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

Abstract

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

Description

Technical Field

[0001] The present invention relates to a photosensitive composition and its use.

Background Art

[0002] A color filter, which is a type of optical filter used in image display devices, solid-state imaging devices, etc., is obtained, for example, by applying a photosensitive composition to a transparent substrate such as glass, removing the solvent from this coating film by drying, irradiating and curing this coating film with radiation (hereinafter referred to as exposure) through a photomask having a desired pattern shape, then washing and removing the unexposed portion of this coating film (hereinafter referred to as development), and then, if necessary, performing a heat treatment (hereinafter referred to as post-bake) to sufficiently cure the cured film to obtain a filter segment pattern of the first color. And by performing the same operation as this, filter segment patterns of other colors can be formed and manufactured.

[0003] In the above development process, an alkaline developer is used as the developer to wash and remove the unexposed portion. At that time, there was a problem that the exposed portion chipped or peeled off, resulting in defects in the pattern shape. Also, when the coating film was exposed to the alkaline developer, there was a problem that a phenomenon of discoloration of the coating film (hereinafter referred to as water stain) occurred. Therefore, a photosensitive composition that does not cause pattern shape defects and water stains in the development process is required. Furthermore, there was also a problem that the color changed during the post-bake process.

[0004] As an effort to improve water stains, Patent Document 1 discloses a colored photosensitive resin composition containing an alkali-soluble resin having a specific structure and an oxime ester fluorene derivative compound as a photopolymerization initiator. Also, Patent Document 2 discloses a resist composition containing a fluorine-based surfactant having a specific structure. As an effort to improve pattern chipping during development, Patent Document 3 discloses a colored composition containing a polymerizable compound having an alkylene oxide structure.

Prior Art Documents

Patent Document

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, none of the compositions described in Patent Documents 1 to 3 could satisfy all of water stain, pattern shape, and heat resistance at a certain level or higher.

[0007] An object of the present invention is to provide a photosensitive composition that suppresses water stain of a film after development, has good heat resistance, and can form an excellent pattern.

Means for Solving the Problems

[0008] The present invention relates to a photosensitive composition containing an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C), wherein the photopolymerization initiator (C) contains a compound (C1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (C2). General formula (1)

Chemical formula

[0009] (In 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.)

Effects of the Invention

[0010] According to the present invention described above, it is possible to provide a photosensitive composition that suppresses water bleeding of the film after development, has good heat resistance, and can form excellent patterns. Further, the present invention can provide an optical filter, an image display device, and a solid-state imaging device.

Mode for Carrying Out the Invention

[0011] Hereinafter, embodiments for implementing the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0012] In the present invention, “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” means “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively, unless otherwise specified. Further, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compound in the present invention, for a low-molecular compound whose molecular weight can be specified, it is the value calculated by calculation (formula weight) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). For a compound having a molecular weight distribution, it is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is a state in which the monomer forms a resin after polymerization. A polymerizable compound is a compound that forms a film by polymerization.

[0013] <Photosensitive Composition> One embodiment of the present invention relates to a photosensitive composition. The photosensitive composition of the present invention is a photosensitive composition containing an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C), characterized in that 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) [Chemical formula]

[0014] (In 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.)

[0015] Although the mechanism by which the photosensitive composition having the above configuration can solve the problems of the present invention is not clear, it is speculated as follows. Compared with 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, which are photopolymerization initiators widely used in the field of color filters, the compound (C1) represented by the general formula (1) has a fluorene skeleton that is rigid, hydrophobic, and has high heat resistance. Therefore, it is speculated that a highly resistant cured film can be obtained. In addition, due to the π-π interaction of the two benzene rings, the cured film has appropriate cohesive force. Therefore, while suppressing defects in the pattern during development, it has a structure that is moderately easy to soften with respect to heat, and it is speculated that heat sag occurs during host baking and the cross-sectional shape of the pattern becomes good. And since the absorption wavelength is different from that of the compound (C1) represented by the general formula (1), by using a specific oxime-based photopolymerization initiator (C2) having high sensitivity in combination, the wavelength region of light available for photopolymerization is widened and the reactivity is improved. Therefore, for example, it is speculated that even for a composition containing a colorant that is difficult to transmit light to the deep part of the film, the reaction proceeds, bleeding of the film after development is suppressed, and the pattern shape and heat resistance are improved.

[0016] Hereinafter, the components contained in or that can be contained in the photosensitive composition of one embodiment will be described in detail.

[0017] [Photoinitiator (C)] The photosensitive composition of the present invention contains, as the photoinitiator (C), a compound (C1) represented by the general formula (1) and an oxime-based photoinitiator (C2).

[0018] (Compound (C1) represented by the general formula (1)) The photosensitive composition of the present invention contains, as the photoinitiator (C), a compound (C1) represented by the general formula (1).

[0019] General formula (1) [Chemical formula] (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.)

[0020] R 1 , R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include linear, branched, cyclic, or those in which they are combined, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. Among them, from the viewpoints of suppressing water stain 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.

[0021] R 3represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group and an ethoxy group; a halogen atom such as F, Cl, Br, and I; 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 tenoyl group which may have a substituent, and the like. Examples of the substituent that the benzoyl group or the tenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and the like. Among them, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferable, and a hydrogen atom is more preferable.

[0022] Examples of the method for producing the compound (C1) represented by the general formula (1) include the methods described in JP-T-2019-507108, JP-T-2019-528331, and the like.

[0023] Specific examples of the compound (C1) represented by the general formula (1) are shown below. However, the present invention is not limited thereto.

[0024]

Chemical formula

[0025] Among the compounds of Chemical formulas (2) to (4), the compound of Chemical formula (2) is preferable from the viewpoints of suppressing water bleeding, pattern shape, and heat resistance.

[0026] The compound (C1) represented by the general formula (1) can be used alone or in combination of two or more.

[0027] (Oxime-based photoinitiator (C2)) The oxime-based photoinitiator (C2) includes a compound (C2a) containing one oxime group in one molecule and a compound (C2b) containing two oxime groups in one molecule. From the viewpoint of suppressing water stain, the compound (C2b) containing two oxime groups in one molecule is more preferable.

[0028] [Compound (C2a) containing one oxime group in one molecule] Commercially available products of the compound (C2a) containing one oxime group in one molecule include, for example, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF, Adeka Arcles N-1919, NCI-730, 831, 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., OMNIRAD1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 06, 07 manufactured by Samyang Corporation, DFI-020, 036, EOX-01, etc. manufactured by Daito Chemicals.

[0029] Specific examples of the compound (C2a) containing one oxime group in one molecule include, for example, the following. Note that the present invention is not limited thereto.

[0030] Chemical formula (5)

Chemical formula

Chemical formula

[0031] Examples of the production methods of the compounds of Chemical formulas (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, Japanese Patent Application Laid-Open No. 2017-512886, etc.

[0032] The compound (C2a) containing one oxime group in one molecule preferably contains at least one selected from the group consisting of the compounds represented by Chemical Formulas (5) to (8) from the viewpoints of pattern shape and heat resistance.

[0033] The compound (C2a) containing one oxime group in one molecule can be used alone or in combination of two or more.

[0034] 〔Compound (C2b) containing two oxime groups in one molecule〕 Examples of the compound (C2b) containing two oxime groups in one molecule include compounds described in JP-A-2005-215378, JP-A-2011-105713, JP-T-2017-523465, JP-A-2021-011486, etc. Among them, the compound represented by the following General Formula (9) is preferable.

[0035] General Formula (9)

Chemical Formula

[0036] In General Formula (9), X 1 and X 2independently represents a carbonyl bond (-CO-) or a single bond. Among them, from the perspective of solubility in organic solvents, X 1 and X 2 at least one of them is preferably a carbonyl bond (-CO-), and it is more preferable that X 1 and X 2 are carbonyl bonds (-CO-).

[0037] In general formula (9), X 3 is a single bond or a sulfur atom, and a single bond is preferred.

[0038] In general formula (9), R 1 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof alkyl group, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. can be mentioned. Among these, an ethyl group, a propyl group, and an isopropyl group are preferred.

[0039] In 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 ring 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 a linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. can be mentioned. Among these, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group are preferable. The heterocyclic group having 2 to 30 carbon atoms includes, for example, a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, etc. The aryl group having 6 to 30 carbon atoms includes, for example, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc. The arylalkyl group having 7 to 30 carbon atoms includes, for example, a benzyl group, an α-methylbenzyl, an α,α-dimethylbenzyl group, a phenylethyl group, etc. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc.

[0040] Among these, R 2 and R 3 From the viewpoint of solubility in an organic solvent, at least one is preferably a linear alkyl group having 1 to 20 carbon atoms, and from the viewpoints of solubility in an organic solvent and suppression of water stain, a linear alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms are more preferable.

[0041] In the general formula (9), R 4and 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 a linear, branched, cyclic, or a combination thereof alkyl group, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, etc. can be mentioned. Among these, from the viewpoint of reactivity, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable. Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, etc. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may also be a group substituted with a halogen atom, an amino group, a nitro group, etc. Among these, from the viewpoint of reactivity, a phenyl group is preferable. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl, an α,α-dimethylbenzyl group, a phenylethyl group, etc. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc.

[0042] Among these, R 4 and R 5 from the viewpoint of reactivity, a methyl group, an ethyl group, or a phenyl group is preferable, and a methyl group or an ethyl group is more preferable.

[0043] The production method of the compound represented by the general formula (9) is not particularly limited, and known methods can be used. For example, the methods described in JP-T-2017-523465, JP-A-2021-011486, etc. can be used.

[0044] Hereinafter, specific examples of the compound (C2b) containing two oxime groups in one molecule are shown. Note that the present invention is not limited thereto.

[0045]

Chemical formula

Chemical formula

[0046] Among the chemical formulas (10) to (13), from the viewpoint of suppressing water stains, the compound of the chemical formula (10) is preferable.

[0047] The compound (C2b) containing two oxime groups in one molecule can be used alone or in combination of two or more.

[0048] From the viewpoints of suppressing water stains, 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, and particularly preferably 70:30 to 30:70.

[0049] From the viewpoints of suppressing water stains, 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, more preferably 80 to 100% by mass in 100% by mass of the photopolymerization initiator (C).

[0050] (Other photopolymerization initiator (C3)) The photosensitive composition of the present invention can contain a compound (C1) represented by the general formula (1) and a photopolymerization initiator (C3) other than the oxime-based photopolymerization initiator (C2) (hereinafter, also referred to as the other photopolymerization initiator (C3)).

[0051] The other photopolymerization initiator (C3) is not particularly limited as long as it is a compound capable of initiating the polymerization of the polymerizable compound (B) by light, and known photopolymerization initiators can be used. For example, acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Triazine-based compounds such as 2,4,6-trichloros-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-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Acylphosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the quinone compounds include 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc.; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

[0052] Other photoinitiators (C3) can be used alone or in combination of two or more.

[0053] From the viewpoint of photocurability, the content of the photoinitiator (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).

[0054] [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.

[0055] The alkali-soluble resin (A) may be any resin that dissolves in an alkali developer, and known resins can be used. The alkali-soluble resin (A) preferably has an alkali-soluble group such as a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Among these, a carboxyl group is preferred. Specific examples include acrylic resins having an acidic group, α-olefin / (meth)maleic anhydride copolymers, styrene / styrenesulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (meth)maleic anhydride copolymers. Further, the alkali-soluble resin (A) can contain a polymerizable unsaturated group such as a vinyl group, a (meth)allyl group, or a (meth)acryloyl group, or a thermosetting group such as an epoxy group or an oxetanyl group.

[0056] 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.

[0057] The acid value of the alkali-soluble resin (A) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g, from the viewpoint of developability.

[0058] The content of the alkali-soluble resin (A) is preferably from 1 to 80 mass %, and more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0059] The alkali-soluble resin (A) can be used alone or in combination of two or more kinds.

[0060] (Alkali-soluble resin (A1)) From the viewpoint of suppressing water stains and heat resistance, the alkali-soluble resin (A) preferably contains an alkali-soluble resin (A1) containing an alicyclic hydrocarbon-containing monomer unit (a1) and a polymerizable unsaturated group-containing monomer unit (a2). It is presumed that the alicyclic hydrocarbon structure, which is highly hydrophobic and has both flexibility and rigidity, has low affinity with the developer and can form a tough film. It is presumed that the presence of a polymerizable unsaturated group allows the resins to crosslink with each other upon exposure to form a tougher cured film, suppressing water stains and obtaining a pattern with good heat resistance.

[0061] The alkali-soluble resin (A1) is not particularly limited as long as it contains an alicyclic hydrocarbon-containing monomer unit (a1) and a polymerizable unsaturated group-containing monomer unit (a2), and known resins can be used. For example, a copolymer of a monomer forming an alicyclic hydrocarbon-containing monomer unit (a1) and a monomer forming a polymerizable unsaturated group-containing monomer unit (a2), a copolymer of a monomer forming an alicyclic hydrocarbon-containing monomer unit (a1) and another monomer copolymerizable therewith, reacting a compound having a polymerizable unsaturated group to introduce a polymerizable unsaturated group-containing monomer unit (a2), or a copolymer obtained by the method described in JP-A-2008-165059, etc. are mentioned. The polymerizable unsaturated group-containing monomer unit (a2) is a unit containing a polymerizable unsaturated group in the unit. The alkali-soluble group may be present at any site of the resin (A1).

[0062] [Alicyclic hydrocarbon-containing monomer unit (a1)] Examples of the monomer that forms the alicyclic hydrocarbon-containing monomer unit (a1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Among these, from the viewpoints of suppressing water stain and pattern shape, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferable.

[0063] From the viewpoints of suppressing water stain and pattern shape, the content of the alicyclic hydrocarbon-containing monomer unit (a1) is preferably 1 to 60 mol%, more preferably 1 to 40 mol%, based on all the constituent units of the alkali-soluble resin (A1).

[0064] [Polymerizable unsaturated group-containing monomer unit (a2)] Examples of the method for incorporating the polymerizable unsaturated group-containing monomer unit (a2) into the alkali-soluble resin (A1) include the following methods (i) to (iii).

[0065] [Method (i)] In method (i), for example, first, a polymer (precursor) of an epoxy group-containing monomer and other monomers is synthesized. Next, a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0066] 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.

[0067] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0068] From the viewpoint of developability, a product obtained by reacting an acid anhydride with a product obtained by adding the carboxyl group of a carboxyl group-containing monomer to the epoxy group of an epoxy group-containing monomer unit is also preferable as the polymerizable unsaturated group-containing monomer unit (a2).

[0069] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

[0070] <Method (ii)> In method (ii), for example, first, a polymer (precursor) of a carboxyl group-containing monomer and other monomers is synthesized. Next, an epoxy group-containing monomer (modifying compound) is added to a part of the carboxyl groups of the precursor to have a carboxyl group and a polymerizable unsaturated group.

[0071] <Method (iii)> In method (iii), for example, first, a polymer (precursor) of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers is synthesized. Next, the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0072] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate.

[0073] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

[0074] From the viewpoint of the pattern shape, the content of the polymerizable unsaturated group-containing monomer unit (a2) is preferably 5 to 80 mol%, more preferably 10 to 80 mol%, based on all the constituent units of the alkali-soluble resin (A1).

[0075] [Monomer unit (a3) in which the glass transition temperature of the homopolymer is 0°C or lower] From the viewpoint of the pattern shape, the alkali-soluble resin (A1) preferably contains a monomer unit (a3) (excluding (a1) and (a2)) in which the glass transition temperature of the homopolymer is 0°C or lower. More preferably, it is a monomer unit (a3) in which the glass transition temperature of the homopolymer is -10°C or lower, and particularly preferably, it is a monomer unit (a3) in which the glass transition temperature of the homopolymer is -30°C or lower. Here, the homopolymer refers to a homopolymer of each monomer, and the value of the glass transition temperature uses the value shown in "Polymer Handbook, Third edition, John wiley & sons, 1989" edited by Brandrup, J. and Immergut, E. H.

[0076] Monomers that form monomer units (a3) with a glass transition temperature of the homopolymer of 0 °C or lower include, for example, phenoxyethyl acrylate (-22 °C), lauryl acrylate (-3 °C), 2-ethylhexyl acrylate (-50 °C), n-hexyl acrylate (-57 °C), n-butyl acrylate (-48 °C), isobutyl acrylate (-40 °C), ethyl acrylate (-24 °C), lauryl methacrylate (-65 °C), n-hexyl methacrylate (-5 °C), 2-ethylhexyl methacrylate (-10 °C), 2-methoxyethyl acrylate (-50 °C), tetrahydrofurfuryl acrylate (-12 °C), and the like. Among these, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred.

[0077] From the viewpoint of the pattern shape, the content of the monomer unit (a3) with a glass transition temperature of the homopolymer of 0 °C or lower is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all the constituent units of the alkali-soluble resin (A1).

[0078] 〔Other monomer units (a4)〕 The alkali-soluble resin (A1) can contain monomer units other than (a1) to (a3) (hereinafter also referred to as other monomer units (a4)).

[0079] Monomers that form other monomer units (a4) include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, benzyl (meth)acrylate; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl methacrylate, glycerin monomethacrylate; Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (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,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl fatty acids such as vinyl acetate or vinyl propionate; N-Substituted maleimides such as phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl maleimide, N-bromomethyl-2,3-dichloro maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine; 2-(Meth)acryloyloxyethyl acid phosphate, phosphate ester group-containing (meth)acrylates such as compounds obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl groups of the above-described hydroxyl group-containing (meth)acrylate; Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate and the like can be mentioned. These monomers can be used alone or in combination of two or more.

[0080] The alkali-soluble resin (A1) can be used alone or in combination of two or more.

[0081] From the viewpoints of suppressing water bleeding and pattern shape, the content of the alkali-soluble resin (A1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass in 100% by mass of the alkali-soluble resin (A).

[0082] (Alkali-soluble resin (A2)) The photosensitive composition of the present invention can contain an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) as the alkali-soluble resin (A) (hereinafter also referred to as the alkali-soluble resin (A2)).

[0083] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0084] The polymerizable compound (B) includes monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group of an ethylenically unsaturated double bond, a (meth)allyl group, a (meth)acryloyl group, and the like. The weight average molecular weight or formula weight of the polymerizable compound (B) is preferably less than 2000.

[0085] (Lactone-modified polymerizable compound (B1)) From the viewpoint of suppressing water stain, the polymerizable compound (B) preferably contains a lactone-modified polymerizable compound (B1).

[0086] The lactone-modified polymerizable compound (B1) is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound (B1) can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethol melamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound (B1) is preferably a compound represented by the following general formula (14).

[0087] General formula (14)

Chemical formula

[0088] In general formula (14), all six Rs are groups represented by the following general formula (15), or 1 to 5 of the six Rs are groups represented by the following general formula (15), and the rest are groups represented by the following general formula (16).

[0089] General formula (15)

Chemical formula

[0090] In general formula (15), R 1 represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond that binds to the oxygen atom of general formula (14).

[0091] General formula (16)

Chemical formula

[0092] In the general formula (16), R 1 represents a hydrogen atom or a methyl group, and * represents a bond that binds to the oxygen atom of the general formula (14).

[0093] The lactone-modified polymerizable compound (B1) is commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. For example, DPCA-20 (in the above general formulas (14) to (16), m = 1, the number of groups represented by the general formula (15) = 2, R 1 is a compound in which all are hydrogen atoms), DPCA-30 (in the above general formulas (14) to (16), m = 1, the number of groups represented by the general formula (15) = 3, R 1 is a compound in which all are hydrogen atoms), DPCA-60 (in the above general formulas (14) to (16), m = 1, the number of groups represented by the general formula (15) = 6, R 1 is a compound in which all are hydrogen atoms), DPCA-120 (in the above general formulas (14) to (16), m = 2, the number of groups represented by the general formula (15) = 6, R 1 is a compound in which all are hydrogen atoms), and the like can be mentioned.

[0094] From the viewpoint of suppressing water bleeding, the lactone-modified polymerizable compound (B1) is preferably a compound in which, in the above general formulas (14) to (16), m = 1, the number of groups represented by the general formula (15) = 2 to 6, and R 1 are all hydrogen atoms, and more preferably a compound in which, in the above general formulas (14) to (16), m = 1, the number of groups represented by the general formula (15) = 2 or 3, and R 1 are all hydrogen atoms.

[0095] The lactone-modified polymerizable compound (B1) can be used alone or in combination of two or more.

[0096] From the viewpoint of suppressing water bleeding, the content of the lactone-modified polymerizable compound (B1) is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, in 100% by mass of the polymerizable compound (B).

[0097] (Polymerizable Compound (B2) Having an 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) include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. Among these, a carboxyl group is preferable.

[0098] Examples of the polymerizable compound (B2) having an acid group include esterified products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, etc. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, etc. Examples of the polyvalent carboxylic acid include trimellitic acid, pyromellitic acid, etc. Examples of the 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, etc.

[0099] Commercially available products of the polymerizable compound (B2) having an acid group include Biscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521, etc. manufactured by Toagosei Co., Ltd.

[0100] The polymerizable compound (B2) having an acid group can be used alone or in combination of two or more.

[0101] From the viewpoint of the pattern shape, the content of the polymerizable compound (B2) having an acid group is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, based on 100% by mass of the polymerizable compound (B).

[0102] (Other polymerizable compound (B3)) The photosensitive composition of the present invention can contain, as the polymerizable compound (B), a polymerizable compound (B1) modified with lactone, and a polymerizable compound other than the polymerizable compound (B2) having an acid group (hereinafter, also referred to as other polymerizable compound (B3)).

[0103] Other polymerizable compounds (B3) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-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, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, urethane (meth)acrylate and other various acrylic acid esters and methacrylic acid esters, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

[0104] Commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330 manufactured by Nippon Kayaku Co., Ltd.; Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A manufactured by Toagosei Co., Ltd.; Biscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Industry Co., Ltd.; AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd.; NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd.; Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd.; EBECRYL 40, 130, 140, 145 manufactured by Daicel Ornex Co., Ltd.; OGSOL EA-0200, 0300 manufactured by Osaka Gas Chemical Co., Ltd., and the like.

[0105] The polymerizable compound (B) can be used alone or in combination of two or more.

[0106] 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 non-volatile content of the photosensitive composition.

[0107] [Sensitizer (D)] From the viewpoint of the pattern shape, the photosensitive composition of the present invention preferably contains a sensitizer (D).

[0108] The sensitizer (D) includes, for example, chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyllin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, or benzophenone compounds, etc. Among these, from the viewpoint of the pattern shape, thioxanthone compounds (D1) or benzophenone compounds (D2) are preferable, and thioxanthone compounds (D1) are more preferable.

[0109] (Thioxanthone compound (D1)) Examples of the thioxanthone compound (D1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferable.

[0110] (Benzophenone compound (D2)) Benzophenone compounds (D2) include, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0111] The sensitizer (D) can be used alone or in combination of two or more.

[0112] 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 with respect to 100 parts by mass of the compound (C1) represented by the general formula (1).

[0113] The photosensitive composition of the present invention can contain a colorant (E).

[0114] The colorant (E) may be either a pigment or a dye and can be used in combination.

[0115] (Pigment) A pigment is a compound classified as a pigment in the Color Index. Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A No. 2014-134712, the pigments described in Patent No. 6368844, and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are preferable, and C.I. Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are more preferable.

[0116] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

[0117] Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in JP-A-2012-226110. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110 are preferred.

[0118] Green pigments include, for example, 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. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

[0119] Blue pigments include, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

[0120] Purple pigments include, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, C.I. Pigment Violet 19 and 23 are preferred.

[0121] Black pigments include, for example, C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc. Also, at least two pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and purple pigments may be used as a black colorant.

[0122] Among the pigments, inorganic pigments include, for example, titanium oxide, barium sulfate, silica, zinc white, lead sulfate, lead yellow, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, navy blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc.

[0123] (Dyes) Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Also, derivatives thereof and lake pigments obtained by lake-forming dyes are also included.

[0124] Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. Also, salt-forming compounds that are salts of acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds are preferred. Also, salt-forming compounds that are salts of resin components having these functional groups and acid dyes are also preferred. Also, salt-forming compounds are likely to obtain a photosensitive composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification to sulfonic acid amide compounds. Also, salt-forming compounds of acid dyes and compounds having an onium base are also preferred because they are excellent in resistance (light resistance, solvent resistance). Note that the compound having an onium base is preferably a resin having a cationic group.

[0125] Basic dyes can be used as they are, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. The salt-forming compounds of basic dyes are preferred because of their excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, among the salt-forming compounds of basic dyes, the anionic component that acts as a counterion is an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed by salting with an acid dye. Note that the salt-forming compound has better resistance when it contains a polymerizable unsaturated group in the molecule.

[0126] The chemical structure of the dye is derived from a dye selected from, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, and anthrapyridone dyes), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes), quinoneimine dyes (such as oxazine dyes and thiazine dyes), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their metal complex dyes, etc.

[0127] Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, 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, and subphthalocyanine dyes is preferable, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferable.

[0128] The colorant (E) can be used alone or in combination of two or more.

[0129] 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 non-volatile components of the photosensitive composition.

[0130] (Micronization of Pigment) The pigment is preferably used after micronization. The micronization method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used. Among these, salt milling treatment by the kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the micronized pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0131] The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing 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 width, and a sharp particle size distribution can be obtained.

[0132] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, and sodium sulfate. From the viewpoint of cost, sodium chloride (table salt) is preferred. 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 the viewpoints of both treatment efficiency and production efficiency.

[0133] The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, is soluble (miscible) in water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high-boiling solvent having a boiling point of 120 °C or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

[0134] For the salt milling treatment, a resin may be added as necessary. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in the above organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass, per 100 parts by mass of the pigment.

[0135] [Dye Derivative (F)] The photosensitive composition of the present invention can contain a dye derivative (F).

[0136] The pigment derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in an organic pigment residue. Examples of the pigment derivative (F) include compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, etc., and amine salts thereof, compounds having a basic substituent such as a sulfonamide group and a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group and a phthalimidoalkyl group. Examples of the organic pigment include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, polyazo, etc.

[0137] Specifically, examples of diketopyrrolopyrrole-based pigment derivatives include those described in JP-A No. 2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A No. 2017-156397; examples of phthalocyanine-based pigment derivatives include those described in JP-A No. 2007-226161, WO 2016 / 163351, JP-A No. 2017-165820, Patent No. 5753266; examples of anthraquinone-based pigment derivatives include those described in JP-A No. 63-264674, JP-A No. 09-272812, JP-A No. 10-245501, JP-A No. 10-265697, JP-A No. 2007-079094, WO 2009 / 025325; examples of quinacridone-based pigment derivatives include those described in JP-A No. 48-54128, JP-A No. 03-9961, JP-A No. 2000-273383; examples of dioxazine-based pigment derivatives include those described in JP-A No. 2011-162662; examples of thiazine indigo-based pigment derivatives include those described in JP-A No. 2007-314785; examples of triazine-based pigment derivatives include those described in JP-A No. 61-246261, JP-A No. 11-199796, JP-A No. 2003-165922, JP-A No. 2003-168208, JP-A No. 2004-217842, JP-A No. 2007-314681; examples of benzisoindole-based pigment derivatives include those described in JP-A No. 2009-57478; examples of quinophthalone-based pigment derivatives include those described in JP-A No. 2003-167112, JP-A No. 2006-291194, JP-A No. 2008-31281, JP-A No. 2012-226110; examples of naphthol-based pigment derivatives include those described in JP-A No. 2012-208329, JP-A No. 2014-5439; examples of azo-based pigment derivatives include those described in JP-A No. 2001-172520, JP-A No. 2012-172092; examples of acidic substituents include those described in JP-A No. 2004-307854; examples of basic substituents include those described in JP-A No. 2002-201377, JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, etc. Known pigment derivatives are included.Note that in these documents, the dye derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds. However, a compound having a substituent such as an acidic group, a basic group, or a neutral group in the above-described organic dye residue is synonymous with a dye derivative.

[0138] The dye derivative (F) can be used alone or in combination of two or more.

[0139] The content of the dye derivative (F) is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the colorant (E).

[0140] [Dispersion resin (G)] The photosensitive composition of the present invention can contain a dispersion resin (G). The dispersion resin (G) is a resin used for dispersing the colorant (E).

[0141] The dispersion resin (G) is preferably a resin having an adsorption group with high affinity for the colorant (E). The adsorption group preferably has at least one of a basic group and an acidic group, and preferably has an acidic group from the viewpoint of developability.

[0142] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0143] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a carboxyl group and a phosphoric acid group are preferable from the viewpoints of adsorption property to the pigment and developability.

[0144] The resin species of the dispersion resin (G) include, for example, urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidine salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group and salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinyl pyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, and the like.

[0145] The molecular structure of the dispersion resin (G) includes, for example, a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, a block structure or a comb structure is preferable.

[0146] Commercially available products of the dispersion resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 manufactured by BYK-Chemie Japan Co., Ltd., or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. manufactured by Lubrizol Japan Ltd., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF Japan Ltd., Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc., resins described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, etc.

[0147] The dispersion resin (G) can be used alone or in combination of two or more kinds.

[0148] 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).

[0149] [Thermosetting compound (H)] From the viewpoint of heat resistance, the photosensitive composition of the present invention preferably contains a thermosetting compound (H). Thereby, the thermosetting compound (H) reacts in the heating step, and the crosslinking density increases, so that the heat resistance is improved.

[0150] The thermosetting compound (H) may be a low molecular 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, an epoxy compound and an oxetane compound are preferable.

[0151] (Epoxy compound (H1)) The epoxy compound (H1) includes, for example, polycondensates of bisphenols (such as bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (such as phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (such as formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (such as dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α’,α’-benzenedimethanol, biphenyldimethanol, α,α,α’,α’-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α,α’-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, etc.

[0152] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, Inc., EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 manufactured by Japan Epoxy Resins Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154, Celloxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S, etc. manufactured by Nissan Chemical Industries, Ltd.

[0153] The content of the epoxy compound (H1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[0154] (Oxetane compound (H2)) The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0155] Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, and the like.

[0156] Commercially available products include, for example, OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 212 manufactured by Toagosei Co., Ltd., and the like.

[0157] The bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, 3-ethyl-3-hydroxy methyloxetane, 3-ethyl-3-(2-ethylhexyloxy methyl)oxetane, 3-ethyl-3-(2-phenoxy methyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanyl methyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanyl methyl)ether, triethylene glycol bis(3-ethyl-3-oxetanyl methyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl methyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanyl methyl)ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanyl methyl)ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanyl methyl)ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl)ether, EO modified bisphenol F(3-ethyl-3-oxetanyl methyl)ether, and the like.

[0158] Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0159] Oxetane compounds having three or more functional groups include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, oxetane-modified phenol novolak resins described in Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0160] 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 non-volatile content of the photosensitive composition.

[0161] The melamine compound is a compound having a melamine ring structure. Melamine compounds are preferably methylol-type or ether-type compounds, and more preferably melamine compounds having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Appropriate numbers of methylol groups and ether groups make it easy to obtain heat resistance without excess or deficiency.

[0162] Commercially available products include, for example, Niclac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 manufactured by Sanwa Chemical Co., Ltd., Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Cytec Industries, Inc., and the like.

[0163] Among these, Niclac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 manufactured by Nippon Cytec Industries, Inc., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferable in terms of increasing the crosslinking density.

[0164] The thermosetting compound (H) can be used alone or in combination of two or more.

[0165] [Hardening agent (hardening accelerator)] The photosensitive composition of the present invention can be used in combination with a curing agent (curing accelerator) in order to assist the curing of the thermosetting compound (H). 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 amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.), and the like.

[0166] The curing agent can be used alone or in combination of two or more kinds.

[0167] 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).

[0168] [Thiol-based chain transfer agent (I)] The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with the photopolymerization initiator (C), thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the photosensitivity of the photosensitive composition is improved.

[0169] The thiol-based 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. When the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0170] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. are mentioned.

[0171] The thiol-based chain transfer agent (I) can be used alone or in combination of two or more.

[0172] The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0173] [Polymerization inhibitor (J)] The photosensitive composition of the present invention can contain a polymerization inhibitor (J).

[0174] The polymerization inhibitor (J) is, for example, alkylcatechol 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-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol, etc.; alkylresorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, etc.; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, etc.; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc.; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide, etc.; phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite, etc.; pyrogallol, phloroglucin, and the like.

[0175] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile components of the photosensitive composition.

[0176] [Ultraviolet absorber (K)] The photosensitive composition of the present invention can contain an ultraviolet absorber (K).

[0177] The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0178] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0179] Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan Ltd., Adeka Stab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA Corporation, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

[0180] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis「2-hydroxy-4-butoxyphenyl」-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and the like.

[0181] Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan Ltd., Adeka Stab LA-46, LA-F70 of ADEKA Corporation, CYASORB UV-1164 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0182] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0183] Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cypro Kasei Co., Ltd., Adeka Stab 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0184] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0185] The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator (C) and the ultraviolet absorber (K).

[0186] [Antioxidant (L)] The photosensitive composition of the present invention can contain an antioxidant (L).

[0187] The antioxidant (L) prevents yellowing due to oxidation of the photopolymerization initiator (C) and the thermosetting compound (H) contained in the photosensitive composition during the heat curing process and the heat treatment during ITO annealing. In particular, when the concentration of the colorant (E) in the photosensitive composition is high, the content of the polymerizable compound (B) relatively decreases. Therefore, if the amount of the photopolymerization initiator (C) is increased or the thermosetting compound (H) is blended to cope with this, the cured film is likely to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process can be prevented.

[0188] Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0189] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0190] Hindered phenol antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and the like can be mentioned.

[0191] Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, Keminox 101, 179, 76, 9425 manufactured by Chemipro, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, and Cyanox CY-1790, CY-2777 manufactured by Sankyo Chemical, etc.

[0192] Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N’-4,7-tetrakis〔4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl〕-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 1,6 - hexamethylenediamine, 2 - methyl - 2 - (2,2,6,6 - tetramethyl - 4 - piperidyl) amino - N - (2,2,6,6 - tetramethyl - 4 - piperidyl) propionamide, etc.

[0193] Commercially available products include, for example, AdekaStab LA - 52, LA - 57, LA - 63P, LA - 68, LA - 72, LA - 77Y, LA - 77G, LA - 81, LA - 82, LA - 87, LA - 402F, LA - 502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Ltd.; and Cyasorb - UV - 3346, UV - 3529, UV - 3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0194] Phosphorus-based antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyldiphosphonite, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisononylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylenebis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc.

[0195] Commercially available products include, for example, Adeka Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation; IRGAFOS 168 manufactured by BASF Japan Ltd.; Hostanox P-EPQ manufactured by Clariant Chemicals, etc.

[0196] Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2'-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc.

[0197] Commercially available products include, for example, Adeka Stab AO-412S, AO-503 manufactured by ADEKA Corporation; Keminox PLS manufactured by Chemipro Kasei Co., Ltd., etc.

[0198] The antioxidant (L) can be used alone or in combination of two or more.

[0199] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile components of the photosensitive composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0200] [Leveling agent (M)] The photosensitive composition of the present invention can contain a leveling agent (M). Thereby, the wettability and drying property with respect to the substrate during coating are further improved.

[0201] Examples of the leveling agent (M) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc.

[0202] Silicone surfactants include, for example, linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or terminals.

[0203] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by 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, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0204] Fluorine-based surfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

[0205] Commercially available products include, for example, Surfron S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; 602A of Phthalgen manufactured by Neo Chemicals Co., Ltd.

[0206] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrylphenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, and the like.

[0207] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amite 102, 105, 105A, 302, 320, Aminon PK-02S, L-02, Homogenol L-95, ADEKA's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical's (meth)acrylic acid-based (co)polymers Polyflow - No.75, No.90, No.95, etc.

[0208] Examples of cationic surfactants include alkylamine salts and alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0209] Commercially available products include, for example, Kao's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0210] Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, and the like.

[0211] Commercially available products include, for example, Ftaigent 100 and 150 manufactured by Neos Co., Ltd., ADEKA Hope YES-25 manufactured by ADEKA Corporation, ADEKA Cole TS-230E, PS-440E, EC-8600, and the like.

[0212] Amphoteric surfactants include, for example, alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocoamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0213] Commercially available products include Unhitole 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0214] The leveling agent (M) can be used alone or in combination of two or more.

[0215] 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 in 100% by mass of the non-volatile content of the photosensitive composition. By being within this range, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[0216] [Storage Stabilizer (N)] The photosensitive composition of the present invention can contain a storage stabilizer (N). Thereby, the viscosity of the photosensitive composition over time is stabilized.

[0217] The storage stabilizer (N) includes, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites.

[0218] The storage stabilizer (N) can be used alone or in combination of two or more.

[0219] The content of the storage stabilizer (N) is preferably 0.1 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0220] [Adhesion improver (O)] The photosensitive composition of the present invention can contain an adhesion improver (O). Thereby, the adhesion between the film and the substrate is improved. Also, it becomes easier to form a narrow-width pattern by the photolithography method.

[0221] The adhesion promoter (O) includes, for example, silane coupling agents. Examples of silane coupling agents include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; amino silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl silanes such as p-styryltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane; sulfide silanes such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane.

[0222] The adhesion promoter (O) can be used alone or in combination of two or more.

[0223] The content of the adhesion promoter (O) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[0224] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0225] The organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, and the like. Among these, from the viewpoints of pigment dispersibility and solubility of alkali-soluble resin, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.,

[0226] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0227] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced, for example, by blending a colorant (E), a dispersion resin (G), a dye derivative (F), an organic solvent (P), etc. and performing a dispersion treatment to produce a dispersion. Then, an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), etc. are blended and mixed with the dispersion. Note that the materials to be blended and the timing of blending are arbitrary. Also, the dispersion step can be performed multiple times.

[0228] Dispersion machines for performing dispersion treatment include, for example, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor, etc.

[0229] The average dispersed particle diameter (secondary particle diameter) of the colorant in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When it has an appropriate particle diameter, a photosensitive composition with high dispersion stability is easily obtained.

[0230] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using Microtrac UPA-EX150 of Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power spectrum method), the particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. As the dilution solvent for measurement, the organic solvents used for dispersion are respectively used, and when measuring the sample immediately after sample preparation for the sample treated with ultrasonic waves, results with less variation are easily obtained and are preferable.

[0231] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means such as centrifugation, filtration through a sintered filter or a membrane filter. 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.

[0232] <Optical Filter> The optical filter of the present invention includes a substrate and filter segments formed from the photosensitive composition of the present invention. The optical filter can be used for various applications. In this specification, the optical filter is preferably a color filter. The filter segment, in the case of a color filter, has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (E) to be used. Instead of or in addition to the filter segment, it can also have a magenta filter segment, a cyan filter segment, a yellow filter segment, a white filter segment, a gray filter segment, and a black filter segment. It can also have a clear filter. Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0233] [Method for manufacturing an optical filter] The method for manufacturing an optical filter can be performed, for example, by the following steps: (1) applying a photosensitive composition on a substrate to form a layer (film) of the composition; (2) exposing the layer in a pattern through a mask; (3) alkali-developing the unexposed portion to form a patterned cured film; and (4) heat-treating (post-baking) the pattern.

[0234] Hereinafter, the method for manufacturing an optical filter will be described in detail. (Step (1)) In the step (1) of forming a layer of the composition, the photosensitive composition is applied on the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and dried (pre-baked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, a hot plate, etc. as necessary. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have, for example, an imaging element such as a CCD or a CMOS formed on its surface. Also, a primer layer may be provided on the substrate as necessary for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface. The film thickness of the layer is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

[0235] (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 stepper, etc. Thereby, a cured film is obtained. Examples of the radiation used for exposure include ultraviolet rays such as g-ray, h-ray, and i-ray.

[0236] (Step (3)) By subjecting the cured film obtained in step (2) to an alkali development treatment, the layer of the composition in the unexposed portion is eluted into an aqueous alkali solution, and only the cured portion remains to obtain a patterned cured film. Examples of the developer include alkaline 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, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. The concentration of the developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved.

[0237] Examples of the development method include the dip method, the spray method, the paddle method, etc. The development temperature is preferably 15 to 40°C. After alkali development, it is preferably washed with pure water.

[0238] (Step (4)) The heat treatment (post-bake) sufficiently cures the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C, and more preferably 150 to 250°C. Also, the heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

[0239] <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 EL display, and the like. The form used in the image display device only needs to function as an image display device and is not particularly limited. For example, the configurations described in "Next-generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, Inc. in 1994) can be mentioned. Regarding the definition of the image display device and the details of each image display device, for example, they are described in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosa Kai, Inc. in 1990), "Display Devices" (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989), and the like.

[0240] <Solid-state imaging device> The solid-state imaging device of the present invention includes the optical filter of the present invention. The form used in the solid-state imaging device is not particularly limited. For example, on a substrate, it has a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., and has a light-shielding film with only the light-receiving part of the photodiode opened on the photodiodes and the transfer electrodes, and has a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film, and has a filter on the device protection film. Further, a configuration having condensing means (such as a microlens, etc. The same applies hereinafter) on the device protection film and under the filter (on the side close to the substrate), or a configuration having condensing means on the filter may be used. Also, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls are preferably of a low refractive index with respect to each colored pixel. The imaging device including the solid-state imaging device of the present invention can be used in various applications such as a digital camera, an electronic device having an imaging function (such as a mobile phone, a smartphone, etc.), an in-vehicle camera, and a surveillance camera.

Examples

[0241] Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the nonvolatile content or the nonvolatile content concentration refers to the mass residue after oven standing at 280°C for 30 minutes.

[0242] Prior to the examples, each measurement method will be described. The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows.

[0243] (Average molecular weight of resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, two separation columns were connected in series, and for both packing materials, "TSK-GEL SUPER HZM-N" was connected in a pair and used. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent composed of 1% by mass of the above eluent and 20 microliters were injected. The average molecular weight is a polystyrene conversion value.

[0244] (Acid value of resin) To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred to dissolve uniformly. Using a 0.1 mol / L KOH aqueous solution as the titrant, titration was performed using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

[0245] (Amine value of resin) The amine value of the resin is a value obtained by converting the total measured amine value (mgKOH / g) into nonvolatile content in accordance with the method of ASTM D 2074.

[0246] (Production of colorant (E)) (Fine - sized Red Pigment (E - 1)) 100 parts of C.I. Pigment Red 254, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 - gallon stainless - steel kneader (manufactured by Inoue Seisakusho), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred with a high - speed mixer for 1 hour while heating to about 80°C to make it into a slurry state, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for a whole day and night, and pulverized to obtain the fine - sized red pigment (E - 1).

[0247] (Fine - sized Red Pigment (E - 2)) 100 parts of C.I. Pigment Red 177, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 - gallon stainless - steel kneader (manufactured by Inoue Seisakusho), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred with a high - speed mixer for 1 hour while heating to about 80°C to make it into a slurry state, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for a whole day and night, and pulverized to obtain the fine - sized red pigment (E - 2).

[0248] (Fine - sized Blue Pigment (E - 3)) 100 parts of C.I.Pigment Blue15:6, 1000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1 - gallon stainless - steel kneader (manufactured by Inoue Seisakusho), and kneaded at 50°C for 12 hours. This mixture was put into 3000 parts of warm water, stirred with a high - speed mixer for about 1 hour while heating to about 70°C to make it into a slurry state, and filtration and washing were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for 24 hours and pulverized to obtain the fine - sized blue pigment (E - 3).

[0249] (Fine - sized 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 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 80 °C for 6 hours. Next, this kneaded product was put into 8,000 parts of warm water, and stirred with a high-speed mixer for 2 hours while heating to 80 °C to make it into a slurry state. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 °C for 24 hours and pulverized to obtain a finely divided purple pigment (E-4).

[0250] (Finely divided 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 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70 °C for 6 hours. This kneaded product was put into 3,000 parts of warm water, and stirred with a high-speed mixer for 1 hour while heating to 70 °C to make it into a slurry state. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night and pulverized to obtain a finely divided green pigment (E-5).

[0251] (Finely divided green pigment (E-6) According to the examples of JP-A-2017-111398, a green pigment (E-6) of the following chemical formula (17) was obtained. 100 parts of the green pigment (E-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70 °C for 6 hours. This kneaded product was put into 3,000 parts of warm water, and stirred with a high-speed mixer for 1 hour while heating to 70 °C to make it into a slurry state. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night and pulverized to obtain a finely divided green pigment (E-6). Chemical formula (17) [Chemical formula]

[0252] (Finely divided 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 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. This mixture was poured into 2,000 parts of warm water and stirred with a high-speed mixer for 1 hour while heating to 80°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night and then pulverized to obtain a finely divided yellow pigment (E-7).

[0253] (Finely divided yellow pigment (E-8)) 100 parts of C.I. Pigment Yellow 139 ("Novoperm Yellow P-M3R" manufactured by Clariant), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. This mixture was poured into 3,000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night and then pulverized to obtain a finely divided yellow pigment (E-8).

[0254] (Finely divided yellow pigment (E-9)) 100 parts of C.I. Pigment Yellow 185 ("Palitol Yellow D1155" manufactured by BASF Japan), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded product was poured into 8 liters of warm water and stirred with a high-speed mixer for 2 hours while heating to 80°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85°C for a whole day and night and then pulverized to obtain a finely divided yellow pigment (E-9).

[0255] (Finely divided yellow pigment (E-10) According to the examples of Japanese Patent Application Laid-Open No. 2012-226110, the yellow pigment (E-10) of the following chemical formula (18) was obtained. 100 parts of the yellow pigment (E-10), 700 parts of crushed sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred with a high-speed mixer for 2 hours while heating to 80°C to make it into a slurry state. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85°C for a whole day and night and pulverized to obtain a refined yellow pigment (E-10). Chemical formula (18) [Chemical formula]

[0256] The average primary particle diameter of the above refined pigment was in the range of 5 to 120 nm.

[0257] (Dye (E-11)) The dye (E-11), which is a salt-forming compound composed of C.I. Acid Red 52 and a resin 1 having a cationic group in the side chain, was produced by the following procedure. 67.3 parts of methyl ethyl ketone was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 °C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were made uniform and then charged into a dropping funnel, attached to the four-neck separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more based on the non-volatile content and the weight average molecular weight (Mw) was 6,830, and it was cooled to 50 °C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, reacted at 50 °C for 2 hours, then heated to 80 °C over 1 hour, and further reacted for 2 hours. Thus, resin 1 having a cationic group in the side chain having an ammonium group of 47 mass% of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g. Next, 30 parts of resin 1 having a cationic group in the side chain in terms of non-volatile content was added to 2,000 parts of water, sufficiently stirred and mixed, and then heated to 60 °C. On the other hand, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water was prepared and dropped little by little into the resin solution prepared above. After dropping, it was stirred at 60 °C for 120 minutes to sufficiently carry out the reaction. As the confirmation of the end point of the reaction, the reaction solution was dropped onto a filter paper, and when there was no bleeding, it was judged that a salt-forming compound was obtained. After allowing to cool to room temperature with stirring, suction filtration was carried out, washed with water, and the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture and dried to obtain 32 parts of a salt-forming compound of C.I. Acid Red 52 and resin 1 having a cationic group in the side chain, dye (E-11). At this time, the content of the component derived from C.I. Acid Red 52 in the dye (E-11) was 25 mass%.

[0258] <Production of alkali-soluble resin (A)> (Alkali-soluble resin (A1-1) solution) A separable four-necked flask was used as a reaction vessel equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer. 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed therein, and while injecting nitrogen gas into the vessel, it was heated to 120 °C. At the same temperature, a mixture of 49.7 parts of 2-ethylhexyl acrylate (hereinafter referred to as 2-EHA), 99.4 parts of glycidyl methacrylate (hereinafter referred to as GMA), 6.6 parts of dicyclopentanyl methacrylate (hereinafter referred to as DCPMA), and 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator in PGMAc was added dropwise over 2.5 hours through a dropping tube. After the addition was completed, stirring was continued at 120 °C for another 2 hours to obtain a precursor. Then, the inside of the flask was purged with air, and 50.4 parts of acrylic acid (hereinafter referred to as AA) as a modifying compound, 0.6 part of triphenylphosphine as a catalyst, and 0.2 part of methylhydroquinone were added, and the reaction was carried out at 110 °C for 10 hours. Thereby, a monomer unit (hereinafter referred to as GMA+AA) in which the epoxy group of GMA and the carboxyl group of AA were reacted was obtained, and a polymerizable unsaturated group-containing monomer unit (a2) was introduced. Next, 21.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) was added as a modifying compound, and the reaction was carried out at 110 °C for 4 hours. Thereby, a part of the hydroxyl groups of GMA+AA was reacted with THPA. Then, PGMAc was added so that the nonvolatile content became 20% by mass, and an alkali-soluble resin (A1-1) solution containing an alicyclic hydrocarbon-containing monomer unit (a1), a polymerizable unsaturated group-containing monomer unit (a2), and a monomer unit (a3) having a glass transition temperature of 0 °C or lower of the homopolymer was prepared. The alkali-soluble resin (A1-1) had an acid value of 38 mgKOH / g and a weight average molecular weight of 12,000.

[0259] (Alkali-soluble resin (A1-2) to (A1-6) solutions) The types and amounts of the components were changed so as to have the composition ratios shown in Table 1, and alkali-soluble resins (A1-2) to (A1-6) were synthesized in the same manner as the alkali-soluble resin (A1-1), and PGMAc was added to make the nonvolatile content 20% by mass.

[0260]

Table 1

[0261] The MAA+GMA described in Table 1 represents a polymerizable unsaturated group-containing monomer unit (a2) in which an epoxy group of GMA is added to a carboxyl group of methacrylic acid (hereinafter referred to as MAA) in a precursor. GMA+AA+SHA represents a polymerizable unsaturated group-containing monomer unit (a2) obtained by reacting a part of the hydroxyl groups of GMA+AA with succinic anhydride (hereinafter referred to as SHA).

[0262] (Alkali-soluble resin (A2-1) solution) 196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirrer in a separable four-necked flask, heated to 80 °C, and the inside of the reaction vessel was purged with nitrogen. Then, 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, 24.1 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours through the dropping tube. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass, thereby preparing an alkali-soluble resin (A2-1) solution. The acid value was 87 mgKOH / g and the weight average molecular weight was 25,000.

[0263] (Alkali-soluble resins (A2-2) and (A2-3) solutions) The compounding types and amounts were changed so as to achieve the composition ratios described in Table 2, and alkali-soluble resins (A2-2) and (A2-3) were synthesized. PGMAc was added to make the nonvolatile content 20% by mass.

[0264]

Table 2

[0265] <Production of the Coincidence Compound (B)> (Polymerizable Compound (B2-2) Having an Acid Group) Into a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70 °C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm -1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were charged, and the reaction was carried out at a temperature of 50 to 60 °C for 6 hours. It was adjusted so that the nonvolatile content became 50% by mass, and a polymerizable compound (B2-2) having an acid group was obtained.

[0266] <Production of the Dispersion Resin (G)> (Dispersion Resin (G-1) Solution) Into a reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc was added while reacting for 7 hours. It was confirmed by nonvolatile content measurement that 95% had reacted. 19 parts of pyromellitic dianhydride, 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, and the reaction was carried out at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added for dilution so that the nonvolatile content became 30% by nonvolatile content measurement, and a dispersion resin (G-1) solution having an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

[0267] (Dispersion Resin (G-2) Solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120 °C for 5 hours (first step). It was confirmed by acid value measurement that more than 95% of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The inside of the reaction vessel was heated to 80 °C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a PGMAc dilution solution of 50% non-volatile content 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 the disappearance of the peak at 2270 cm -1 based on the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (G-2) solution with a non-volatile content of 30%. The acid value of the obtained dispersion resin (G-2) was 68 mgKOH / g, the unsaturated double bond equivalent was 1,593, and the weight average molecular weight was 13,000.

[0268] (Dispersion resin (G-3) solution) A reaction apparatus equipped with a gas inlet tube, 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. While flowing nitrogen, it was stirred at 50 °C for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and while under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcrile FA-711MM) as the second block (A block) monomer were added to this reaction apparatus, and it was stirred while maintaining the temperature at 110 °C in a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added for dilution so that the non-volatile content became 30% in the non-volatile content measurement, and a dispersion resin (G-3) solution with an amine value of 57 mgKOH / g per non-volatile content and a number average molecular weight of 4,500 (Mn) was obtained.

[0269] (Dispersion resin (G-4) solution) Into a 500 mL round-bottom four-neck separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, stirrer, and digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyltrimethylsilyl acetal as an initiator were added via the addition funnel, and sufficient nitrogen substitution was performed. 0.5 part by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 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, which are monomers for a block having parent solvent solubility, were added dropwise over 60 minutes using the addition funnel. The reaction flask was cooled in an ice bath to keep the temperature below 40 °C. After 1 hour, 18.3 parts by mass of dimethylaminopropylmethacrylamide, which is a monomer for a colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained THF solution of the block copolymer was reprecipitated in hexane and purified by filtration and vacuum drying. Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalent relative to dimethylaminopropylmethacrylamide), which is a salt-forming component, was added, and the mixture was stirred at a reaction temperature of 30 °C for 20 hours, adjusted by adding PGMAc, and a dispersion resin (G-4) solution having a nonvolatile content of 30% was obtained.

[0270] <Production of Dispersion> (Dispersion 1) Using zirconia beads with a diameter of 0.5 mm, dispersion was carried out for 3 hours using an Eiger mill (「Mini Model M-250 MKII」manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1 having the following composition. The organic solvent (P-1) is PGMAc. Fine blue pigment (E-3): 9.05 parts by mass Fine purple pigment (E-4): 0.31 part by mass Dye (E-11): 4.16 parts by mass Pigment Derivative (F-1): 1.04 parts by mass Dispersion Resin (G-1) Solution: 3.47 parts by mass Alkali-Soluble Resin (A2-1) Solution: 10.0 parts by mass Organic Solvent (P-1): 71.97 parts by mass

[0271] Pigment Derivative (F-1): The following structure [Chemical Formula] pc represents a phthalocyanine skeleton.

[0272] Dispersions 2 to 9 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 3 were changed.

[0273] [Table 3]

[0274] Pigment Derivative (F-2) in Table 3: The following structure [Chemical Formula]

[0275] Pigment Derivative (F-3) in Table 3: The following structure [Chemical Formula]

[0276] [Manufacture of Photosensitive Composition] [Example 1] (Photosensitive Composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. Dispersion 1: 28.85 parts by mass Alkali-Soluble Resin (A1-2) Solution: 9.0 parts by mass Polymerizable Compound (B1-1): 5.0 parts by mass Polymerizable Compound (B2-1): 1.2 parts by mass Compound (C1-1) represented by the general formula (1): 0.70 part by mass Oxime-based photopolymerization initiator (C2b-1): 0.50 part by mass Sensitizer (D1-1): 0.30 part by mass Thermosetting compound (H1-1): 0.30 part by mass Polymerization inhibitor (J): 0.01 part by mass Leveling agent (M): 1.00 part by mass Organic solvent (P): 53.14 parts by mass

[0277] [Examples 2 to 35, Comparative Examples 1 to 3] (Photosensitive Compositions 2 to 38) Photosensitive Compositions 2 to 38 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 4-1 to 4-4 were changed for the photosensitive composition 1 of Example 1.

[0278]

Table 4-1

[0279]

Table 4-2

[0280]

Table 4-3

[0281]

Table 4-4

[0282] For each of the raw materials described in Tables 4-1 to 4-4, it is as follows.

[0283] [Polymerizable Compound (B)] (Lactone-modified Polymerizable Compound (B1)) B1-1: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.) B1-2: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)

[0284] (Polymerizable compound having an acid group (B2)) B2-1: Aronix M-520 (manufactured by Toagosei Co., Ltd.)

[0285] (Other polymerizable compound (B3)) B3-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[0286] [Photoinitiator (C)] (Compound (C1) represented by the general formula (1)) C1-1: Compound of the above chemical formula (2) C1-2: Compound of the above chemical formula (3) C1-3: Compound of the above chemical formula (4)

[0287] (Oxime-based photoinitiator (C2)) C2a-1: TRONLY TR-PBG-3057 (manufactured by Changzhou Qiangli New Materials Co., Ltd., compound containing one oxime group in one molecule) C2a-2: Compound of the above chemical formula (5) C2a-3: Compound of the above chemical formula (6) C2a-4: Compound of the above chemical formula (7) C2a-5: Compound of the above chemical formula (8) C2b-1: Compound of the above chemical formula (10) C2b-2: Compound of the above chemical formula (13)

[0288] (Other photoinitiator (C3)) C3-1: Omnirad 907 (manufactured by IGM Resins, acetophenone-based compound) C3-2: Omnirad 369 (manufactured by IGM Resins, acetophenone-based compound)

[0289] [Sensitizer (D)] (Thioxanthone-based compound (D1)) D1-1: 2,4-Diethylthioxanthone (Benzophenone compound (D2)) D2-1: 4,4'-Bis(diethylamino)benzophenone

[0290] [Thermosetting compound (H)] (Epoxy compound (H1)) H1-1: EHPE-3150 (manufactured by Daicel Corporation)

[0291] [Polymerization inhibitor (J)] J-1: 4-Methylcatechol J-2: Methylhydroquinone J-3: t-Butylhydroquinone The above (J-1) to (J-3) were mixed in the same amount respectively to obtain the polymerization inhibitor (J).

[0292] [Leveling agent (M)] M-1: BYK-330 (manufactured by BYK-Chemie GmbH) M-2: Megafac F-551 (manufactured by DIC Corporation) The above (M-1) and (M-2) were each mixed in 1 part and dissolved in 98 parts of PGMAc to obtain a mixed solution as the leveling agent (M).

[0293] [Organic solvent (P)] P-1: 30 parts of Propylene glycol monomethyl ether acetate P-2: 30 parts of Cyclohexanone P-3: 10 parts of Ethyl 3-ethoxypropionate P-4: 10 parts of Propylene glycol monomethyl ether P-5: 10 parts of Cyclohexanol acetate P-6: 10 parts of Dipropylene glycol methyl ether acetate The above (P-1) to (P-6) were mixed in the above mass parts respectively to obtain the organic solvent (P).

[0294] [Evaluation of the photosensitive composition] For the obtained photosensitive compositions 1 to 38 (Examples 1 to 35, Comparative Examples 1 to 3), evaluation of water stain, pattern shape (adhesion, cross-sectional shape), and heat resistance was carried out by the following methods. The evaluation results are shown in Table 5.

[0295] [Water stain evaluation] For the obtained photosensitive composition, by the spin coating method, it was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm × width of 100 mm and a thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, through a mask having a 100-μm-wide stripe pattern, ultraviolet exposure was carried out using a high-pressure mercury lamp under the conditions of an illuminance of 30 mW / cm 2 , 50 mJ / cm 2 . Then, it was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 °C for 40 seconds for development, and washed with pure water. The surface of the obtained pattern was observed using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation, and the degree of the discolored part was evaluated. The evaluation criteria are as follows, and 3 or more is considered practical. 5: There was no water stain. 4: The water stain was less than 10% of the whole. 3: The water stain was 10% or more and less than 20% of the whole. 2: The water stain was 20% or more and less than 30% of the whole. 1: The water stain was 30% or more of the whole.

[0296] [Pattern shape evaluation (1): Adhesion] The obtained photosensitive composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm × width of 100 mm and a thickness of 0.7 mm by the spin coating method so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, through a photomask of a stripe pattern with a width of 5 to 25 μm in 5-μm-width increments, an illuminance of 30 mW / cm 2 , 50 mJ / cm 2It was exposed. Then, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes. The spray development was carried out for each film of the photosensitive composition in the shortest time capable of forming a pattern without any remaining development. Regarding the patterns with widths of 5, 10, 15, 20, and 25 μm on the obtained substrate, they were observed with an optical microscope, and the minimum line width of the remaining patterns was confirmed. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: Fine lines of 25 μm remain. 1: No fine lines remain.

[0297] [Pattern Shape Evaluation (2): Cross-Section Shape] The obtained photosensitive composition was applied by the spin coating method onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying would be 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Then, after cooling this substrate to room temperature, using a high-pressure mercury lamp, through a photomask of a 100-μm-wide stripe pattern, the illuminance was 30 mW / cm 2 50 mJ / cm 2 It was exposed. Then, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes. The spray development was carried out for each film of the photosensitive composition in the shortest time capable of forming a pattern without any remaining development. The cross-sectional shape of the pattern was confirmed using a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000H"). For the evaluation, SEM images of the cross-section of a stripe pattern with a width of 100 μm were captured, and the cross-sectional shape was evaluated by measuring the taper angle between the substrate and the end of the pattern cross-section. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Taper angle is 30 degrees or more and less than 50 degrees 4: Taper angle is 50 degrees or more and less than 60 degrees 3: Taper angle is less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle is 70 degrees or more and less than 90 degrees 1: Taper angle is 90 degrees or more

[0298] [Heat resistance evaluation] For the obtained photosensitive composition, it was coated on a glass substrate (Corning's Eagle 2000) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm by the spin coating method so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, it was exposed using a high-pressure mercury lamp at an illuminance of 30 mW / cm 2 , 50 mJ / cm 2 . Then, it was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 40 seconds at 23°C for development, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes. The chromaticity ([L*(1), a*(1), b*(1)]) of the obtained coating film under a C light source was measured using a microspectrophotometer (Olympus Optical Co., Ltd.'s "OSP-SP100"). Furthermore, after that, as a heat resistance evaluation, it was heated at 230°C for 1 hour, the chromaticity ([L*(2), a*(2), b*(2)]) under a C light source was measured, and the color difference ΔEab* was obtained by the following calculation formula. The evaluation criteria are as follows, and a value of 3 or more is considered practical. ΔEab* = ((L*(2) - L*(1)) 2 + (a*(2) - a*(1)) 2 + (b*(2) - b*(1)) 2 ) 1 / 2 5: ΔEab* is less than 1 4: ΔEab* is 1 to 2 3: ΔEab* is 2 to 3 2: ΔEab* is 3 to 5 1: ΔEab* is 5 or more

[0299]

Table 5

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a photopolymerization initiator (C), wherein the alkali-soluble resin (A) includes an alkali-soluble resin (A1) containing an alicyclic hydrocarbon-containing monomer unit (a1) and a polymerizable unsaturated group-containing monomer unit (a2), and the photopolymerization initiator (C) includes a compound (C1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (C2). A photosensitive composition. General formula (1) 【Chemical 1】 (In 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.)

2. The photosensitive composition according to claim 1, wherein the content of the alicyclic hydrocarbon-containing monomer unit (a1) is 1 to 60 mol% in all the constituent units of the alkali-soluble resin (A1).

3. The photosensitive composition according to claim 1 or 2, wherein the oxime-based photopolymerization initiator (C2) includes a compound (C2b) containing two oxime groups in one molecule.

4. The photosensitive composition according to claim 3, wherein the compound (C2b) containing two oxime groups in one molecule includes a compound represented by the following general formula (9). General formula (9) [Chemical Formula 2] (In general formula (9), X1 and X2 each independently represent a carbonyl bond (—CO—) or a single bond. X3 represents a single bond or a sulfur atom. R1 represents an alkyl group having 1 to 20 carbon atoms, and R2 and R3 each independently represent 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. R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

5. The photosensitive composition according to any one of claims 1 to 4, wherein the alkali-soluble resin (A1) is a resin containing a monomer unit (a3) having a glass transition temperature of the homopolymer of 0° C. or lower.

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

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

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

9. A solid-state imaging device having the optical filter according to claim 7.

Images