P, aimu root (Emulgen) 350, aimu root (Emulgen) 404, aimu root (Emulgen) 408, emulgen (Emulgen) 409, aimu root (Emulgen) 420, and Emulgen 409 the plant growth regulator is prepared from the following raw materials, by weight, amur root (Emulgen) 705, amur root (Emulgen) 707, amur root (Emulgen) 709, amur root (Emulgen) 1108, amur root (Emulgen) 1118S-70, amur root (Emulgen) 1135S-70, amur root (Emulgen) 1150S-60, amur root (Emulgen) 2020G-HA, amur root (Emulgen) 2025G, amur root (Emulgen) LS-106, amur root (Emulgen) LS-110, amur root (Emulgen) LS-114, amur root (Emulgen) MS-110, amur root (Emulgen) A-60, amur root (Emulgen) PD-90, amur root (Emulgen) B-66, amur root (Emulgen) MS-290, amur root (Emulgen) PP-420, and Amur root (Emulgen) PP-420, latamimul (Latemul) PD-430, latamimul (Latemul) PD-430S, latamimul (Latemul) PD-450, laodelu (Rheodol) SP-L10, laodelu (Rheodol) SP-P10, laodelu (Rheodol) SP-S10V, laodelu (Rheodol) SP-S20, laodelu (Rheodol) SP-S30V, laodelu (Rheodol) SP-O10V, laodelu (Rheodol) SP-O30V, laodelu super (Rheodol) SP-L10, laodelu (Rheodol) AS-AO 10V, laodelu (Rheodol) TW-10V, latamoul (Rheodol) PD-430, latamoul (Latemul) PD-430S, latamoulu (Rheodol) PD-S10, latemul (Rheodol) SP-S10V, laodelu (Rheodol) SP-S10V, laodell (Rheodol) SP-S10V, laodel, raleodol (Rheodol) SP-S10V, and L10V LyodeRou (Rheodol) TW-L106, lyodeRou (Rheodol) TW-P120, lyodeRou (Rheodol) TW-S120V, lyodeRou (Rheodol) TW-S320V, lyodeRou (Rheodol) TW-O120V, lyodeRou (Rheodol) TW-O106V, lyodeRou (Rheodol) TW-IS399C, lyodeRou super (Rheodol) TW-L120, lyodeRou (Rheodol) 430V, lyodeRou (Rheodol) 440V, lyodeRou (Rheodol) 460V, lyodeRou super (Rheodol) MS-50, lyodero (Rheodol) MS-60, lyodero (Rheodol) MO-60, lyodero (Rheodol) MS-1112, and Rou (Rheodol) 1112V-S165V, amur (Emanon) 3199V, amur (Emanon) 3299RV, amur (Emanon) 4110, aminon (Emanon) CH-25, amano (Emanon) CH-40, amino (Emanon) CH-60 (K), amiet (Amiet) 102, amiet (Amiet) 105A, amiet (Amiet) 302, amiet (Amiet) 320, aminon (Aminon) PK-02S, aminon (Aminon) L-02, fire Mogonol (Homogenol) L-95, adeka Pluronic L-23, adeka Pluronic L-31, adeka Pluronic L-44, adeka Pluronic L-61, adeka Pluronic L-62, adeka Pluronic L-64, adeka Pluronic L-71, adeka Pluronic L-72, adeka Pluronic L-704, adeka Pluronic L-101, adeka Pluronic L-121, adeka Pluronic 701, adeka Pluronic R-702, adeka Pluronic, adeka Pluronic TR-913R, (meth) acrylic (co) polymers Pelizafelo (Polyflow) No.75, pelizafelo (Polyflow) No.90, pelizafelo (Polyflow) No.95 manufactured by Cogrong chemical Co., ltd.

Examples of the cationic surfactant include: alkyl quaternary ammonium salts such as alkylamine salts, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof.

Examples of commercially available products include asethamine (Acetamin) 24, cortolamine (quaramin) 24P, cortolamine (quaramin) 60W, and cortolamine (quaramin) 86PCONC manufactured by Kao corporation.

Examples of the anionic surfactant include: polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphate, and the like.

Examples of commercially available products include: fojirt (Ftergent) 100 and Fojirt (Ftergent) 150 manufactured by Niaus (NEOS), adeko hoppe (ADEKA HOPE) YES-25 manufactured by Adeko (ADEKA), adekouru (ADEKA COL) TS-230E, adekouru (ADEKA COL) PS-440E, and Adekouru (ADEKACOL) EC-8600.

Examples of amphoteric surfactants include: alkyl betaines such as lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; alkyl amine oxides such as lauryl dimethyl amine oxide, and the like.

Commercially available products include: amphiol (AMPHITOL) 20AB, AMPHITOL 20BS, AMPHITOL 24B, AMPHITOL 55AB, AMPHITOL 86B, AMPHITOL 20Y-B, AMPHITOL 20N, etc., manufactured by Kao corporation.

The leveling agent (M) may be used alone or in combination of two or more.

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 the nonvolatile component of the photosensitive composition. When the amount is within the above range, the balance between the coating property and the adhesion of the photosensitive composition is further improved.

[ storage stabilizer (N) ]

The photosensitive composition of the present invention may contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive composition with time.

Examples of the storage stabilizer (N) include: quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid, organic phosphines such as methyl ether, t-butylcatechol, tetraethylphosphine, and tetraphenyl, and phosphites.

The storage stabilizer (N) may be used alone or in combination of two or more.

The content of the storage stabilizer (N) is preferably 0.1 to 10% by mass in 100% by mass of nonvolatile components of the photosensitive composition.

[ adhesion improver (O) ]

The photosensitive composition of the present invention may contain an adhesion improving agent (O). This improves the adhesion between the coating and the substrate. In addition, a pattern having a narrow width is easily formed by photolithography.

Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include: vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxysilanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; aminosilanes such as hydrochloride of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto groups such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureido groups such as 3-ureidopropyltriethoxysilane; thioethers such as bis (triethoxysilylpropyl) tetrasulfide; and isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane.

The adhesion improver (O) may 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 the nonvolatile component of the photosensitive composition.

[ organic solvent (P) ]

The photosensitive composition of the present invention may contain an organic solvent (P).

Examples of the organic solvent (P) include: 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol (1, 3-butandiol), 1,3-butanediol (1, 3-butylene glycol), 1,3-butanediol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1, 3-propanediol, 3, 5-trimethyl-2-cyclohexene-1-one, 3, 5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1, 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N-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-butyl benzene, gamma-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol dimethyl ether, and mixtures thereof, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, 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 (triacetin), tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic ester, and the like. Of these, from the viewpoints of dispersibility of the colorant and solubility of the binder resin, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferable; alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

The organic solvent (P) may be used alone or in combination of two or more.

[ method for producing photosensitive composition ]

The photosensitive composition of the present invention is prepared by, for example, preparing a colorant (E), a dispersion resin (G), a pigment derivative (F), an organic solvent (P), and the like, and dispersing them to prepare a dispersion. Then, the aqueous dispersion can be prepared by blending and mixing the alkali-soluble resin (a), the polymerizable compound (B), the photopolymerization initiator (C), and the like into the dispersion. In addition, the materials to be blended and the timing of blending thereof are arbitrary. In addition, the dispersing step may be performed a plurality of times.

Examples of the dispersing machine for performing the dispersing treatment include: two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular (annular type) bead mills or attritors, etc.

The average dispersed particle diameter (secondary particle diameter) of the colorant in the dispersion is preferably 30nm to 200nm, more preferably 40nm to 200nm. When the particle size is appropriate, a photosensitive composition having high dispersion stability can be easily obtained.

The average dispersed particle size (secondary particle size) is measured by, for example, a method using a micro orbit (micro orbit) UPA-EX150 of japanese machine tools, which employs a dynamic light scattering method (fast Fourier transform (FFT) power spectrum method), and the particle transmittance is set to an absorption mode, the particle shape is set to a non-spherical shape, and the D50 particle size is set to an average diameter. The dilution solvent for measurement is preferably an organic solvent used for dispersion, and is more likely to give a result with less variation when a sample treated with ultrasonic waves is measured immediately after sample adjustment.

The photosensitive composition is preferably subjected to removal of coarse particles having a particle size of 5 μm or more, preferably coarse particles having a particle size of 1 μm or more, and more preferably coarse particles having a particle size of 0.5 μm or more, and dust mixed therein by means of centrifugation, filtration using a sintered filter or a membrane filter, or the like. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

< Filter >

The optical filter of the present invention includes a substrate and a filter segment formed of the photosensitive composition of the present invention. The optical filter may be used for various purposes. In the present specification, the optical filter is preferably a color filter.

In the case of a color filter, the filter has a red filter, a green filter, and a blue filter by appropriately selecting the kind of the colorant (E) to be used. Instead of or in addition to the filter segments, there may be magenta, cyan, yellow, white, gray, black filter segments. In addition, a transparent filter may be provided.

The substrate includes a transparent substrate and a reflective substrate. The transparent substrate may be, for example, a glass substrate. Examples of the reflective substrate include substrates using aluminum electrodes or metal thin films as reflective surfaces.

[ method for producing optical Filter ]

The method of manufacturing the optical filter can be manufactured, for example, by performing the following steps: a step (1) for coating a photosensitive composition on a substrate to form a layer (coating film) of the composition; a step (2) of exposing the layer in a pattern shape through a mask; a step (3) of forming a patterned cured film by alkali development of the unexposed portion; and (4) performing a heat treatment (post-baking) on the pattern.

Hereinafter, a method for manufacturing the optical filter will be described in detail.

(step (1))

The step (1) of forming the composition layer is to apply the photosensitive composition onto a substrate by a method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, and dry (prebake) the photosensitive composition at a temperature of 50 to 120 ℃ for 10 to 120 seconds, using an oven, a hot plate, or the like as necessary.

Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an image sensor such as a Charge Coupled Device (CCD) or a Complementary Metal Oxide Semiconductor (CMOS) formed on the surface thereof. Further, if necessary, an undercoat layer may be provided on the substrate to improve adhesion to an upper layer, prevent diffusion of a substance, and planarize the substrate surface.

The film thickness of the layer is preferably 0.05 to 10.0. Mu.m, 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 apparatus such as a lithography machine (stepper). Thereby obtaining a hardened film.

Examples of the radiation used for exposure include: ultraviolet rays such as g-ray, h-ray, i-ray, etc.

(step (3))

The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the layer of the composition in the unexposed area is eluted into an alkali aqueous solution, and only the cured portion remains, thereby obtaining a patterned cured film.

Examples of the developer include: basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo- [5.4.0] -7-undecene.

The concentration of the developer is preferably 0.001 to 10 mass%, more preferably 0.01 to 1 mass%.

The pH of the alkali developing solution is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughening and peeling are suppressed, and the residual film ratio after development is improved.

Examples of the developing method include a dipping method, a spraying method, and a liquid coating (puddle) method. The development temperature is preferably from 15 ℃ to 40 ℃. After the alkali development, it is preferable to wash with pure water.

(step (4))

The heat treatment (post-baking) is a treatment of sufficiently curing the patterned cured film obtained in step (3) by heating. The heating temperature of the postbaking is preferably 100 ℃ to 300 ℃, more preferably 150 ℃ to 250 ℃. The heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

< image display device >

The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display, an organic Electroluminescence (EL) display, and the like.

The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the structure described in "next generation liquid crystal display technology (available from the national dragon male, the institute of industry, 1994), and the like can be cited.

The definition of the image display devices and the details of the respective image display devices are described in, for example, "electronic display devices (published by showa (stock) industrial survey, 1990)", "display devices (published by eizu chapters, industrial books (stock), 1989)", and the like.

< solid-state imaging element >

The solid-state imaging element of the present invention includes the optical filter of the present invention.

The form used for the solid-state imaging element is not particularly limited, and is, for example, the following structure: the image sensor includes a substrate, a plurality of photodiodes and a transfer electrode made of polysilicon or the like, which constitute a light receiving region of a solid-state image sensor (such as a CCD image sensor or a CMOS image sensor), a light shielding film which is provided on the photodiodes and the transfer electrode and is open only to a light receiving portion of the photodiodes, a device protection film made of silicon nitride or the like and provided on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiodes, and a filter provided on the device protection film. Further, the structure may be one having a light condensing member (for example, a microlens) on the device protective film and below the filter (on the side close to the substrate), or one having a light condensing member on the filter. The filter may have a structure in which a cured film for forming each color pixel is embedded in a space partitioned into, for example, a lattice shape by a partition wall. The partition wall in this case is preferably low in refractive index for each colored pixel.

An imaging device including the solid-state imaging element of the present invention can be used for various applications such as a digital camera, an electronic device (e.g., a mobile phone or a smartphone) having an imaging function, an onboard camera, and a monitoring camera.

[ examples ]

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Further, "part" is "part by mass" and "%" is "% by mass".

In the present invention, the nonvolatile matter or nonvolatile matter concentration means the mass residual component after being left to stand in an oven at 280 ℃ for 30 minutes.

Before the examples, the respective measurement methods 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 the weight average molecular weight (Mw) of the resin were measured by Gel Permeation Chromatography (GPC) equipped with a Refractive Index (RI) detector. HLC-8220GPC (manufactured by Tosoh) was used as an apparatus, two separation columns were connected in series, two TSK GEL SUPER HZM-N (TSK-GEL SUPER HZM-N) were connected to each other as a packing material, and measurement was performed at an oven temperature of 40 ℃ and a flow rate of 0.35ml/min using a Tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent containing 1 mass% of the eluent, and 20. Mu.l was injected. The average molecular weight is in terms of polystyrene.

(acid value of resin)

80ml of acetone and 10ml of water were added to 0.5g to 1g of the resin solution and uniformly dissolved by stirring, and an automatic titrator ("COM-555", manufactured by TOKIN DAMPU INDUSTRY CO., LTD.) was used to titrate a 0.1mol/L potassium hydroxide (KOH) aqueous solution as a titrating solution, and an acid value (mgKOH/g) was measured. Then, the acid value per unit nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(amine number of resin)

The amine value of the resin is a value obtained by converting the total amine value (mgKOH/g) measured by the method of American Society for Testing Materials (ASTM) D2074 into a nonvolatile content.

< production of colorant (E) >

(micronized Red pigment (E-1))

100 parts of c.i. pigment red 254, 1,200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by uphole manufacturing company) and kneaded at 60 ℃ for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour with a high-speed mixer while being heated to about 80 ℃ to prepare a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, dried at 80 ℃ for a whole day and night, and pulverized, thereby obtaining a finely divided red pigment (E-1).

(micronized Red pigment (E-2))

100 parts of c.i. pigment red 177, 1,200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by uphole manufacturing company) and kneaded at 60 ℃ for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour with a high-speed mixer while being heated to about 80 ℃ to prepare a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, dried at 80 ℃ for a whole day and night, and pulverized to obtain a finely divided red pigment (E-2).

(micronized blue pigment (E-3))

100 parts of c.i. Pigment Blue (Pigment Blue) 15, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by uphole manufacturing company) and kneaded at 50 ℃ for 12 hours. The mixture was put into 3,000 parts of warm water, stirred by a high-speed mixer for about 1 hour while being heated to about 70 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 80 ℃ for 24 hours and pulverized to obtain a micronized blue pigment (E-3).

(micronized purple pigment (E-4))

100 parts of c.i. pigment violet 23, 1,200 parts of sodium chloride and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by uphole manufacturing company) and kneaded at 80 ℃ for 6 hours. Next, the kneaded mixture was put into 8,000 parts of warm water, stirred for 2 hours with a high-speed mixer while being heated to 80 ℃ to be made into a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing, it was dried for 24 hours at 85 ℃ and pulverized to obtain a micronized violet pigment (E-4).

(micronized Green pigment (E-5))

100 parts of c.i. pigment green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by uphole production), and kneaded at 70 ℃ for 6 hours. The kneaded mixture was put into 3000 parts of warm water, stirred with a high-speed mixer for 1 hour while being heated to 70 ℃ to prepare a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ℃ for a whole day and night and pulverized to obtain a micronized green pigment (E-5).

(micronized Green pigment (E-6))

According to examples of Japanese patent laid-open publication No. 2017-111398, a green pigment (E-6) of the following chemical formula (17) was obtained. 100 parts of green pigment (E-6), 1,200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by UK Co., ltd.), and kneaded at 70 ℃ for 6 hours. The kneaded mixture was put into 3000 parts of warm water, stirred with a high-speed mixer for 1 hour while being heated to 70 ℃ to prepare a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ℃ for a whole day and night and pulverized to obtain a micronized green pigment (E-6).

Chemical formula (17)

[ solution 13]

(micronized yellow pigment (E-7))

100 parts of c.i. pigment yellow 150, 700 parts of sodium chloride and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by uphole production), and kneaded at 80 ℃ for 6 hours. The mixture was put into 2,000 parts of warm water, stirred for 1 hour with a high-speed mixer while being heated to 80 ℃ to prepare a slurry, and the slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ℃ for a whole day and night and pulverized to obtain a finely pulverized yellow pigment (E-7).

(micronized yellow pigment (E-8))

100 parts of c.i. pigment Yellow 139 ("tovoperm Yellow P-M3R" manufactured by Clariant corporation), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1-gallon kneader (manufactured by uphole corporation), and kneaded at 70 ℃ for 12 hours. The mixture was put into 3000 parts of warm water, stirred by a high-speed mixer for about 1 hour while being heated to about 70 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 80 ℃ for a whole day and night and pulverized to obtain a yellow pigment (E-8) having a fine particle size.

(micronized yellow pigment (E-9))

100 parts of c.i. pigment Yellow 185 ("pailotol Yellow) D1155" manufactured by BASF corporation, japan, 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by uphole manufacturing corporation), and kneaded at 80 ℃ for 6 hours. Subsequently, the kneaded mixture was put into 8 liters of warm water, stirred by a high-speed mixer for 2 hours while being heated to 80 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 85 ℃ for a whole day and night and pulverized to obtain a yellow pigment (E-9) having fine particles.

(micronized yellow pigment (E-10))

According to examples of Japanese patent laid-open No. 2012-226110, a yellow pigment (E-10) of the following chemical formula (18) was obtained. 100 parts of yellow pigment (E-10), 700 parts of pulverized sodium chloride and 180 parts of diethylene glycol were charged in a stainless 1-gallon kneader (manufactured by UK Co., ltd.), and kneaded at 80 ℃ for 6 hours. Subsequently, the kneaded mixture was put into 8 liters of warm water, stirred by a high-speed mixer for 2 hours while being heated to 80 ℃ to prepare a slurry, and after removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the slurry was dried at 85 ℃ for a whole day and night and pulverized to obtain a yellow pigment (E-10) having a fine particle size.

Chemical formula (18)

[ solution 14]

The micronized pigment has an average primary particle diameter in the range of 5nm to 120 nm.

(dye (E-11))

A dye (E-11) as a salt-forming compound of the resin 1 containing c.i. acid red 52 and a cationic group in a side chain was produced in the following order.

67.3 parts of methyl ethyl ketone was charged in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube and a cooler, and the temperature was raised to 75 ℃ under a nitrogen stream. Further, 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, 6.5 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized and charged into a dropping funnel, and the dropping funnel was mounted in a four-necked separable flask and dropped over 2 hours. 2 hours after the completion of the dropwise addition, the polymerization yield was 98% or more and the weight-average molecular weight (Mw) was 6,830, as confirmed from nonvolatile components, and the mixture was cooled to 50 ℃. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50 ℃ for 2 hours, and then heated to 80 ℃ over 1 hour, followed by reaction for 2 hours. Thus, resin 1 having a cationic group in a side chain having an ammonium group was obtained with a resin component of 47 mass%. The ammonium salt value of the obtained resin was 34mgKOH/g.

Next, 30 parts of resin 1 having a cationic group in a side chain was added to 2,000 parts of water in terms of nonvolatile content, sufficiently stirred and mixed, and then heated to 60 ℃. On the other hand, an aqueous solution in which 10 parts of c.i. acid red 52 was dissolved in 90 parts of water was prepared, and this was added dropwise to the resin solution immediately before. After the dropwise addition, the mixture was stirred at 60 ℃ for 120 minutes to sufficiently react. As the end point of the reaction, the reaction solution was dropped on the filter paper, and it was judged that the salt-forming compound was obtained at the end point when the bleeding disappeared. After leaving to cool to room temperature with stirring, the mixture was suction-filtered and washed with water, and then the salt-forming compound remaining on the filter paper was dried by removing water with a dryer to obtain 32 parts of a dye (E-11) which is a salt-forming compound of c.i. acid red 52 and resin 1 having a cationic group in a side chain. In this case, the content of the component derived from c.i. acid red 52 in the dye (E-11) was 25% by mass.

< production of alkali-soluble resin (A) >

(alkali soluble resin (A1-1) solution)

To a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device in a separable four-necked flask, 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed, and heated to 120 ℃ while injecting nitrogen into the vessel, and a mixture of 99.4 parts of 2-ethylhexyl acrylate (hereinafter, 2-EHA (2-ethylhexyl acrylate)), 49.7 parts of glycidyl methacrylate (hereinafter, GMA (glycidyl methacrylate)), 6.6 parts of dicyclopentyl methacrylate (hereinafter, DCPMA (dicyclopentyl methacrylate)), and 19.0 parts of peroxy-tert-butyl-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from a dropping tube at the above temperature over 2.5 hours.

After the completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 2 hours to obtain a precursor. Subsequently, the flask was charged with air, 50.4 parts of acrylic acid (hereinafter referred to as AA (acrylic)) as a modified compound, 0.6 part of triphenylphosphine as a catalyst, and 0.2 part of methylhydroquinone were charged, and the mixture was reacted at 110 ℃ for 10 hours. Thereby, a monomer unit (hereinafter, GMA + AA) obtained by reacting the epoxy group of GMA and the carboxyl group of AA is obtained, and the polymerizable unsaturated group-containing monomer unit (a 2) is introduced.

Then, 21.3 parts of tetrahydrophthalic anhydride (hereinafter, THPA) as a modified compound was added thereto, and the mixture was reacted at 110 ℃ for 4 hours. Thereby, a part of the hydroxyl groups of GMA + AA is reacted with THPA. Thereafter, PGMAc was added so that the nonvolatile content became 20% by mass, to prepare an alkali-soluble resin (A1-1), wherein the alkali-soluble resin (A1-1) contained a monomer unit (A1) containing an alicyclic hydrocarbon, a monomer unit (a 2) containing a polymerizable unsaturated group, and a monomer unit (a 3) having a homopolymer glass transition temperature of 0 ℃ or lower. The acid value of the alkali-soluble resin (A1-1) was 38mgKOH/g, and the weight-average molecular weight was 12,000.

(alkali-soluble resin (A1-2) solution to alkali-soluble resin (A1-6) solution)

The alkali-soluble resins (A1-2) to (A1-6) were synthesized in the same manner as the alkali-soluble resin (A1-1) by changing the kind and amount of the formulation so as to obtain the composition ratios shown in Table 1, and PGMAc was added to make the nonvolatile content 20% by mass.

[ Table 1]

MAA + GMA shown in table 1 represents a polymerizable unsaturated group-containing monomer unit (a 2) obtained by adding an epoxy group of GMA to a carboxyl group of methacrylic acid (hereinafter referred to as MAA (methacrylic acid)) in a precursor. GMA + AA + SAH represents a polymerizable unsaturated group-containing monomer unit (a 2) obtained by reacting a part of the hydroxyl groups of GMA + AA with succinic anhydride (hereinafter referred to as SAH).

(alkali-soluble resin (A2-1) solution)

Into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device in a separable four-necked flask was charged 196 parts of cyclohexanone, the temperature was raised to 80 ℃ and the inside of the reaction vessel was replaced with nitrogen, and then, over 2 hours, a mixture of 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, and 24.1 parts of p-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toyo Seisakusho Co., ltd.) and 1.1 parts of 2,2' -azobisisobutyronitrile was dropped from the dropping tube. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, dried by heating at 180 ℃ for 20 minutes, and the nonvolatile content was measured, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20 mass%, to prepare an alkali-soluble resin (A2-1) solution. The acid value was 87mgKOH/g, and the weight-average molecular weight was 25,000.

(alkali-soluble resin (A2-2) solution and alkali-soluble resin (A2-3) solution)

The alkali-soluble resin (A2-2) and the alkali-soluble resin (A2-3) were synthesized by changing the kind and amount of the formulation so as to have the composition ratios shown in Table 2, and PGMAc was added to make the nonvolatile content 20% by mass.

[ Table 2]

< production of polymerizable Compound (B) >

(polymerizable Compound (B2-2) having acid group)

Five parts including a stirrer, a reflux cooling tube, a nitrogen inlet tube, a thermometer and a dropping tubeA flask was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine, heated to 70 ℃ and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise over 2 hours from a dropping tube. After the dropwise addition, the reaction was carried out at 50 ℃ to 70 ℃ for 8 hours, and 2180cm was confirmed by Infrared Spectroscopy (IR) ^-1 Disappearance of the isocyanate absorption. Then, 35 parts of thioglycolic acid and 0.6 part of 4-methoxyphenol were charged and reacted at 50 ℃ to 60 ℃ for 6 hours. The nonvolatile content was adjusted to 50% by mass, and a polymerizable compound (B2-2) having an acid group was obtained.

< production of Dispersion resin (G) >

(Dispersion resin (G-1) solution)

10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and were replaced with nitrogen. The reaction vessel was heated to 50 ℃ with stirring, and 12 parts of 3-mercapto-1, 2-propanediol was added thereto. The reaction mixture was heated to 90 ℃ and reacted for 7 hours while adding a solution prepared by adding 0.1 part of 2,2' -azobisisobutyronitrile to 90 parts of PGMAc. The nonvolatile content measurement confirmed that 95% of the reaction had occurred. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1, 8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added thereto, and the mixture was reacted at 100 ℃ for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified to complete the reaction, and PGMAc was added to the nonvolatile matter measurement to dilute the solution so that the nonvolatile matter became 30%, thereby obtaining a dispersant (G-1) solution having an acid value of 70mgKOH/G and a weight average molecular weight of 8,500.

(Dispersion resin (G-2) solution)

A reaction vessel equipped with a gas inlet, a thermometer, a condenser and a stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc and 0.2 part of monobutyltin oxide as a catalyst, and the mixture was replaced with nitrogen gas and reacted at 120 ℃ for 5 hours (first step). It was confirmed that the acid value was 95% of the acid anhydride is half-esterified. Then, the compound obtained in the first step, 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, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged in an amount of 160 parts in terms of nonvolatile matter, the inside of the reaction vessel was heated to 80 ℃ and 1.2 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added to the reaction vessel to conduct a reaction for 12 hours (second step). The nonvolatile content measurement confirmed that 95% of the reaction had occurred. Finally, 500 parts of a PGMAc diluted solution containing 50% nonvolatile components 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 reaction was carried out until 2270cm of isocyanate groups were confirmed by IR ^-1 The peak of (4) disappears (third step). After the disappearance of the peak was confirmed, the reaction solution was cooled and the nonvolatile content was adjusted by PGMAc to obtain a dispersion resin (G-2) solution having a nonvolatile content of 30%. The acid value of the obtained dispersion resin (G-2) was 68mgKOH/G, the unsaturated double bond equivalent was 1,593, and the weight-average molecular weight was 13,000.

(Dispersion resin (G-3) solution)

A reaction apparatus equipped with a gas inlet, a condenser, a stirring blade and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ℃ for 1 hour while flowing nitrogen gas, thereby substituting nitrogen gas in the system. 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 ℃ under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion was 98% or more in terms of nonvolatile content.

Then, 61 parts of PGMAc and 20 parts of 1,2, 6-pentamethylpiperidine methacrylate (manufactured by Hitachi chemical Co., ltd., faNCRYL) FA-711MM as a second block (A block) monomer were charged into the reaction apparatus, and the reaction was continued by stirring while maintaining the temperature at 110 ℃ under a nitrogen atmosphere. After 2 hours from the charging of 1,2,2,6,6-pentamethylpiperidine methacrylate, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion of the second block (A block) was 98% or more in terms of nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization. Then, PGMAc was added to the nonvolatile matter measurement and diluted so that the nonvolatile matter became 30%, to obtain a dispersion resin (G-3) solution having an amine value of 57mgKOH/G per nonvolatile matter and a number average molecular weight of 4,500 (Mn).

(Dispersion resin (G-4) solution)

To a 500mL round-bottom four-necked separable flask equipped with a cooling tube, an addition funnel, an inlet for nitrogen gas, a stirrer, and a digital thermometer, 250 parts by mass of Tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyltrimethylacetal as an initiator were added through the addition funnel, and then nitrogen gas substitution was sufficiently performed. 0.5 part by mass of a 1mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected by a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 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 as a solvent-philic block monomer were added dropwise over 60 minutes by using an addition funnel. The temperature was maintained at less than 40 ℃ by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide as a block monomer having a colored material adsorbing function was added dropwise over 20 minutes. After 1 hour of the reaction, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, filtered, and vacuum dried to purify the product.

Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100mL round-bottomed flask, and 1.1 parts by mass of phenylphosphonic acid (0.5 molar equivalent to dimethylaminopropyl methacrylamide) as a salt-forming component was added thereto, and the mixture was stirred at a reaction temperature of 30 ℃ for 20 hours, followed by addition of PGMAc to adjust the reaction temperature, thereby obtaining a dispersion resin (G-4) solution having a nonvolatile content of 30%.

Production of Dispersion

(Dispersion 1)

After dispersion for 3 hours using zirconia beads having a diameter of 0.5mm by an Eigermall mill ("mini model) M-250 MKII" manufactured by Eiger Japan, the following was made, and filtration was performed using a filter having a pore size of 1.0 μ M to prepare a dispersion 1 having the following composition. The organic solvent (P-1) is PGMAc.

[ solution 15]

pc denotes 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.

[ Table 3]

Pigment derivatives (F-2) of Table 3: the following structure

[ solution 16]

Pigment derivatives (F-3) of Table 3: the following structure

[ solution 17]

< production of photosensitive composition >

[ example 1]

(photosensitive composition 1)

The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.

Examples 2 to 35 and comparative examples 1 to 3

(photosensitive composition 2 to photosensitive composition 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.

[ Table 4-1]

The raw materials described in tables 4-1 to 4-4 are as follows.

[ polymerizable Compound (B) ]

(lactone-modified polymerizable Compound (B1))

B1-1: kayarad (KAYARAD) DPCA-30 (manufactured by Nippon chemical Co., ltd.)

B1-2: kayarad (KAYARAD) DPCA-20 (manufactured by Nippon chemical Co., ltd.)

(polymerizable Compound (B2) having acid group)

B2-1: aronix M-520 (manufactured by Toya Synthesis Co., ltd.)

(other polymerizable Compound (B3))

B3-1: kayarad DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon chemical Co., ltd.)

[ photopolymerization initiator (C) ]

(Compound (C1) represented by the general formula (1))

C1-1: the compound of the formula (2)

C1-2: the compound of the formula (3)

C1-3: the compound of the formula (4)

(Oxime photopolymerization initiator (C2))

C2a-1: strong (TRONLY) TR-PBG-3057 (a compound containing an oxime group in one molecule, manufactured by Changzhou Strong New Material Co., ltd.)

C2a-2: the compound of the formula (5)

C2a-3: the compound of the formula (6)

C2a-4: the compound of the formula (7)

C2a-5: the compound of the formula (8)

C2b-1: the compound of the formula (10)

C2b-2: the compound of the formula (13)

(other photopolymerization initiator (C3))

C3-1: onnirad (Omnirad) 907 (acetophenone-based compound, manufactured by IGM resins (IGMResins))

C3-2: ohniera ni rad (Omnirad) 369 (acetophenone Compounds, manufactured by IGM resins Ltd.)

[ sensitizer (D) ]

(thioxanthone-based Compound (D1))

D1-1:2, 4-diethylthioxanthone

(benzophenone-series Compound (D2))

D2-1:4,4' -bis (diethylamino) benzophenone

[ thermosetting Compound (H) ]

(epoxy Compound (H1))

H1-1: EHPE-3150 (manufactured by Daicel corporation)

[ polymerization inhibitor (J) ]

J-1: 4-Methylcatechol

J-2: methyl hydroquinone

J-3: tert-butyl hydroquinone

As described above, (J-1) to (J-3) were mixed in the same amount as the polymerization inhibitor (J).

[ leveling agent (M) ]

M-1: BYK-330 (manufactured by BYK-Chemie)

M-2: meijiafa (Megafac) F-551 (manufactured by Diegon (DIC))

As described above, 1 part each of (M-1) and (M-2) was mixed, and the resulting mixture was dissolved in 98 parts of PGMAc to prepare a leveling agent (M).

[ organic solvent (P) ]

P-1: propylene glycol monomethyl ether acetate 30 parts

P-2: cyclohexanone 30 parts

P-3: 10 portions of 3-ethoxy ethyl propionate

P-4: 10 portions of propylene glycol monomethyl ether

P-5: 10 portions of cyclohexanol acetic ester

P-6: 10 parts of dipropylene glycol methyl ether acetate

As the organic solvent (P), the organic solvents (P) mentioned above were mixed in the above amounts of (P-1) to (P-6), respectively.

< evaluation of photosensitive composition >

The obtained photosensitive compositions 1 to 38 (examples 1 to 35 and comparative examples 1 to 3) were evaluated for water stain, pattern shape (adhesion and cross-sectional shape), and heat resistance by the following methods. The evaluation results are shown in table 5.

[ evaluation of Water stain ]

The obtained photosensitive composition was applied to a glass substrate (eagle 2000 manufactured by Corning) having a thickness of 100mm in the vertical direction by 100mm in the horizontal direction and 0.7mm in the thickness by a spin coating method so that the film thickness after drying became 2.0 μm, and dried at 70 ℃ for 1 minute by a hot plate. Then, through a mask having a stripe pattern of 100 μm width, a high pressure mercury lamp was used at an illuminance of 30mW/cm ² 、50mJ/cm ² Ultraviolet exposure was performed under the conditions of (1). Thereafter, the resultant was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ℃ for 40 seconds to develop the resist, and then washed with pure water. The surface of the obtained pattern was observed with an optical microscope of Model (Model) LV100POL (ECLIPSE) manufactured by Nikon (Nikon) to evaluate the degree of discolored portion. The evaluation criteria are as follows, and 3 or more is considered to be practical.

5: no water stain.

4: the water stain is less than 10 percent of the whole body.

3: the water stain accounts for more than 10 percent to less than 20 percent of the whole body.

2: the water stain accounts for more than 20 percent to less than 30 percent of the whole body.

1: the water stain accounts for more than 30 percent of the whole body.

[ evaluation of pattern shape (1): adaptation of adhesion

The obtained photosensitive composition was applied to a glass substrate (eagle 2000 manufactured by Corning) having a thickness of 100mm in the vertical direction x 100mm in the horizontal direction and 0.7mm in the thickness by a spin coating method so that the film thickness after drying became 2.0 μm, and dried at 70 ℃ for 1 minute by a hot plate. Then, the substrate was cooled to room temperature, and then a high-pressure mercury lamp was used to illuminate 30mW/cm through a photomask having a stripe pattern of 5 μm width in the range of 5 μm to 25 μm in width ² 、50mJ/cm ² And (6) carrying out exposure. Thereafter, the substrate was spray-developed using an aqueous developing solution containing 0.12 mass% of a nonionic surfactant and 0.04 mass% of potassium hydroxide at 23 ℃, and then washed with ion-exchanged water, air-dried, and subjected to dryingHeating in a clean oven at 230 ℃ for 30 minutes. The spray development is performed in the shortest time for forming a pattern without any development residue on the film formed from each photosensitive composition.

The patterns having widths of 5 μm, 10 μm, 15 μm, 20 μm and 25 μm on the obtained substrate were observed by an optical microscope, and the minimum line width of the remaining pattern was confirmed. The evaluation criteria are as follows, and 3 or more is considered to be practical.

5: thin lines of 10 μm or less remain.

4: there remain fine lines of 15 μm or more.

3: thin lines of 20 μm or more remain.

2: thin lines of 25 μm were left.

1: no fine lines remained.

[ evaluation of pattern shape (2): section shape

The obtained photosensitive composition was applied to a glass substrate (eagle 2000 manufactured by Corning) having a thickness of 100mm in the vertical direction by 100mm in the horizontal direction and 0.7mm in the thickness by a spin coating method so that the film thickness after drying became 2.0 μm, and dried at 70 ℃ for 1 minute by a hot plate. Then, the substrate was cooled to room temperature, and then, a high-pressure mercury lamp was used to set an illuminance of 30mW/cm through a photomask having a stripe pattern of 100 μm width ² 、50mJ/cm ² And (6) carrying out exposure. Thereafter, the substrate was spray-developed using an aqueous developer containing 0.12 mass% of a nonionic surfactant and 0.04 mass% of potassium hydroxide at 23 ℃, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ℃ for 30 minutes. The spray development is performed in the shortest time for forming a pattern without any development residue on the film formed from each photosensitive composition.

The cross-sectional shape of the pattern was confirmed using a scanning electron microscope ("S-3000H" manufactured by hitachi high and new technologies). Evaluation was carried out by taking an SEM image of a cross section of a stripe pattern 100 μm wide and measuring the taper angle between the substrate and the end of the pattern cross section. The evaluation criteria are as follows, and 3 or more are considered to be practical.

5: the taper angle is more than 30 degrees and less than 50 degrees

4: the cone angle is more than 50 degrees and less than 60 degrees

3: the taper angle is less than 30 degrees or more than 60 degrees and less than 70 degrees

2: the taper angle is more than 70 degrees and less than 90 degrees

1: the cone angle is more than 90 degrees

[ evaluation of Heat resistance ]

The obtained photosensitive composition was applied to a glass substrate (eagle 2000 manufactured by Corning) having a thickness of 100mm in the vertical direction x 100mm in the horizontal direction and 0.7mm in the thickness by a spin coating method so that the thickness after drying became 2.0 μm, and dried at 70 ℃ for 1 minute by a hot plate. Then, the substrate was cooled to room temperature, and then the substrate was irradiated with light at an illuminance of 30mW/cm using a high-pressure mercury lamp ² 、50mJ/cm ² And (6) carrying out exposure. Thereafter, the resultant was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ℃ for 40 seconds to develop, followed by washing with ion-exchanged water, air-drying, and heating at 230 ℃ for 30 minutes in a clean oven.

The chromaticity ([ L × 1, a × 1, b × 1) ] of the obtained coating film under a C light source was measured using a microspectrophotometer ("OSP-SP 100" manufactured by Olympus optics corporation). Further, as a heat resistance evaluation, chromaticity ([ L × (2), a × (2), b × (2)) under a C light source was measured by heating at 230 ℃ for 1 hour, and a color difference Δ Eab was obtained by the following calculation formula. The evaluation criteria are as follows, and 3 or more is considered to be practical.

ΔEab*＝((L*(2)-L*(1)) ² +(a*(2)-a*(1)) ² +(b*(2)-b*(1)) ² ) ^1/2

5: delta Eab is less than 1

4: delta Eab is 1-2

3: delta Eab is 2-3

2: delta Eab is 3-5

1: delta Eab is more than 5

[ Table 5]

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B) and a photopolymerization initiator (C),

the photopolymerization initiator (C) comprises a compound (C1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (C2),

general formula (1)

In the general formula (1), R ₁ 、R ₂ Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; r is ₃ Represents a hydrogen atom or a monovalent substituent.

2. The photosensitive composition according to claim 1, wherein the oxime-based photopolymerization initiator (C2) comprises a compound (C2 b) having two oxime groups in one molecule.

3. The photosensitive composition according to claim 1 or 2, wherein the alkali-soluble resin (a) comprises an alkali-soluble resin (A1), and the alkali-soluble resin (A1) comprises a monomer unit (A1) containing an alicyclic hydrocarbon and a monomer unit (a 2) containing a polymerizable unsaturated group.

4. The photosensitive composition according to claim 3, wherein the alkali-soluble resin (A1) is a resin containing a monomer unit (a 3) having a homopolymer glass transition temperature of 0 ℃ or lower.

5. The photosensitive composition according to any one of claims 1 to 4, further comprising a sensitizer (D).

6. An optical filter having: a substrate; and a filter segment formed from the photosensitive composition according to any one of claims 1 to 5.

7. An image display device having the optical filter according to claim 6.

8. A solid-state image pickup element having the optical filter according to claim 6.