TWI886098B - Photosensitive resin composition, method for producing patterned cured film, and cured film - Google Patents

Abstract

The subject of the present invention is to provide a photosensitive resin composition having excellent patterning properties, a method for producing a cured film, and a cured product. The solution of the present invention is a photosensitive resin composition comprising an alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C), wherein the crosslinking agent (B) comprises a monofunctional (meth) acrylic monomer (B1), and the monofunctional (meth) acrylic monomer (B1) contains a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent.

Description

Photosensitive resin composition, method for producing patterned cured film, and cured film

The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film, and the cured film.

Since a cured film having a specific shape patterned therein can be easily formed by photolithography, a photosensitive resin composition containing an alkali-soluble resin is widely used in display devices such as liquid crystal displays, semiconductor devices, and other fields.

In the photosensitive composition, a photopolymerization initiator included as a part of its components generates free radicals by exposure. The free radicals polymerize the polymerizable compounds included in the photosensitive composition, and the photosensitive composition is cured. In addition, in the photosensitive resin composition, a crosslinking agent component is formulated for the purpose of improving the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing, while utilizing the free radicals generated by the photopolymerization initiator to polymerize the polymerizable compounds. For the above-mentioned purpose, this crosslinking agent component has been conventionally selected from monomers having an unsaturated vinyl group, and polyfunctional (meth)acrylate monomers having five or more functions, especially dipentaerythritol penta- and hexa-acrylates, have been used.

In recent years, from the perspective of improving productivity, there is an urgent need for highly sensitive photosensitive resin compositions that can form patterns with low exposure. On the other hand, in the case of a cured film with a complex pattern, there are more areas in the film formed by the photosensitive resin composition as the exposure object where the exposure light source that serves as a trigger for curing the photosensitive resin composition does not penetrate. At this time, in the case of a photosensitive resin composition composed of the above-mentioned composition, it is easy to have a defect that the part is not fully cured after exposure. In addition, the application of the photosensitive resin composition to a cured film with a thickness of more than tens of μm is also widely reviewed. However, when forming such a thick cured film, the following undesirable situation is also likely to occur: the exposure light source does not fully reach the far side of the film formed by the photosensitive resin composition that is farther from the light source, that is, usually near the contact surface between the substrate and the photosensitive resin layer, and an insufficiently cured portion is formed in the cured film. In addition, in the case where the photosensitive resin composition contains a colorant, the problem of the insufficiently cured portion being formed in the cured film due to the absorption of the exposure light source by the colorant is significant.

Patent document 1 proposes a photosensitive resin composition of a specific composition for the purpose of achieving good curing of areas in the photosensitive resin composition that cannot be directly reached by activation energy even at low exposure. Patent document 1 specifically proposes a curable composition containing a monofunctional (meth) acrylic monomer (A) having an aromatic group, a compound (B) other than component (A) having an average of at least one polymerizable carbon-carbon double bond in the molecule, and (C) a photopolymerization initiator. Specifically, as component (A), o-phenylphenoxyethyl acrylate is used, and as component (B), acrylate polymers are used. Prior art documents Patent document

Patent document 1: Japanese Patent Application No. 2014-51618

Problem to be solved by the invention

However, even the curable composition described in Patent Document 1 cannot adequately address the problem of insufficiently cured portions being formed in the cured film. In addition, even if the formation of insufficiently cured portions can be suppressed, in this case, although the rectangularity (taper) of the formed line pattern can be improved to a certain extent, on the other hand, further improvement is expected in terms of the linear progression (reproducibility) or resolution of the line pattern. Therefore, a photosensitive resin composition with better sensitivity is required.

The present invention was completed in view of the above-mentioned problems of the prior art. The purpose of the present invention is to provide a photosensitive resin composition with high sensitivity and excellent patterning characteristics such as good line width stability, resolution and rectangularity, a method for producing a patterned cured film using the photosensitive resin composition, and a cured film. Means for solving the problem

The inventors of the present invention have found that the photosensitive resin composition has high sensitivity by mixing a monofunctional (meth)acrylate compound having a specific structure. For example, even in a location where active energy rays are difficult to directly reach when forming a thick cured film or a cured film of a complex shape, good curing can be performed, and the rectangularity (taper) of the pattern is good. The resolution is high and the linear running property (reproducibility) of the pattern is also good, which can improve the patterning characteristics, and thus the present invention has been completed. That is, the present invention is as follows.

The first aspect of the present invention is a photosensitive resin composition, which comprises an alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C), wherein the crosslinking agent (B) comprises a monofunctional (meth)acrylate monomer (B1), and the monofunctional (meth)acrylate monomer (B1) contains a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent.

The second aspect of the present invention is a method for producing a patterned cured film, which comprises the following steps: coating the photosensitive resin composition of the first aspect on a substrate to form a photosensitive resin layer; exposing the aforementioned photosensitive resin layer in a position-selective manner; and developing the exposed aforementioned photosensitive resin layer using a developer.

The third aspect of the present invention is a cured film, which is formed by curing the photosensitive resin composition of the first aspect. Effect of the invention

According to the present invention, a photosensitive resin composition having high sensitivity and excellent patterning characteristics such as good line width stability, resolution and rectangularity, a method for producing a patterned cured film using the photosensitive resin composition, and a cured film can be provided. Form of the invention

The following describes the embodiments of the present invention in detail, but the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the purpose of the present invention.

≪Photosensitive resin composition≫ The photosensitive resin composition comprises an alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C). In the photosensitive resin composition, as the crosslinking agent (B), a monofunctional (meth)acrylate monomer (B1) is included, and the monofunctional (meth)acrylate monomer (B1) contains a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent. The components contained in the photosensitive resin composition are described in order below.

<Alkali-soluble resin (A)> The photosensitive resin composition includes an alkali-soluble resin (A). Herein, in this specification, the alkali-soluble resin (A) refers to a resin having a functional group (e.g., a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) in the molecule that makes it alkali-soluble. The type of the alkali-soluble resin (A) is not particularly limited, and various alkali-soluble resins that have been formulated in the photosensitive resin composition can be used. Below, as preferred specific examples of the alkali-soluble resin (A), a resin having a cardo structure (A1), an acrylic resin (A2), and a novolac resin (A3) are described.

[Resin (A1) having a Cardo structure] The photosensitive resin composition may contain a resin (A1) having a Cardo structure (hereinafter also referred to as "Cardo resin (A1)") as the alkali-soluble resin (A).

As the cardo resin (A1), a resin having a cardo skeleton in its structure and having the desired alkali solubility can be used. The so-called cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to a ring carbon atom constituting the first ring structure. In addition, the second ring structure and the third ring structure may be the same structure or different structures. As a representative example of the cardo skeleton, a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the carbon atom at the 9th position of the fluorene ring can be cited.

The cardo resin (A1) is not particularly limited, and any conventionally known resin can be used. Among them, a resin represented by the following formula (a-1) is preferred. (In formula (a-1), ^Xa represents a group represented by the following formula (a-2). m1 represents an integer of 0 to 20.)

(In formula (a-2), ^Ra1 each independently represents a hydrogen atom, a alkyl group having 1 to 6 carbon atoms, or a halogen atom, ^Ra2 each independently represents a hydrogen atom or a methyl group, ^Ra3 each independently represents a linear or branched alkylene group, m2 represents 0 or 1, and ^Wa represents a group represented by the following formula (a-3)).

(Ring A in formula (a-3) represents an aliphatic ring which can be condensed with an aromatic ring and which can have a substituent. The aliphatic ring can be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring).

In formula (a-2), R ^a3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms, and most preferably ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl.

Regarding the ring A in formula (a-3), as the aliphatic ring, monocyclic alkanes, dicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, etc. can be cited. Specifically, monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane can be cited. The aromatic ring that can be condensed with the aliphatic ring can be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, benzene ring and naphthyl ring are preferred.

Preferred examples of the divalent group represented by formula (a-3) include the following groups.

The divalent group ^Xa in the formula (a-1) can be introduced into the cardo resin (A1) by reacting a tetracarboxylic dianhydride which provides a residual group ^Za with a diol compound represented by the following formula (a-2a).

In formula (a-2a), ^Ra1 , ^Ra2 , ^Ra3 , and m2 are the same as those described for formula (a-2). Ring A in formula (a-2a) is the same as those described for formula (a-3).

The diol compound represented by formula (a-2a) can be produced, for example, by the following method. First, if necessary, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is substituted with a group represented by ^-Ra3 -OH according to a conventional method, and then glycidylation is performed using epichlorohydrin or the like to obtain an epoxide compound represented by the following formula (a-2c).

Next, the epoxy compound represented by formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain a diol compound represented by formula (a-2a). In formula (a-2b) and formula (a-2c), ^Ra1 , ^Ra3 , and m2 are the same as those described for formula (a-2). Ring A in formula (a-2b) and formula (a-2c) is the same as that described for formula (a-3).

In addition, the method for producing the diol compound represented by formula (a-2a) is not limited to the above-mentioned method.

Preferred examples of the diol compound represented by formula (a-2b) include the following diol compounds.

In the above formula (a-1), ^Ra0 is a hydrogen atom or a group represented by -CO-Ya ^- COOH. Here, ^Ya represents a residue obtained by removing the anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

In the above formula (a-1), ^Za represents a residue after removing two anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, etc. In the above formula (a-1), m1 represents an integer of 0 or more and 20 or less.

(In formula (a-4), ^Ra4 , ^Ra5 , and ^Ra6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 represents an integer of 0 to 12.)

The alkyl group that can be selected as R ^a4 in formula (a-4) is an alkyl group having a carbon number of 1 or more and 10 or less. By setting the carbon number of the alkyl group to the above range, the heat resistance of the obtained carboxylic acid ester can be further improved. When ^{R a4} is an alkyl group, from the viewpoint of easily obtaining a cardo resin with excellent heat resistance, the carbon number is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less. When R ^a4 is an alkyl group, the alkyl group may be a straight chain or a branched chain.

As ^Ra4 in formula (a-4), it is more preferred that each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. ^Ra4 in formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and is particularly preferably a hydrogen atom or a methyl group. From the viewpoint of easily preparing a tetracarboxylic dianhydride with high purity, a plurality of ^Ra4 in formula (a-4) are preferably the same group.

m3 in formula (a-4) represents an integer greater than or equal to 0 and less than or equal to 12. By setting the value of m3 to less than or equal to 12, the tetracarboxylic dianhydride can be easily purified. From the viewpoint of easy purification of tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, and more preferably 3. From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2. m3 in formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as ^Ra5 and ^Ra6 in formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as ^Ra4 . From the viewpoint of easy purification of tetracarboxylic dianhydride, ^Ra5 and ^Ra6 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, particularly preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnorbornane)-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride"). Hexanone-6'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride"), methyl norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-(methyl norbornane)-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloacetone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride Octanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone (Decanone)-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride -spiro-α-cyclotridecanone-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α’-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride, etc.

The weight average molecular weight of the cardo resin (A1) is preferably 1000 to 40000, more preferably 2000 to 30000. Within the above range, good developing properties can be obtained, and sufficient heat resistance and film strength can be obtained.

[Acrylic resin (A2)] As the alkali-soluble resin (A), an acrylic resin (A2) can also be preferably used. When using an acrylic resin (A2), various properties of the photosensitive resin composition can be easily adjusted by appropriately adjusting the type of monomer or the ratio of structural units.

As the acrylic resin (A2), a resin containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylic acid ester can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. (Meth)acrylic acid ester is a compound represented by the following formula (a-5), and there is no particular limitation as long as it does not hinder the purpose of the present invention.

In the above formula (a-5), ^Ra7 is a hydrogen atom or a methyl group, and ^Ra8 is a monovalent organic group. The organic group may contain a bond or a substituent other than a carbon group such as a heteroatom in the organic group. In addition, the organic group may be any of a linear chain, a branched chain, and a ring.

The substituent other than the hydrocarbon group in the organic group of R ^a8 is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include a halogen atom, a hydroxyl group, a hydroxyl group, a sulfide group, a cyano group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfinyl group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate ... group), hydroxyimino group, alkyl ether group, alkyl thioether group, aryl ether group, aryl thioether group, amine group (-NH ₂ , -NHR, -NRR': R and R' each independently represent a alkyl group), etc. The hydrogen atom contained in the above substituents may be substituted with a alkyl group. In addition, the alkyl group contained in the above substituents may be any of linear, branched, and cyclic.

As ^Ra8 , an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group is preferred, and these groups may be substituted by a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. In addition, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, iso-decyl, and the like.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, preferred alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

The compound represented by formula (a-5) is preferably an unsaturated compound containing an epoxy group having an epoxy group in R ^a8 . Preferred examples of the unsaturated compound containing an epoxy group represented by formula (a-5) include epoxyalkyl (meth)acrylates such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc.; epoxyalkyl (α-alkyl)acrylates such as glycidyl (α-ethyl)acrylate, glycidyl (α-n-propyl)acrylate, glycidyl (α-n-butyl)acrylate, 6,7-epoxyheptyl (α-ethyl)acrylate, etc.; etc. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate are preferred from the viewpoint of copolymerization reactivity, strength of the cured resin, etc. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

In addition, the acrylic resin (A2) may be a resin obtained by polymerizing monomers other than (meth)acrylates. Examples of such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers may be used alone or in combination of two or more.

Examples of the (meth)acrylamide include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-hydroxyethyl-N-methyl(meth)acrylamide.

Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, liraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and the like.

Examples of the allyl compound include allyl acetate, allyl caproate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetylacetate, allyl lactate and the like; allyloxyethanol; and the like.

Examples of the vinyl ethers include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; and vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; and the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetylacetate, vinyl lactate, vinyl β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

Examples of the styrenes include styrene; alkyl styrenes such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetyloxymethyl styrene; alkoxy styrenes such as methoxy styrene, 4-methoxy-3-methyl styrene, and dimethoxy styrene; halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.

The amount of the structural unit derived from (meth)acrylic acid in the (A3) acrylic resin and the amount of the structural unit derived from other monomers are not particularly limited within the range not hindering the purpose of the present invention. The amount of the structural unit derived from (meth)acrylic acid in the (A3) acrylic resin is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, relative to the mass of the acrylic resin.

The weight average molecular weight of the acrylic resin (A2) is preferably 2000 to 50000, more preferably 5000 to 30000. By setting it within the above range, it tends to be easy to obtain a good balance between the film forming ability of the photosensitive resin composition and the developability after exposure.

[Novolac (phenolic varnish) resin (A3)] The alkali-soluble resin (A) may contain a Novolac resin (A3). When the alkali-soluble resin (A) contains a Novolac resin (A3), a cured film having good heat resistance and being less likely to deform due to heating can be easily formed.

As the Novolac resin (A3), various Novolac resins that have been conventionally formulated in photosensitive resin compositions can be used. As the Novolac resin (A3), preferably, a Novolac resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and an aldehyde in the presence of an acid catalyst is used.

(Phenols) Phenols that can be used to prepare Novolac resin (A3) include phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, and p-butylphenol; Alkylphenols such as phenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, o-catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and pyrogallol; alkylpolyphenols such as alkylresorcinol, alkylo-catechol, and alkylhydroquinone (the number of carbon atoms of all alkyl groups is 1 or more and 4 or less); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferred, and m-cresol and p-cresol are more preferred. In this case, by adjusting the mixing ratio of the two, various properties such as heat resistance of the cured film formed using the photosensitive resin composition can be adjusted. The mixing ratio of m-cresol and p-cresol is not particularly limited, and the molar ratio of m-cresol/p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in a ratio within this range, it is easy to obtain a photosensitive resin composition that can form a cured film with excellent heat resistance.

In addition, Novolac resin produced by combining m-cresol and 2,3,5-trimethylphenol is also preferred. When such a Novolac resin is used, it is particularly easy to obtain a photosensitive resin composition that can form a cured film that is not easily excessively flowed by heating during post-baking. The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, and the molar ratio of m-cresol/2,3,5-trimethylphenol is preferably 70/30 or more and 95/5 or less.

(Aldehydes) As aldehydes that can be used in the preparation of Novolac resin (A3), there can be mentioned, for example, formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

(Acid catalyst) As the acid catalyst that can be used in the preparation of Novolac resin (A3), there can be cited inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts can be used alone or in combination of two or more.

(Molecular weight) The polystyrene-equivalent weight average molecular weight (Mw; hereinafter also referred to as "weight average molecular weight") of the Novolac resin (A3) is preferably 2000 as the lower limit, more preferably 5000, particularly preferably 10000, still more preferably 15000, and most preferably 20000, and the upper limit is preferably 50000, more preferably 45000, still more preferably 40000, and most preferably 35000, from the viewpoint of the resistance of the cured film formed using the photosensitive resin composition to flow due to heating.

As the Novolac resin (A3), at least two resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using resins having different weight average molecular weights in combination, it is possible to achieve a balance between the developability of the photosensitive resin composition and the heat resistance of a cured film formed using the photosensitive resin composition.

The content of the alkali-soluble resin (A) is preferably 30% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 80% by mass or less, relative to the total mass of the solid components of the photosensitive resin composition. By setting the content within the above range, a photosensitive resin composition having excellent developability can be easily obtained.

<(B) Crosslinking agent> (Monofunctional (meth)acrylic monomer (B1)) The photosensitive resin composition includes a crosslinking agent (B), wherein the crosslinking agent (B) includes a monofunctional (meth)acrylic monomer (B1), wherein the monofunctional (meth)acrylic monomer (B1) contains a biphenyl skeleton which may have a substituent or a terphenyl skeleton which may have a substituent. The so-called "(meth)acrylic monomer" refers to an acryl and/or methacrylic monomer which can be derived from (meth)acrylic acid.

Specific examples of the monofunctional (meth)acrylic monomer (B1) include compounds of the following formula.

In the above formula, ^Rx is a hydrogen atom or a methyl group. BP is a biphenyl group which may have a substituent, and the specific skeleton is 1,1'-biphenyl-4-yl, 1,1'-biphenyl-3-yl, or 1,1'-biphenyl-2-yl, preferably 1,1'-biphenyl-2-yl or 1,1'-biphenyl-4-yl. TP is a terphenyl group which may have a substituent, and the specific skeleton is any one of the groups represented by the following formula.

As the monofunctional (meth)acrylic monomer (B1), a monofunctional (meth)acrylic monomer (B1a) having a biphenyl skeleton which may have a substituent is particularly preferred.

In the monofunctional (meth)acrylic monomer (B1), examples of the substituent that the biphenyl skeleton and the terphenyl skeleton may have include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, or a nitro group.

Preferred examples of the monofunctional (meth)acrylic monomer (B1a) include compounds represented by the following formula (B1-1). (In formula (B1-1), R ^b1 is a hydrogen atom or a methyl group, R ^b2 is an alkylene group having 1 to 4 carbon atoms, BP is a biphenyl group which may have a substituent, t1 is an integer from 0 to 10, when t1 is 0, X ^b1 is -O- or -NH-, when t1 is an integer from 1 to 10, X ^b1 is a linking group selected from the group consisting of a single bond, -O-, -NH-, -O-CO-*, -NH-CO-*, -O-CO-O-, and -NH-CO-O-*, and the bond marked with * in the asymmetric linking group among the linking groups is a bond to BP).

The substituents which the biphenyl group may have are the same as the substituents which the biphenyl skeleton and the terphenyl skeleton may have as exemplified above.

The carbon number of the alkylene group as R ^b2 is 1 or more and 4 or less, preferably 2 or 3. Examples of the alkylene group include a straight chain or branched chain alkylene group such as a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, and a butane-1,2-diyl group. Among these, an ethylene group, a 1,3-propylene group, and a 1,2-propylene group are preferred.

t1 is preferably 0, 1 or 2.

The compound represented by the formula (B1-1) is not particularly limited. Preferred examples of the compound represented by the formula (B1-1) include the following compounds.

As the compound represented by the above formula (B1-1), B1-1-a, B1-1-c, B1-1-e, B1-1-f, B1-1-i, and B1-1-m are preferred, and B1-1-a and B1-1-c are particularly preferred.

(Multifunctional (meth)acrylic monomer (B2)) The photosensitive resin composition may contain a crosslinking agent (B) other than the monofunctional (meth)acrylic monomer (B1). Examples of the crosslinking agent (B) other than the monofunctional (meth)acrylic monomer (B1) include a multifunctional (meth)acrylic monomer (B2).

Preferred examples of the polyfunctional (meth)acrylic monomer (B2) include polyfunctional (meth)acrylates represented by the following formula (B2-1). (In formula (B2-1), R ^b3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^b4 is a t2-valent residue obtained by donating t2 hydroxyl groups among the m hydroxyl groups of the polyol R ^b5 (OH) _m to the ester bond in formula (B2-1), m and t2 are each independently an integer of 2 to 20, and m is greater than t2).

Specific examples of the multifunctional (meth)acrylic monomer represented by formula (B2-1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-modified trihydroxymethylpropane tri(meth)acrylate, propylene oxide-modified trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, glycerol di(meth)acrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, (meth) 2-Hydroxy-3-(meth)acryloyloxypropyl acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl di(meth)acrylate, epichlorohydrin-modified hexahydrophthalic acid di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate Ester, urethane (meth) acrylate (i.e., the reaction product of toluene diisocyanate, trimethyl-1,6-hexanediisocyanate, or 1,6-hexanediisocyanate and 2-hydroxyethyl (meth) acrylate), hydroxy neopentyl glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide-modified neopentyl glycol di(meth) acrylate, propylene oxide-modified (meth)acrylates such as (meth)acrylate methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensates of polyols and N-hydroxymethyl(meth)acrylamide, and triacrylformal, etc. These polyfunctional monomers may be used alone or in combination of two or more.

Among the specific examples of the polyfunctional (meth)acrylate monomer represented by the above formula (B2-1), from the viewpoint of improving the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing, a polyfunctional monomer having three or more functions is preferred, a polyfunctional monomer having four or more functions is more preferred, and a polyfunctional monomer having five or more functions is further preferred. Particularly preferred are dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and mixtures thereof.

The content of the crosslinking agent (B) in the photosensitive resin composition is preferably 10% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 50% by mass or less, relative to the total mass of the solid components of the photosensitive resin composition. By setting the content within the above range, it is easy to achieve a balance between sensitivity, developability, and resolution.

In addition, the content of the monofunctional (meth)acrylic monomer (B1) is 1% by mass or more and 100% by mass or less, preferably 3% by mass or more and 70% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, relative to the total mass of the crosslinking agent (B), of the total crosslinking agent component (B). By making the content of the (meth)acrylic monomer (B1) within the above range, the curing of the portion that cannot be directly reached by the active energy during the position-selective exposure of the photosensitive resin composition can be promoted, and when a thick film, specifically, a cured film of 5 μm or more and 50 μm or less is formed, sufficient curing can be performed even near the substrate side located far from the exposure side.

As a further preferred embodiment, the crosslinking agent (B) preferably comprises 1% by mass or more and 99% by mass or less of the monofunctional (meth)acrylic monomer (B1) and 1% by mass or more and 99% by mass or less of the polyfunctional (meth)acrylic monomer (B2), and preferably comprises 3% by mass or more and 50% by mass or less of (B1) and 50% by mass or more and 97% by mass or less of the polyfunctional (meth)acrylic monomer (B2), relative to the total mass of the crosslinking agent (B). In this case, when the photosensitive resin composition is used to form a thick coating film as described above, the coating film as a whole is fully cured as described above. Therefore, it is easy to make the taper angle of the patterned cured film formed by position selective exposure and development a good angle close to vertical.

<Photopolymerization initiator (C)> The photosensitive resin composition further contains a photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited, and a conventionally known photopolymerization initiator can be used.

Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)-2-hydroxy-2-methylpropane-1-one, and the like. ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyl oxime, 2-(benzoyl)hydroxy amino)-1-[4-(phenylthio)phenyl]-1-octanone, 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazole-3-yl]ethanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 4-benzyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl -β-methoxyethyl acetal, benzyl dimethyl ketone, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, isopropylbenzene hydroperoxide, 2-butylbenzimidazole, 2-butylbenzoxazole, 2-butylbenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p '-Bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, diphenylethanedione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butylacetophenone Trichloroacetophenone, tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, dibenzosuberone, 4-dimethylaminobenzoic acid pentyl ester, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran- 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)phenylphenyl-s-triazine, 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)phenylphenyl-s-triazine, 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)phenylphenyl-s-triazine, etc. These photopolymerization initiators may be used alone or in combination of two or more.

As the photopolymerization initiator (C), an oxime compound represented by the following formula (c1) is preferably used. (R ^c1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen group, a nitro group, and a cyano group, n1 is an integer of 0 to 4, n2 is 0 or 1, R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, and R ^c3 is a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms).

In formula (c1), R ^c1 is not particularly limited within the range not hindering the purpose of the present invention, and can be appropriately selected from various organic groups. Preferred examples of ^Rc1 when it is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, an amino group, an amino group substituted by one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen group, a nitro group, and a cyano group. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. The number of carbon atoms of a substituent does not include the number of carbon atoms of a substituent further possessed by the substituent.

When R ^c1 is an alkyl group, it is preferably 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. In addition, when R ^c1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of R ^c1 when it is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. In addition, when R ^c1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and the number of carbon atoms is more preferably 1 or more and 6 or less. In addition, when R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. As specific examples of R ^c1 being an alkoxy group, there can be cited a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, a n-nonyloxy group, an isononyloxy group, a n-decyloxy group, and an isodecyloxy group. In addition, when R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 6. Specific examples of R ^c1 being a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples of R ^c1 being a cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7. Specific examples of R ^c1 being a saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentyl, 2,2-dimethylpropionyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, and n-hexadecyl. Specific examples of R ^c1 when it is a saturated aliphatic acyloxy group include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-pentanoyloxy, 2,2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanyloxy, and n-hexadecanoyloxy.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7. Specific examples of R ^c1 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10. In addition, when R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14. Specific examples of R ^c1 when it is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples of R ^c1 when it is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclic group formed by condensing the monocyclic rings with each other or condensing the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, oxazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^c1 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c1 is an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of these preferred organic groups are the same as those for R ^c1 . Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino.

When the phenyl group, naphthyl group, and heterocyclic group included in R ^c1 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclic group included in R ^c1 further have a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclic group included in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

In terms of chemical stability, small steric hindrance, and easy synthesis of oxime ester compounds, R ^c1 is preferably a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms. An alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

With respect to the phenyl group to which R ^c1 is bonded, when the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is the 1 position and the position of the methyl group is the 2 position, the position at which R ^c1 is bonded to the phenyl group is preferably the 4 position or the 5 position, and more preferably the 5 position. In addition, n1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. When R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted by an alkyl group having 1 or more and 6 or less carbon atoms.

In R ^c2 , the substituents possessed by the phenyl group or the carbazolyl group are not particularly limited within the scope that does not hinder the purpose of the present invention. Examples of preferred substituents that the phenyl group or the carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyloxy group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, and the like.

When R ^c2 is a carbazolyl group, examples of preferred substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent and has a carbon number of 7 to 20 which may have a substituent, a naphthyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylalkyl group which may have a carbon number of 11 to 20 which may have a substituent, a heterocyclic group which may have a substituent, and a heterocycliccarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

Specific examples of the substituent that the phenyl group or the carbazolyl group may have are the same as those for R c1, including an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group that may have a substituent, a naphthylalkyl group that may have a substituent, a heterocyclic group that may have a substituent, and an amino ^group substituted with one or two organic groups.

In R ^c2 , when the phenyl group, naphthyl group, and heterocyclic group included in the substituent group possessed by the phenyl group or carbazolyl group further possess a substituent group, examples of the substituent group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms. ; phenyl; naphthyl; benzoyl; naphthyl; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl; halogen; nitro; cyano. When the phenyl, naphthyl, and heterocyclic group included in the substituents possessed by the phenyl or carbazolyl group further have a substituent, the number of the substituent is not limited within the range that does not hinder the purpose of the present invention, and is preferably 1 to 4. When the phenyl, naphthyl, and heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c2 , from the viewpoint of easily obtaining a photopolymerization initiator with excellent sensitivity, a group represented by the following formula (c2) or (c3) is preferred, a group represented by the following formula (c2) is more preferred, and a group represented by the following formula (c2) wherein A is S is particularly preferred.

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen group, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 to 4).

(R ^c5 and R ^c6 are each a monovalent organic group).

When R ^c4 in formula (c2) is an organic group, it can be selected from various organic groups within the scope not hindering the purpose of the present invention. Preferred examples of R ^c4 in formula (c2) when it is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; a halogen group; a nitro group; and a cyano group.

Among R ^c4 , preferably benzoyl; naphthyl; benzoyl substituted with a group selected from the group consisting of alkyl having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; nitro, more preferably benzoyl; naphthyl; 2-methylphenylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

In formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n3 is 1, the bonding position of R ^c4 is preferably para relative to the bond between the phenyl group to which R ^c4 is bonded and the oxygen atom or sulfur atom.

R ^c5 in formula (c3) can be selected from various organic groups within the range that does not hinder the purpose of the present invention. Preferred examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent and have a carbon number of 7 to 20 which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a carbon number of 11 to 20 which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent.

In R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

R ^c6 in formula (c3) is not particularly limited within the scope that does not hinder the purpose of the present invention, and can be selected from various organic groups. Specific examples of preferred groups as R ^c6 include alkyl groups having 1 to 20 carbon atoms, phenyl groups which may have a substituent, naphthyl groups which may have a substituent, and heterocyclic groups which may have a substituent. Among these groups, R ^c6 is more preferably phenyl groups which may have a substituent, and particularly preferably 2-methylphenyl groups.

When the phenyl group, naphthyl group and heterocyclic group included in ^Rc4 , ^Rc5 or ^Rc6 further has a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen group, a nitro group and a cyano group. When the phenyl group, naphthyl group, or heterocyclic group included in R ^c4 , R ^c5 , or R ^c6 further has a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, and is preferably 1 to 4. When the phenyl group, naphthyl group, or heterocyclic group included in ^{R c4} , R ^c5 , or R ^c6 has a plurality of substituents, the plurality of substituents may be the same or different.

R ^c3 in formula (c1) is a hydrogen atom or an alkyl group having a carbon number of 1 to 6. R ^c3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

Among the oxime ester compounds represented by the formula (c1), particularly preferred compounds include the following PI-1 to PI-42.

In addition, as the photopolymerization initiator (C), an oxime ester compound represented by the following formula (c4) is preferred.

( ^Rc7 is a hydrogen atom, a nitro group or a monovalent organic group, ^Rc8 and ^Rc9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, ^Rc8 and ^Rc9 may bond to each other to form a ring, ^Rc10 is a monovalent organic group, ^Rc11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n4 is an integer of 0 to 4, and n5 is 0 or 1).

Here, as the oxime compound used for producing the oxime ester compound of the formula (c4), a compound represented by the following formula (c5) is preferred.

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 and n5 are the same as in formula (c4)).

In formula (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. ^{R c7} is bonded to a six-membered aromatic ring on the fluorene ring in formula (c4) that is different from the six-membered aromatic ring to which the group represented by -(CO) _n5 - is bonded. In formula (c4), the bonding position of R ^c7 relative to the fluorene ring is not particularly limited. When the compound represented by formula (c4) has one or more R ^c7 , it is preferred that one of the one or more R ^c7 is bonded to the 2-position in the fluorene ring from the perspective of easiness in synthesizing the compound represented by formula (c4). When there are multiple R ^c7 , the multiple R ^c7 may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited within the range not hindering the object of the present invention, and can be appropriately selected from various organic groups. Preferred examples of R ^c7 when it is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, and more preferably 1 to 6. In addition, when R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of R ^c7 when it is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. In addition, when R ^c7 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. In addition, when R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. As specific examples of R ^c7 when it is an alkoxy group, there can be cited a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, a n-nonyloxy group, an isononyloxy group, a n-decyloxy group, and an isodecyloxy group. In addition, when R ^c7 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples of R ^c7 when it is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples of R ^c7 when it is a cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples of R ^c7 being a saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentyl, 2,2-dimethylpropionyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, and n-hexadecyl. Specific examples of R ^c7 when it is a saturated aliphatic acyloxy group include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-pentanoyloxy, 2,2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanyloxy, and n-hexadecanoyloxy.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, and more preferably 2 to 7. Specific examples of R ^c7 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

When R ^c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. In addition, when R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of when R ^c7 is a phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. Specific examples of when R ^c7 is a naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c7 is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing one or more N, S, and O, or a heterocyclic group formed by condensing the monocyclic rings with each other or condensing the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, oxazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ^c7 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c7 is a heterocyclic carbonyl group, the heterocyclic group included in the heterocyclic carbonyl group is the same as when R ^c7 is a heterocyclic group.

When R ^c7 is an amino group substituted with one or two organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of these preferred organic groups are the same as those for R ^c7 . Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino.

When the phenyl group, naphthyl group, and heterocyclic group included in R ^c7 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclic group included in ^{R c7} further have a substituent, the number of the substituent is not limited within the range not hindering the purpose of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclic group included in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, when R ^c7 is a nitro group or a group represented by R ^c12 -CO-, the sensitivity tends to be improved, so it is preferred. R ^c12 is not particularly limited within the scope that does not hinder the purpose of the present invention, and can be selected from various organic groups. Examples of preferred groups as R ^c12 include alkyl groups with a carbon number of 1 to 20, phenyl groups that may have a substituent, naphthyl groups that may have a substituent, and heterocyclic groups that may have a substituent. Among these groups, 2-methylphenyl, thiophene-2-yl, and α-naphthyl are particularly preferred as R ^c12 . In addition, when R ^c7 is a hydrogen atom, the transparency tends to be good, so it is preferred. When R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be further improved.

In formula (c4), ^Rc8 and ^Rc9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. ^Rc8 and ^Rc9 may be bonded to each other to form a ring. Among these groups, ^Rc8 and ^Rc9 are preferably a chain alkyl group which may have a substituent. When ^Rc8 and ^Rc9 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When ^Rc8 and ^Rc9 are unsubstituted chain alkyl groups, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of ^Rc8 and ^Rc9 when they are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, sec-octyl, tert-octyl, n-nonyl, iso-nonyl, n-decyl, and iso-decyl. When ^Rc8 and ^Rc9 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl.

When R ^c8 and R ^c9 are chain alkyl groups having substituents, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the number of carbon atoms of the chain alkyl group does not include the number of carbon atoms of the substituent. The chain alkyl group having substituents is preferably straight chain. The substituents that the alkyl group may have are not particularly limited within the scope that does not hinder the purpose of the present invention. Preferred examples of substituents include cyano groups, halogen atoms, cyclic organic groups, and alkoxycarbonyl groups. As halogen atoms, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms are listed. Among these, fluorine atoms, chlorine atoms, and bromine atoms are preferred. As the cyclic organic group, a cycloalkyl group, an aromatic alkyl group, and a heterocyclic group can be cited. As specific examples of the cycloalkyl group, the same as the preferred examples when R ^c7 is a cycloalkyl group. As specific examples of the aromatic alkyl group, phenyl, naphthyl, biphenyl, anthracenyl, and phenanthrenyl can be cited. As specific examples of the heterocyclic group, the same as the preferred examples when R ^c7 is a heterocyclic group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be a straight chain or a branched chain, preferably a straight chain. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When ^Rc8 and ^Rc9 are cyclic organic groups, the cyclic organic groups may be alicyclic groups or aromatic groups. Examples of the cyclic organic groups include aliphatic cyclic alkyl groups, aromatic alkyl groups, and heterocyclic groups. When ^Rc8 and ^Rc9 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as those when ^Rc8 and ^Rc9 are chain alkyl groups.

When ^Rc8 and ^Rc9 are aromatic alkyl groups, the aromatic alkyl group is preferably: phenyl, or a group formed by a plurality of benzene rings bonded via carbon-carbon bonds, or a group formed by condensation of a plurality of benzene rings. When the aromatic alkyl group is phenyl, or a group formed by bonding or condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic alkyl group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic alkyl group include phenyl, naphthyl, biphenylyl, anthracenyl, and phenanthryl.

When ^Rc8 and ^Rc9 are aliphatic cyclic alkyl groups, the aliphatic cyclic alkyl group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic alkyl group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

When R ^c8 and R ^c9 are heterocyclic groups, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, or O, or is a heterocyclic group formed by condensing the monocyclic rings with each other or condensing the monocyclic ring with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, oxazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

R ^c8 and R ^c9 may bond to each other to form a ring. The group including the ring formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 bond to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

When the group formed by the bonding of ^Rc8 and ^Rc9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.

Among the R ^c8 and R ^c9 described above, a preferred example of the group is a group represented by the formula -A ¹ -A ² , wherein A ¹ is a linear alkyl group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkyl group of ^A1 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When ^A2 is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When ^A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. When ^A2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, preferably linear. When ^A2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that ^Rc8 and ^Rc9 have as a substituent. When ^A2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group ^that Rc8 and ^Rc9 have as a substituent.

Preferred specific examples of ^Rc8 and ^Rc9 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; alkoxyalkyl groups such as 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; -cyanopropyl, 4-cyanobutyl, 5-cyanopentyl, 6-cyanohexyl, 7-cyanoheptyl, and 8-cyanooctyl; phenylalkyl such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentyl cycloalkylalkyl such as 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, and 8-methoxycarbonyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, and 8-methoxycarbonyl-n-octyl; 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, and 8-methoxycarbonyl-n-octyl. [0063] The invention also includes alkoxycarbonylalkyl such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, and 8-chloro-n-octyl; and halogenated alkyl such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

Among the above, preferred groups for R ^c8 and R ^c9 are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

As an example of a preferred organic group for R ^c10 , Similarly, ^{for c7} , alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzyl which may have a substituent, phenoxycarbonyl which may have a substituent, benzyloxy which may have a substituent, phenylalkyl which may have a substituent, naphthyloxy which may have a substituent, naphthyloxy which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino group substituted by one or two organic groups, oxoline-1-yl group, and piperazin-1-yl group may have a substituent, and the like may be listed. Specific examples of these groups are the same as those described for R ^c7 . In addition, R ^c10 is preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituents that may be possessed by the phenoxyalkyl group and the phenylthioalkyl group are the same as the substituents that may be possessed by the phenyl group included in R ^c7 .

Among the organic groups, R ^c10 is preferably an alkyl group, a cycloalkyl group, a phenyl group or a cycloalkylalkyl group which may have a substituent, or a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and a methyl group is most preferred. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

Furthermore, R ^c10 is preferably a group represented by -A ³ -CO-OA ^{4. A 3} is a divalent organic group, preferably a divalent alkyl group, preferably an alkylene group. ^{A 4} is a monovalent organic group, preferably a monovalent alkyl group.

When ^A3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When ^A3 is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

Preferred examples of ^A4 include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Preferred specific examples of ^A4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

Preferred specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonylethyl, 2-n-butyloxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl.

R ^c10 has been described above, and R ^c10 is preferably a group represented by the following formula (c4a) or (c4b). (In formulas (c4a) and (c4b), ^Rc13 and ^Rc14 are each an organic group, n6 is an integer greater than 0 and less than 4, when ^Rc13 and ^Rc14 are present at adjacent positions on the benzene ring, ^Rc13 and ^Rc14 can bond with each other to form a ring, n7 is an integer greater than 1 and less than 8, n8 is an integer greater than 1 and less than 5, n9 is an integer greater than 0 and less than (n8+3), and ^Rc15 is an organic group).

Examples of organic groups related to R ^c13 and R ^c14 in formula (c4a) are the same as those for R ^c7 . R ^c13 is preferably an alkyl group or a phenyl group. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by formula (c4a) in which R ^c13 and R ^c14 form a ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, and the like. In the above formula (c4a), n6 is an integer greater than or equal to 0 and less than or equal to 4, preferably 0 or 1, and more preferably 0.

In the above formula (c4b), R ^c15 is an organic group. As the organic group, the same groups as those described for R ^c7 can be cited. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R ^c15 , methyl, ethyl, propyl, isopropyl, butyl, etc. can be preferably exemplified, and among these, a methyl group is more preferred.

In the above formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (c4b), n9 is 0 to (n8+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0. In the above formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, particularly preferably 1 or 2.

In formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. When R ^c11 is an alkyl group, the substituent may be preferably phenyl, naphthyl, etc. When R ^c7 is an aryl group, the substituent may be preferably alkyl group having 1 to 5 carbon atoms, alkoxy group, halogen atom, etc.

In the formula (c4), R ^c11 is preferably exemplified by a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like. Among these, a methyl group or a phenyl group is more preferred.

The compound represented by formula (c4) can be prepared by a method comprising the step of converting the oxime group (>C=N-OH) contained in the compound represented by formula (c5) to an oxime ester group represented by>C=NO-COR ^c11 . R ^c11 is the same as R ^c11 in formula (c4).

The conversion of the oxime group (＞C＝N-OH) to the oxime ester group represented by ＞C＝NO-COR ^c11 can be carried out by reacting the compound represented by the above formula (c5) with an acylation agent. Examples of the acylation agent for providing the acyl group represented by -COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O or an acyl halide represented by R ^c11 COHal (Hal is a halogen atom).

Preferred specific examples of the compound represented by formula (c4) include the following PI-43 to PI-83.

Among these, in terms of sensitivity, it is preferred to use an oxime-based photopolymerization initiator, and more preferably at least one selected from the group consisting of an oxime compound represented by formula (c1), an oxime ester compound represented by formula (c4), or an oxime ester compound having a fluorene skeleton or a carbazolyl skeleton and a nitro group.

The content of the photopolymerization initiator (C) in the photosensitive resin composition is not particularly limited within the range not hindering the purpose of the present invention. The content of the photopolymerization initiator (C) is preferably 0.1 mass % to 20 mass %, more preferably 0.3 mass % to 10 mass %, relative to the mass of the solid component of the photosensitive resin composition.

<(D) Sensitizer> The photosensitive resin composition may contain the above-mentioned (C) photopolymerization initiator and (D) sensitizer. By simultaneously containing the (C) photopolymerization initiator and (D) sensitizer, the photosensitive resin composition can be cured well even when using a light source with low irradiation energy such as LED exposure.

As the sensitizer (D), any compound conventionally used for sensitizing a photopolymerization initiator in a photosensitive resin composition can be used without particular limitation.

As the (D) sensitizer, a compound having one or more substituents selected from the group consisting of an alkoxy group, a substituted carbonyloxy group (carbonyloxy), and an oxo group (=O) is preferred. As the compound having the substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferred. The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O). Examples of such substituents include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, an aromatic acyl group having 7 to 11 carbon atoms (aroyl group), a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and a hydroxyl group.

The alkoxy group may be straight chain or branched chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 6 or less. Preferred examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyl, n-nonyloxy, and n-decyloxy.

The substituted carbonyloxy group is a group represented by -O-CO-A ^d . ^{A d} is not particularly limited as long as the sensitizer (D) has the desired sensitizing effect, and can be various organic groups. A is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.

The aryl group or aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as it does not hinder the purpose of the present invention. When the aryl group or aryloxy group has multiple substituents, the multiple substituents may be the same or different. Preferred examples of substituents include alkoxy groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, aliphatic acyl groups having 2 to 7 carbon atoms, aromatic acyl groups having 7 to 11 carbon atoms (aromatic acyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, and hydroxyl groups.

When A ^d is an alkyl group or an alkoxy group, these groups may be straight chain or branched chain. Preferred examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl. Preferred examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, etc. Preferred examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, and 2-ethylhexyloxy.

In the condensed polycyclic aromatic hydrocarbon compound or condensed polycyclic aromatic heterocyclic compound substituted with one or more selected from the group consisting of alkoxy, substituted carbonyloxy, and oxo (=O), the number of rings constituting the condensed ring is not particularly limited as long as the desired sensitization effect can be obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 or more and 6 or less, and most preferably 3 or 4. In addition, the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound only needs to have aromaticity, and the monocyclic ring forming the condensed polycyclic ring does not have to be an aromatic ring.

Preferred examples of the condensed polycyclic ring contained in the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound include acenaphthene ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, xanthene ring, and thiazolidine ring. Among these rings, anthracene ring, condensed tetraphenyl ring, and thiazolidine ring are preferred.

Specific examples of the anthracene ring-containing compound suitable for use as the (D) sensitizer include 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9,10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutyl 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(n-heptylcarbonyloxy)anthracene, 9,10-bis(2-ethylhexanoyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10-bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n-decylcarbonyloxy)anthracene 9,10-bis(benzyloxy)anthracene, 9,10-bis(4-methylbenzyloxy)anthracene, 9,10-bis(2-naphthoyloxy)anthracene, 2-methyl-9,10-bis(acetyloxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2- Methyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-methyl-9,10-bis(benzene 1-methyl-9,10-bis(4-methylbenzyloxy)anthracene, 2-methyl-9,10-bis(2-naphthyloxy)anthracene, 1-methyl-9,10-bis(acetyloxy)anthracene, 1-methyl-9,10-bis(propionyloxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isopropylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9,10-bis(benzyloxy)anthracene 1-Methyl-9,10-bis(4-methylbenzyloxy)anthracene, 1-Methyl-9,10-bis(2-naphthoyloxy)anthracene, 2-ethyl-9,10-bis(acetyloxy)anthracene, 2-ethyl-9,10-bis(propionyloxy)anthracene, 2-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-ethyl- 9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(benzoyloxy)anthracene 1-ethyl-9,10-bis(acetyloxy)anthracene, 1-ethyl-9,10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-ethyl- 9,10-bis(isopropylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(benzoyloxy)anthracene anthracene, 1-ethyl-9,10-bis(4-ethyl-benzyloxy)anthracene, 1-ethyl-9,10-bis(2-naphthoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-butyl 1-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene (4-(tert-butyl)-benzoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, -(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(4-(tert-butyl) -benzoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-pentyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isobutylcarbonyloxy)anthracene anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(benzoyloxy)anthracene, 2-pentyl-9,10-bis(4-(tert-butyl)-benzoyloxy)anthracene, and 2-pentyl-9,10-bis(2-naphthoyloxy)anthracene.

Alternatively, the sensitizer (D) is preferably an anthracene compound substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the anthracene compounds substituted with a halogen atom which are preferred as the sensitizer (D) include 2-chloro-9,10-bis(acetyloxy)anthracene, 2-chloro-9,10-bis(propionyloxy)anthracene, 2-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-butylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2 -Chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-chloro-9,10-bis(benzyloxy)anthracene, 2-chloro-9,10-bis(4-methylbenzyloxy)anthracene, 2-chloro-9,10-bis(2-naphthyloxy)anthracene, 1-chloro-9,10-bis(acetyloxy)anthracene, 1-chloro-9,10-bis(propionyloxy)anthracene, 1-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-chloro-9,10-bis( (n-butylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-chloro-9,10-bis(benzyloxy)anthracene, 1-chloro-9,10-bis(4-methylbenzyloxy)anthracene, 1-chloro-9,10-bis(2-naphthyloxy)anthracene, 2-fluoro-9,10-bis(acetyloxy)anthracene, 2-fluoro-9,10-bis(propionyloxy)anthracene , 2-fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(benzyloxy)anthracene, 2-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 2-fluoro-9, 10-bis(2-naphthoyloxy)anthracene, 1-fluoro-9,10-bis(acetyloxy)anthracene, 1-fluoro-9,10-bis(propionyloxy)anthracene, 1-fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isobutylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene ) anthracene, 1-fluoro-9,10-bis(benzyloxy)anthracene, 1-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 1-fluoro-9,10-bis(2-naphthyloxy)anthracene, 2-bromo-9,10-bis(acetyloxy)anthracene, 2-bromo-9,10-bis(propionyloxy)anthracene, 2-bromo-9,10-bis(n-propylcarbonyloxy)anthracene, 2-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-butylcarbonyloxy)anthracene, 2-bromo-9,1 0-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-bromo-9,10-bis(benzyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzyloxy)anthracene, 2-bromo-9,10-bis(2-naphthoyloxy)anthracene, 1-bromo-9,10-bis(acetyloxy)anthracene, 1-bromo-9,10-bis(propionyloxy)anthracene, 1-bromo-9,10-bis(n-propylcarbonyloxy)anthracene 1-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-butylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-bromo-9,10-bis(benzyloxy)anthracene, 1-bromo-9,10-bis(4-methylbenzyloxy)anthracene, and 1-bromo-9,10-bis(2-naphthoyloxy)anthracene.

In addition, as the (D) sensitizer, an anthracene compound substituted with an alkoxy group is preferred. Specific examples of the anthracene compound substituted with an alkoxy group as the (D) sensitizer include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis(n-propoxy)anthracene, 9,10-bis(n-butoxy)anthracene, 9,10-bis(n-pentyloxy)anthracene, 9,10-bis(isopentyloxy)anthracene, 9,10-bis(n-hexyloxy)anthracene, 9,10-bis(n-heptyloxy)anthracene, 9,10-bis(n-octyloxy)anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-(n-propoxy)anthracene, 9-(n-butoxy)anthracene oxy)anthracene, 9-(n-pentyloxy)anthracene, 9-(isopentyloxy)anthracene, 9-(n-hexyloxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy)anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-bis(n-propoxy)anthracene, 2-methyl-9,10-bis(n-butoxy)anthracene, 2-methyl-9,10-bis(n-pentyloxy)anthracene, 2-methyl-9,10-bis(isopentyloxy)anthracene, 2-methyl-9,10-bis(n-hexyloxy)anthracene , 2-methyl-9,10-bis(n-heptyloxy)anthracene, 2-methyl-9,10-bis(n-octyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-bis(n-propoxy)anthracene, 2-ethyl-9,10-bis(n-butoxy)anthracene, 2-ethyl-9,10-bis(n-pentyloxy)anthracene, 2-ethyl-9,10-bis(isopentyloxy)anthracene, 2-ethyl-9,10-bis(n-hexyloxy)anthracene, 2-ethyl-9,1 0-bis(n-heptyloxy)anthracene, 2-ethyl-9,10-bis(n-octyloxy)anthracene, 2-ethyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-methyl-9-methoxyanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl-9-(n-propyloxy)anthracene, 2-methyl-9-(n-butoxy)anthracene, 2-methyl-9-(n-pentyloxy)anthracene, 2-methyl-9-(isopentyloxy)anthracene, 2-methyl-9-(n-hexyloxy)anthracene, 2-methyl-9-(n-heptyloxy)anthracene, 2-methyl-9-(n-octyloxy)anthracene, 2-methyl-9-(2-ethylhexyloxy)anthracene 2-ethyl-9-(n-propoxy)anthracene, 2-ethyl-9-(n-butoxy)anthracene, 2-ethyl-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxy)anthracene, 2-ethyl-9-(n-hexyloxy)anthracene, 2-ethyl-9-(n-heptyloxy)anthracene, 2-ethyl-9-(n-octyloxy)anthracene, 2-ethyl-9-(2-ethylhexyloxy)anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis(n-propoxy)anthracene 2-chloro-9,10-bis(n-butoxy)anthracene, 2-chloro-9,10-bis(n-pentyloxy)anthracene, 2-chloro-9,10-bis(isopentyloxy)anthracene, 2-chloro-9,10-bis(n-hexyloxy)anthracene, 2-chloro-9,10-bis(n-heptyloxy)anthracene, 2-chloro-9,10-bis(n-octyloxy)anthracene, 2-chloro-9,10-bis(2-ethylhexyloxy)anthracene, 2-bromo-9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo-9,10-bis(n-propoxy)anthracene, 2-bromo-9,10-bis(n-butoxy)anthracene ) anthracene, 2-bromo-9,10-bis(n-pentyloxy) anthracene, 2-bromo-9,10-bis(isopentyloxy) anthracene, 2-bromo-9,10-bis(n-hexyloxy) anthracene, 2-bromo-9,10-bis(n-heptyloxy) anthracene, 2-bromo-9,10-bis(n-octyloxy) anthracene, 2-bromo-9,10-bis(2-ethylhexyloxy) anthracene, 2-chloro-9-methoxy anthracene, 2-chloro-9-ethoxy anthracene, 2-chloro-9-(n-propoxy) anthracene, 2-chloro-9-(n-butoxy) anthracene, 2-chloro-9-(n-pentyloxy) anthracene, 2-chloro-9-(isopentyloxy) anthracene, 2- Chloro-9-(n-hexyloxy)anthracene, 2-chloro-9-(n-heptyloxy)anthracene, 2-chloro-9-(n-octyloxy)anthracene, 2-chloro-9-(2-ethylhexyloxy)anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9-(n-propoxy)anthracene, 2-bromo-9-(n-butoxy)anthracene, 2-bromo-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxy)anthracene, 2-bromo-9-(n-hexyloxy)anthracene, 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, and 2-bromo-9-(2-ethylhexyloxy)anthracene.

Among the anthracene compounds described above, 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9,10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis( The present invention also includes 9,10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis(2-ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.

Specific examples of compounds containing fused tetraphenyl rings suitable for use as (D) sensitizers include: 2-methyl-5,11-dioxo-6,12-bis(acetyloxy)fused tetraphenyl (naphthacene), 2-methyl-5,11-dioxo-6,12-bis(propionyloxy)fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-propylcarbonyl) 2-Methyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-butylcarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)condensed tetraphenyl, 2-Methyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-heptylcarbonyloxy)condensed tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(acetyloxy)condensed tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(propionyloxy)condensed tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(propionyloxy)condensed tetraphenyl 6,12-bis(n-propylcarbonyloxy)tetraphenylene dioxo, 2-ethyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)tetraphenylene, 2-ethyl-5,11-dioxo-6,12-bis(n-butylcarbonyloxy)tetraphenylene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)tetraphenylene, 2-ethyl-5,11-dioxo-6,1 Alkylcarbonyloxy-substituted tetraphenyl compounds such as 2-bis(n-pentylcarbonyloxy)tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)tetraphenyl, and 2-ethyl-5,11-dioxo-6,12-bis(n-heptylcarbonyloxy)tetraphenyl; 2-methyl-5,11-dioxo-6,12-bis(benzoyloxy)tetraphenyl, 2-methyl-5,1 1-dioxo-6,12-bis(o-toluoyloxy)-fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(m-toluoyloxy)-fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(p-toluoyloxy)-fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(α-naphthoyloxy)-fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(β-naphthoyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(benzoyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(o-toluoyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(m-toluoyloxy) fused tetraphenyl, 2- Aromatic acyloxy-substituted tetraphenyl compounds such as ethyl-5,11-dioxo-6,12-bis(p-toluenecarbonyloxy)tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(α-naphthoyloxy)tetraphenyl, and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)tetraphenyl; 2-methyl-5,11-dioxo-6,12-bis(methoxy)tetraphenyl 2-Methyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-propyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-butyloxycarbonyloxy)condensed tetraphenyl 2-Methyl-5,11-dioxo-6,12-bis(isobutoxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-pentyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-heptyloxycarbonyloxy)condensed tetraphenyl ) fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(n-propoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(isopropoxycarbonyloxy)condensed tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(n-butoxycarbonyloxy)condensed tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(isobutoxycarbonyloxy)condensed tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(n-pentyloxycarbonyloxy)condensed tetraphenyl, 2-ethyl Alkoxycarbonyloxy-substituted tetraphenyl compounds such as 2-ethyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(n-heptyloxycarbonyloxy)tetraphenyl, and 2-ethyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)tetraphenyl; and 2-methyl-5,11-dioxo-6,12 -Bis(phenoxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)condensed tetraphenyl, 2-methyl-5,11-dioxo-6,12- Bis(α-naphthyloxycarbonyloxy) fused tetraphenyl, 2-methyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy) fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy) fused tetraphenyl Aroyloxycarbonyloxy-substituted fused tetraphenyl compounds such as (m-tolyloxycarbonyloxy)-fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)-fused tetraphenyl, 2-ethyl-5,11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)-fused tetraphenyl, and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)-fused tetraphenyl.

Among the above-mentioned compounds containing fused tetraphenyl rings, 5,11-dioxo-6,12-bis(methoxycarbonyloxy)fused tetraphenyl, 5,11-dioxo-6,12-bis(ethoxycarbonyloxy)fused tetraphenyl, 5,11-dioxo-6,12-bis(isopropoxycarbonyloxy)fused tetraphenyl, 5,11-dioxo-6,12-bis(isobutoxycarbonyloxy)fused tetraphenyl, 5,11-dioxo-6,12-bis(n-butylcarbonyloxy)fused tetraphenyl, 5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)fused tetraphenyl, and 5,11-dioxo-6,12-bis(n-heptyloxy)fused tetraphenyl are preferred. From the viewpoint of compatibility with the photopolymerizable compound (A), preferred are 5,11-dioxo-6,12-bis(isopropoxycarbonyloxy)-fused tetraphenyl, 5,11-dioxo-6,12-bis(isobutoxycarbonyloxy)-fused tetraphenyl, 5,11-dioxo-6,12-bis(n-butyryloxy)-fused tetraphenyl, 5,11-dioxo-6,12-bis(n-pentyryloxy)-fused tetraphenyl, and 5,11-dioxo-6,12-bis(heptyloxy)-fused tetraphenyl.

Specific examples of the compound containing a thiathione ring suitable for use as the (D) sensitizer include thiathion-9-one, 2-methyl-9H-thiathion-9-one, 2-isopropyl-9H-thiathion-9-one, 1,4-dimethylthiathion-9-one, and 3-methyl-9-oxo-9H-thiathion-2-yl acetate.

The content of the sensitizer of the component (D) is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 15 parts by mass or more and 50 parts by mass or less, relative to a total of 100 parts by mass of the photopolymerization initiator component (C) in the photosensitive resin composition. When the photosensitive resin composition contains the sensitizer within the above range, the curing reaction based on exposure proceeds uniformly, and a patterned cured film with a particularly good edge angle is easily formed.

<(E) Colorant> Depending on the application, the photosensitive resin composition may not contain a colorant and may be a substantially colorless and transparent composition. On the other hand, for other applications, the photosensitive resin composition may further contain a (D) colorant. Since the photosensitive resin composition contains a colorant such as a black pigment as the (D) component, it can be suitable for use in, for example, forming a black matrix (or black bank) in a color filter of a display device. In addition, a colored colorant can be suitable for use in, for example, forming a color filter of a display device.

The colorant (D) contained in the photosensitive resin composition is not particularly limited. When the colorant is used as a light-shielding agent, a black pigment is preferably used as the light-shielding agent. As the black pigment, various pigments (whether organic or inorganic) such as carbon black, titanium black, metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver can be cited. Among these, carbon black having high light-shielding properties is preferably used.

As carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, and channel black having excellent light-shielding properties is preferably used. In addition, resin-coated carbon black can also be used.

Compared with carbon black not coated with resin, carbon black coated with resin has lower conductivity. Therefore, when used as a black matrix of a liquid crystal display element such as a liquid crystal display, a low power consumption display with less current leakage and high reliability can be manufactured. As black pigments other than carbon black, for example, (D2a) perylene-based pigments and (D2b) lactam-based pigments can be cited. These pigments can be used in combination of two or more.

The perylene pigment (D2a) is not particularly limited as long as it is a black pigment formed by a compound having a perylene skeleton. Specific examples of the perylene pigment (D2a) include a perylene pigment represented by the following formula (d-1), a perylene pigment represented by the following formula (d-2), and a perylene pigment represented by the following formula (d-3). Among the commercially available products, it is preferred to use products K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, and 34 as the perylene pigment (D2a).

In formula (d-1), ^Rd1 and ^Rd2 each independently represent an alkylene group having 1 to 3 carbon atoms, and ^Rd3 and ^Rd4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group.

In formula (d-2), R ^d5 and R ^d6 each independently represent an alkylene group having 1 to 7 carbon atoms.

In formula (d-3), ^Rd7 and ^Rd8 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P. When ^Rd7 and ^Rd8 are alkyl groups, the alkyl group may be linear or branched.

The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) can be synthesized by the method described in Japanese Patent Publication No. 62-1753 and Japanese Patent Publication No. 63-26784, for example. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials and heated in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent or a mixed solvent thereof, thereby obtaining the target product.

In order to disperse the perylene pigment (D2a) well in the photosensitive resin composition and form a cured film with low transmittance to light in a wide wavelength range, the volume average particle size of the perylene pigment is preferably 10 nm or more and 1000 nm or less, more preferably 10 nm or more and 500 nm or less, and particularly preferably 10 nm or more and 200 nm or less. In addition, when the volume particle size of the perylene pigment is within the above range, it is easy to stably form a cured film with a low arithmetic average roughness Ra and a smooth surface.

Examples of the lactam pigment (D2b) include compounds represented by the following formula (d-4).

In formula (d-4), ^Xd represents a double bond, and as a geometric isomer, each independently is an E-body or a Z-body, ^Rd9 each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group, ^Rd10 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and ^Rd11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom. The compound represented by formula (d-4) can be used alone or in combination of two or more. From the viewpoint of easy preparation of the compound represented by formula (d-4), ^Rd9 is preferably bonded to the 6-position of the dihydroindolinone ring, and ^Rd11 is preferably bonded to the 4-position of the dihydroindolinone ring. From the same viewpoint, ^Rd9 , ^Rd10 , and ^Rd11 are preferably hydrogen atoms. The compound represented by formula (d-4) has EE isomers, ZZ isomers, and EZ isomers as geometric isomers, and may be a single compound of any of these isomers or a mixture of these geometric isomers. The compound represented by formula (d-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the lactam pigment well in the photosensitive resin composition, the volume average particle size of the lactam pigment is preferably 10 nm or more and 1000 nm or less.

In addition, in order to adjust the hue of black pigments such as carbon black, as auxiliary pigments, organic pigments as shown below can be appropriately added. In addition, instead of using black pigments such as carbon black, a variety of organic pigments as shown below can be combined, for example, the colorants of the three primary colors are mixed to form black.

As the organic pigment, for example, a compound classified as a pigment in the Color Index (C.I.; issued by The Society of Dyers and Colourists) is preferably used. Specifically, a pigment with a Color Index (C.I.) number as described below is preferably used.

As an example of a yellow pigment that can be suitably used, C.I. Pigment Yellow 1 (hereinafter referred to as "C.I. Pigment Yellow", and similarly, only the number is described) can be cited. , 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, and 185.

Examples of orange pigments that can be suitably used include C.I. Pigment Orange 1 (hereinafter referred to as "C.I. Pigment Orange", also simply by the number), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of purple pigments that can be suitably used include C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is also referred to by the number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter referred to as "C.I. Pigment Red", and only the number is described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97 , 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be suitably used include C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is also referred to by the number), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.

Examples of pigments of hues other than those mentioned above that can be suitably used include green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 37, brown pigments such as C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, and C.I. Pigment Brown 28, and black pigments such as C.I. Pigment Black 1 and C.I. Pigment Black 7.

In order to evenly disperse the colorant in the photosensitive resin composition, a dispersant may be further used. As such a dispersant, preferably a high molecular weight dispersant of polyethyleneimine, polyurethane resin, or acrylic resin is used. In particular, when carbon black is used as the colorant, an acrylic resin dispersant is preferably used as the dispersant.

In addition, the inorganic pigment and the organic pigment can be used alone or in combination of two or more. When used in combination, the organic pigment is preferably used in an amount of 10 or more and 80 or less parts by mass, and more preferably in an amount of 20 or more and 40 or less parts by mass, relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment.

The amount of the colorant used in the photosensitive resin composition can be appropriately determined according to the purpose of the photosensitive resin composition. For example, it is preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the total mass of the components other than the solvent in the photosensitive resin composition. By setting it within the above range, a black matrix or each coloring layer can be formed in the intended pattern, so it is preferred.

In particular, when a black matrix (or black bank) is formed using a photosensitive resin composition, it is preferred to adjust the amount of the light shielding agent in the photosensitive resin composition so that the OD value per 1 μm of the film of the black matrix becomes 0.1 or more. When the OD value per 1 μm of the film of the black matrix is 0.1 or more, sufficient display contrast can be obtained when used as a black matrix of a display device.

It is preferred that the colorant is added to the photosensitive resin composition after preparing a dispersion liquid dispersed at an appropriate concentration using a dispersant.

<Solvent (S)> The photosensitive resin composition may or may not contain a solvent (S). When a solvent (S) is contained, examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ... (Poly) alkylene glycol monoalkyl ethers such as propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate , ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more.

The photosensitive resin composition can be prepared by dispersing and dissolving the components in a solvent. If the aforementioned component (A) is in liquid form, no solvent may be used. When a solvent is included, examples of the solvent that can be used in the photosensitive resin composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and other (poly) alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, Other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxypropionate Butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more.

The solvent (S) may be appropriately determined according to the application of the photosensitive resin composition. For example, the solid content concentration in the photosensitive resin composition may be appropriately adjusted within a range of 1 mass % to 50 mass %.

<(E) Hydrophobic agent> The photosensitive resin composition may further contain a hydrophobic agent. For example, in order to significantly improve the printing quality by utilizing the hydrophobicity or even the liquid-repellent property in areas such as a flat printing plate or the nozzle surface of an inkjet head, it is desirable to form a hydrophobic film having a pattern shape by using the photosensitive resin composition.

As (E) hydrophobic agent, it is not particularly limited, preferably comprising a compound having fluorine. For example, as a hydrophobic agent, a perfluoroalkyl composition with cationic polymerization and a perfluoropolyether composition with cationic polymerization can be cited. Specifically, it is preferably a composition containing an ink repellent, and the ink repellent has a side chain comprising a group represented by the following formula (E-1) or a group represented by the following formula (E-2). In formula (1), X represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, ^Rf represents a fluoroalkyl group having 20 or less carbon atoms in which at least one hydrogen atom of an etheric oxygen atom is substituted by a fluorine atom; or a fluorine atom. In formula (2), ^Re1 , ^Re2 , ^Re3 , and ^Re4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, ^Re5 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200. In addition, a condensate of a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having a cationically polymerizable group can be cited. As an example, for example, a compound represented by the following formula can be cited. (wherein n is an integer greater than or equal to 0 and less than or equal to 7.) When n exceeds the above range, the compatibility in the photosensitive resin composition decreases, making it difficult to uniformly impart hydrophobicity to the entire coating film.

The proportion of the hydrophobic agent in the photosensitive resin composition is not particularly limited, but is preferably 20 parts by mass or less, and more preferably 0.05 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total mass of the components other than the solvent in the photosensitive resin composition. When the hydrophobic agent is used in an amount within the above range, the alkali-soluble resin (A) and the hydrophobic agent are well soluble in each other, and it is easy to achieve good hardness of the cured film, good hydrophobicity of the cured film, and good angle characteristics of the edge of the cured film in a well-balanced manner.

<Other ingredients> The photosensitive resin composition may contain various other additives if necessary. Specifically, they include dispersing aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoaming agents, surfactants, etc.

Examples of thermal polymerization inhibitors that can be used in the photosensitive resin composition include hydroquinone, hydroquinone monoethyl ether, etc. In addition, examples of defoaming agents include polysiloxane-based, fluorine-based, etc. compounds, and examples of surfactants include anionic, cationic, nonionic, etc. compounds.

[Preparation method of photosensitive resin composition] The photosensitive resin composition can be prepared by mixing all the above components using a stirrer. When the prepared photosensitive resin composition does not contain insoluble components such as pigments, the photosensitive resin composition can be filtered using a filter to make it uniform.

≪Curing film forming method≫ The method for producing a curing film includes the following steps: a step of applying a photosensitive resin composition to a substrate to form a photosensitive resin layer (hereinafter, also referred to as "resin layer forming step"), a step of exposing the resin layer in a position-selective manner (hereinafter, also referred to as "exposure step"), and a step of developing the exposed photosensitive resin layer with a developer to form a pattern (hereinafter, also referred to as "development step").

The substrate (substrate or support) can be selected according to various uses, for example, there are quartz, glass, optical film, ceramic material, evaporated film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), polymer substrates such as polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass, transparent plastic substrate, ITO, metal and other conductive substrates, insulating substrates, silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon and other semiconductor manufacturing substrates, etc., without particular limitation. In addition, when a layered structure is formed on a substrate, for example, any layer that has been formed on the substrate to become a lower structure is also included in the concept of the substrate as a photosensitive resin layer. In addition, the shape of the substrate is not particularly limited, and can be a plate or a roll. The substrate can further have a surface with unevenness, for example, by various patterns. In addition, as the above-mentioned substrate, a translucent or non-translucent substrate can be selected.

First, in the resin layer forming step, for example, a contact transfer coating device such as a roller coater, a reverse coater, or a rod coater, or a non-contact coating device such as a spin coater (rotary coating device), a dispenser, an inkjet, a spray, a screen printer, or a curtain flow coater is used to apply a photosensitive resin composition to a substrate on which a cured product is to be formed. If necessary, the solvent is removed by drying (pre-baking) to form a photosensitive resin layer.

The thickness of the photosensitive resin layer is not particularly limited, but is preferably 0.05 μm or more, more preferably 1 μm or more, still more preferably 7 μm or more, and particularly preferably 10 μm or more. The upper limit is not particularly limited, but is, for example, 50 μm or less, preferably 20 μm or less. As described above, for the photosensitive resin composition, curing can be promoted even in the portion where the active energy does not directly reach during exposure. Therefore, for example, in the form of a photosensitive resin layer having a thick film of 1 μm or more and 15 μm or less, sufficient curing can be performed even near the substrate side located farther from the exposure side.

In addition, for the sake of convenience, the photosensitive resin composition such as the droplets accumulated on the substrate, the photosensitive resin composition filled in the concave portions of the substrate having projections and recesses, or the photosensitive resin composition filled in the concave portions of the mold is referred to as a "photosensitive resin layer".

The formed photosensitive resin layer can then be cured by exposure. The exposure method is not particularly limited as long as it is a method that can cure the photosensitive resin composition, and can also be combined with a heat treatment if necessary.

For exposure, the light source is not particularly limited, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an LED. Using such a light source, the coating film can be irradiated with radiation or electromagnetic waves such as ArF excimer laser, KrF excimer laser, _F2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, g-ray, i-ray, h-ray, j-ray, and k-ray to expose the coating film. Exposure of the coating film can be performed in a position-selective manner through a negative mask. The exposure dose varies depending on the composition of the curable composition, and is preferably, for example, 10 mJ/cm ² or more and 2000 mJ/cm ² or less, more preferably 100 mJ/cm ² or more and 1500 mJ/cm ² or less, and still more preferably 200 mJ/cm ² or more and 1200 mJ/cm ² or less. The exposure illuminance varies depending on the composition of the photosensitive resin composition, and is preferably in the range of 1 mW/cm ² or more and 50 mW/cm ² or less. The temperature during heating is not particularly limited, and is preferably 180° C. or more and 280° C. or less, more preferably 200° C. or more and 260° C. or less, and particularly preferably 220° C. or more and 250° C. or less. Typically, the heating time is preferably 1 minute to 60 minutes, more preferably 10 minutes to 50 minutes, and particularly preferably 20 minutes to 40 minutes.

The step of curing the photosensitive resin layer is performed by selective exposure, and the photosensitive resin layer exposed in a selective manner is developed to obtain a patterned cured film. The curable composition is not easily excessively dissolved in the developer after exposure. Therefore, by using the curable composition, a well-shaped patterned cured product can be formed in which the exposed part is a convex part and the unexposed part is a concave part.

In the developing step, the exposed coating is developed with a developer to form a solidified product patterned in a desired shape. The developing method is not particularly limited, and an immersion method, a spray method, a puddle method, a dynamic dispense method, etc. can be used. Specific examples of the developer containing an organic solvent include alcohol solvents such as PE (propylene glycol monomethyl ether) or glycol ether solvents, ether solvents such as tetrahydrofuran, ester solvents such as butyl acetate, acetone, ketone solvents such as methyl amyl ketone, etc. Specific examples of the alkaline developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Furthermore, if necessary, the cured product after exposure or the cured product after patterning after development may be post-baked to further heat cure. The post-baking temperature is preferably 150° C. or higher and 270° C. or lower.

≪Cured Product≫ The cured product is formed by curing the aforementioned curable composition. Therefore, the cured product can also have a good fine pattern, and also has good heat resistance and transparency. When the cured product is a cured film, the thickness of the cured film is not particularly limited, but is preferably 0.05 μm or more and 50 μm or less. In addition, since the patterned cured film is formed from the aforementioned cured product, it can have the aforementioned good fine pattern.

The aforementioned solidified material can be used for a bank formed in the form of dividing the substrate surface into a plurality of regions for forming dots. It should be noted that a dot represents the smallest region in an optical element that can modulate light. In organic EL elements, quantum dot displays, TFT arrays, and thin-film solar cells, in the case of black and white display, 1 dot = 1 pixel, and in the case of color display, for example, 3 dots (R (red), G (green), B (blue), etc.) = 1 pixel.

The aforementioned cured product is formed from a photosensitive resin composition having excellent patterning properties. Therefore, when used in optical elements (especially organic EL elements, quantum dot displays, TFT arrays or thin-film solar cells made using an inkjet method), ink can be evenly applied to the opening to form dots with high precision.

When the cured product is used for a bank, the width of the bank is preferably 100 μm or less, and particularly preferably 20 μm or less. In addition, the distance between adjacent banks (pattern width) is preferably 300 μm or less, and particularly preferably 100 μm or less. The height of the bank is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 20 μm.

The following describes an example in which the cured product is used for a bank and dots are formed at the opening of the bank by an inkjet method in order to obtain an optical element, but the present invention is not limited to this.

A method for manufacturing a quantum dot display as an example of an optical element using banks formed on a substrate (for example, banks formed in a grid pattern) is described.

Here, the partition on the substrate is formed in a manner such that the opening portion is consistent with the pattern of dots of the quantum dot display to be manufactured.

The substrate is a film of a light-transmitting electrode such as ITO formed on a light-transmitting substrate such as glass by sputtering or the like. The light-transmitting electrode may be patterned as necessary.

Ink is dripped from the inkjet head into the opening surrounded by the dam, and a specific amount of ink is injected into the opening. As the ink, known inks for quantum dot displays (e.g., inks using materials for hole injection layers, hole transport layers, quantum dot layers, hole blocking layers, and electron injection layers) can be appropriately selected according to the functions of the dots.

Next, depending on the type of ink used, for example, in order to remove the solvent or solidify, drying and/or heating are performed to form a desired dot layer adjacent to the bank. Then, a reflective electrode such as aluminum or a light-transmitting electrode such as ITO is formed by evaporation to obtain a quantum dot display.

Furthermore, the quantum dot display can be a blue light conversion type quantum dot display. In this case, a planar grid-shaped partition is formed along the outline of each dot on a light-transmitting substrate such as glass. Then, in the opening for dot formation, a nanoparticle solution that converts blue light into green light, a nanoparticle solution that converts blue light into red light, and a blue color ink as needed are applied by inkjet and dried to make a module. The light source that develops blue light is used as a backlight, and the aforementioned module is used as a substitute for a color filter, thereby obtaining a display with excellent color reproduction.

By using the partition formed by the solidified material of the present invention, the ink can be evenly applied to the opening separated by the solidified material (partition) with high pattern accuracy during the manufacturing process, thereby obtaining an optical element (organic EL element, quantum dot display, TFT array or thin-film solar cell) having dots formed with high accuracy.

Embodiment

Hereinafter, the present invention will be described in further detail with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

In Examples 1 to 23 and Comparative Examples 1 to 5 described below, as the alkali-soluble resin (A), any one of resins (a-1-1), (a-1-2) and (a-2-1) was used in the blending amounts shown in Table 1, respectively.

First, in a 500ml four-necked bottle, add 235g of bisphenol fluorene epoxy resin (epoxy equivalent 235), 110mg of tetramethylammonium chloride, 100mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0g of acrylic acid, and heat and dissolve at 90℃~100℃ while blowing air at a rate of 25ml/min. Next, slowly raise the temperature while the solution remains cloudy, and heat it to 120℃ to completely dissolve it. At this point, the solution gradually becomes transparent and viscous, and it is kept in this state and stirred continuously. During this period, the acid value is measured, and heating and stirring are continued until the acid value becomes less than 1.0mgKOH/g. It takes 12 hours until the acid value reaches the target. Then, the mixture was cooled to room temperature to obtain bisphenol fluorene type epoxy acrylate.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-obtained bisphenol fluorene type epoxy acrylate, and after dissolving it, 80.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was slowly raised to react at 110°C to 115°C for 4 hours. After confirming the disappearance of the anhydride, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to obtain resin (a-1-1) (weight average molecular weight: 3400). The disappearance of the anhydride was confirmed by IR spectroscopy.

Resin (a-1-2) was obtained in the same manner as in the preparation of Resin (a-1-1), except that 80.5 g of biphenyltetracarboxylic dianhydride in the preparation of Resin (a-1-1) was replaced with 59.7 g of pyromellitic dianhydride. The weight average molecular weight was 2,500.

(In the above formula of acrylic resin a-2-1, the digit on the lower right of each unit represents the content (mass %) of each unit in the alkali-soluble resin.) The weight average molecular weight of the above alkali-soluble resin is 7,000.

In each of the Examples and Comparative Examples, dipentaerythritol hexaacrylate (b-2-1) as a polyfunctional (meth)acrylic monomer (B2) was used as the crosslinking agent (B).

In addition, regarding the monofunctional (meth)acrylic monomer as the crosslinking agent (B), the compounds represented by the following formulae (b-1-1) to (b-1-4) were used in the amounts shown in Table 1, respectively.

In each of the Examples and Comparative Examples, compounds c1 to c2 represented by the following formulae were used as the photopolymerization initiator (C).

In each of the Examples and Comparative Examples, 2-isopropylthiazolone (Compound d1: 2-isopropyl-9H-thiazol-9-one) was used as the sensitizer (D).

In addition, in each of Examples 1 to 18, 22 to 26 and Comparative Examples 1 to 4, a carbon black dispersion (27% by mass of furnace black in PGMEA solvent) (e1) or an organic pigment mixed black (20% by mass of organic pigment in PGMEA solvent (Red-256/Violet-23/Blue-156=40/20/40 (mass ratio))) (e2) was used as a colorant (E) in the amounts shown in Table 1 (the amounts of only the colorant component in each dispersion converted into numbers).

In each of the embodiments and comparative examples, an active agent (f1: BYK310) and (f3) a fluorine-based surfactant (a copolymer comprising structural units derived from perfluorobutylethyl methacrylate, polyethylene glycol methacrylate and n-butyl methacrylate, with a weight average molecular weight of 20,000) were added as an additive (F). In addition, N-phenyl-3-aminopropyltrimethoxysilane (f2) was added as an additive.

In the examples, the above-mentioned active agents (f1), (f3) and additives (f2) are added. However, in the photosensitive resin composition, even if these active agents and additives are not essential components and are not mixed, the same evaluation results as those of the examples disclosed herein can be obtained.

In each of the Examples and Comparative Examples, 3-methoxybutyl acetate (g1) and propylene glycol monomethyl ether acetate (g2) were used as a solvent at a ratio of 15/85 (mass ratio).

[Examples 1 to 26 and Comparative Examples 1 to 5] At room temperature (25°C±2°C), the types and amounts of alkali-soluble resin (A), crosslinking agent (B), photopolymerization initiator (C), sensitizer (D), colorant (E), additive (E) and solvent (G) listed in Table 1 below were uniformly mixed using a stirrer to obtain photosensitive resin compositions of each example and comparative example. In addition, in Examples 19 to 21 and Comparative Example 5, no colorant (E) was added, and a transparent resin composition was obtained.

[Line pattern evaluation] The photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were coated on a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 100°C for 120 seconds to form a coating film. Next, a proximity exposure machine (product name: TME-150RTO, manufactured by TOPCON CORPORATION) was used to irradiate the coating film with ultraviolet light through a negative mask formed with a line pattern of 20 μm in width with an exposure gap of 50 μm. The exposure amount was set to 200 mJ/cm ² . The exposed coating film was developed using a 0.04 mass % KOH aqueous solution at 26° C. for 50 seconds and then post-baked at 230° C. for 30 minutes to form a line pattern with a film thickness of 10 μm as a cured film.

(Pattern Straightness Evaluation) The formed line pattern is observed under an optical microscope to evaluate the pattern straightness. The pattern straightness is evaluated as "good" when there is no undulation on the line edge, and "poor" when there is undulation on the line edge.

(Taper angle) The taper angle of the line pattern formed with an exposure amount of 200mJ/ ^cm2 was evaluated. The taper angle was measured using a scanning electron microscope as the bonding angle between the pattern and the substrate. The measured taper angles are shown in Table 1. The closer the taper angle is to 90°, the closer the shape of the pattern cross section is to the desired rectangular shape. When the taper angle is much smaller than 90°, the shape of the pattern cross section is not the desired rectangular shape. In addition, based on the measurement results of the taper angle, the cross-sectional shape of the line pattern is judged based on the following judgment criteria. The results are shown together in Table 1. ◎: The taper angle is greater than 80° and less than 90°. ○: The taper angle is greater than 70° and less than 80°. △: The taper angle is 50° or more and less than 70°. ×: The taper angle is less than 50°.

[Evaluation of OD value] The photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 5 were coated on a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 100°C for 120 seconds to form a coating film. Next, the photosensitive resin layer was exposed using a proximity exposure machine (product name: TME-150RTO, manufactured by TOPCON CORPORATION) with an exposure dose of 200 mJ/cm ² and an exposure gap of 50 μm. The exposed photosensitive resin layer was post-baked at 230°C for 30 minutes to form a cured film. The thickness of the formed light-shielding film was 10 μm. The OD value of each 10 μm of the formed light-shielding film was measured using a transmittance meter (D-200II, manufactured by GretagMacbeth), and the OD value of each 1 μm was calculated using a fitting curve. The results of the OD value measurement are shown in Table 1. The OD values of the cured films formed using the photosensitive resin compositions of Examples 1 to 18, 22 to 26 and Comparative Examples 1 to 4 containing a black colorant were all 0.45/μm, indicating that a cured film with excellent light-shielding properties was formed. On the other hand, the OD values of the cured films formed using the photosensitive resin compositions of Examples 19 to 21 and Comparative Example 5 that did not contain a colorant were all 0.01/μm, indicating that a cured film with high transmittance was formed.

Claims (9)

A photosensitive resin composition comprising: an alkali-soluble resin (A), a crosslinking agent (B), and a photopolymerization initiator (C), wherein the crosslinking agent (B) comprises a monofunctional (meth) acrylic monomer (B1a) represented by the following formula (B1-1) and a multifunctional (meth) acrylic monomer (B2) having two or more functional groups, and the photopolymerization initiator (C) is an oxime ester having a nitro group. The photosensitive resin composition is exposed at an exposure amount of 200 mJ/ ^cm2 , and after the exposure, it is developed using a 0.04 mass% KOH aqueous solution at 26°C, and after the development, it is post-baked at 230°C for 30 minutes, so that the cone angle of the formed cured film is 70° or more and 90° or less, and _CH2 = ^CRb1 -CO-( ^ORb2- ) _n1 -X ^b1 -BP‧‧‧(B1-1) (In formula (B1-1), R ^b1 is a hydrogen atom or a methyl group, R ^b2 is an ethylene group, BP is a biphenyl group having no substituent, n1 is 0 or 1, and X ^b1 is -O- or -NH-. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin (A) comprises a resin having a cardo structure. The photosensitive resin composition of claim 1, wherein the content of the monofunctional (meth) acrylic monomer (B1) is 5% by mass or more and 50% by mass or less relative to the total mass of the crosslinking agent (B). The photosensitive resin composition of any one of claims 1 to 3 further comprises a sensitizer (D). The photosensitive resin composition of any one of claims 1 to 3 further comprises a colorant (E). As in claim 5, the photosensitive resin composition, wherein the colorant (E) is a black pigment. The photosensitive resin composition of any one of claims 1 to 3 further comprises a hydrophobic agent (F). A method for producing a patterned cured film, comprising the following steps: applying a photosensitive resin composition as described in any one of claims 1 to 7 on a substrate to form a photosensitive resin layer, exposing the photosensitive resin layer in a position-selective manner, and developing the exposed photosensitive resin layer using a developer. A cured film, which is formed by curing the photosensitive resin composition as described in any one of claims 1 to 7.