JP7249119B2 - Photosensitive resin composition, method for producing patterned cured film, and cured film - Google Patents

Description

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

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

In the photosensitive composition, a photopolymerization initiator included as part of its components generates radicals upon exposure. The radicals polymerize the polymerizable compound contained in the photosensitive composition, thereby curing the photosensitive composition. Further, in the photosensitive resin composition, while polymerizing a polymerizable compound with radicals generated by such a photopolymerization initiator, the adhesion of the photosensitive resin composition to the substrate and the photosensitive resin composition A cross-linking agent component is blended for the purpose of increasing the strength after curing. As the cross-linking agent component, conventionally, for the purpose as described above, polyfunctional among monomers having ethylenically unsaturated groups, in particular, penta- or higher-functional (meth)acrylate monomers such as dipentaerythritol penta and hexaacrylate was used.

In recent years, from the viewpoint of improving productivity, there has been a demand for a highly sensitive photosensitive resin composition capable of forming a pattern with a low exposure dose. On the other hand, when forming a cured film patterned into a complicated shape, the film made of the photosensitive resin composition to be exposed does not transmit the exposure light that serves as a trigger for curing the photosensitive resin composition. area may increase. In this case, the photosensitive resin composition having the composition described above tends to cause a problem that insufficiently cured portions are formed after exposure. In addition, application of the photosensitive resin composition to a mode in which a relatively thick cured film of several tens of μm or more is to be obtained has been widely studied. However, even when such a thick cured film is formed, the side of the film made of the photosensitive resin composition farther than the light source, that is, the contact surface between the substrate and the photosensitive resin layer is generally Insufficient exposure light does not reach the vicinity of the cured film, resulting in a problem that insufficiently cured portions are likely to occur in the cured film. Furthermore, in the embodiment in which the photosensitive resin composition contains a colorant, there is a significant problem that the absorption of the exposure light by the colorant results in the formation of insufficiently cured portions in the cured film.

Patent Literature 1 proposes a photosensitive resin composition having a specific composition for the purpose of satisfactorily curing regions of the photosensitive resin composition to which the activation energy does not directly reach even with a low exposure dose. In Patent Document 1, specifically, a monofunctional (meth)acrylic monomer (A) having an aromatic group and a polymerizable carbon-carbon double bond in a molecule other than the component (A) are averaged Curable compositions containing at least one compound (B) and (C) a photoinitiator have been proposed. Specifically, ethoxylated o-phenylphenyl acrylate and the like are used as component (A), and acrylic acid ester polymers and the like are specifically used as component (B).

JP 2014-51618

However, even the curable composition as described in Patent Document 1 may not be able to sufficiently meet the demand for solving the problem of insufficiently cured portions being formed in the cured film. Further, even if the formation of the insufficiently cured portion can be suppressed, in this case, while the rectangularity (taperedness) of the formed line pattern is improved to some extent, the straightness (reproducibility) of the line pattern is improved. ) and resolution are desired to be further improved. Therefore, there is a demand for a photosensitive resin composition with even better sensitivity.

The present invention has been made in view of the above-mentioned problems of the prior art, and provides a photosensitive resin composition having excellent patterning properties such as high sensitivity, line width stability, resolution and rectangularity. An object of the present invention is to provide a method for producing a patterned cured film using the method and the cured film.

The present inventors have found that the photosensitive resin composition contains a mixture of a monofunctional (meth)acrylate compound having a specific structure, so that the sensitivity of the photosensitive resin composition is high and, for example, the cured film is formed thick. Good curing progresses even in places where it is difficult to directly reach the active energy ray forming a cured film with a complicated shape, good rectangularity (tapering) of the pattern, and high resolution and straightness of the pattern. (Reproducibility) is also good, and the inventors have found that the patterning characteristics can be improved, leading to the completion of the present invention. That is, the present invention is as follows.

A first aspect of the present invention is
A photosensitive resin composition comprising an alkali-soluble resin (A), a cross-linking agent (B), and a photopolymerization initiator (C),
A photosensitive resin containing, as the cross-linking agent (B), a monofunctional (meth)acrylate monomer (B1) having an optionally substituted biphenyl skeleton or an optionally substituted terphenyl skeleton. composition.

A second aspect of the present invention is to apply the photosensitive resin composition according to the first aspect on a substrate to form a photosensitive resin layer, and position-selectively expose the photosensitive resin layer. and developing the exposed photosensitive resin layer with a developer.

A third aspect of the present invention is a cured film obtained by curing the photosensitive resin composition according to the first aspect.

INDUSTRIAL APPLICABILITY According to the present invention, a photosensitive resin composition having excellent patterning properties such as high sensitivity, good line width stability, good resolution and rectangularity, a method for producing a patterned cured film using the same, and curing. A membrane can be provided.

Embodiments of the present invention will be described in detail below, but the present invention is by no means limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the purpose of the present invention.

<<Photosensitive resin composition>>
The photosensitive resin composition contains an alkali-soluble resin (A), a cross-linking agent (B), and a photopolymerization initiator (C). The photosensitive resin composition contains, as the cross-linking agent (B), a monofunctional (meth)acrylate monomer (B1 )including.
Components contained in the photosensitive resin composition will be described in order below.

<Alkali-soluble resin (A)>
The photosensitive resin composition contains an alkali-soluble resin (A).
Here, (A) the alkali-soluble resin in this specification refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) that imparts alkali-solubility in the molecule.
The type of alkali-soluble resin (A) is not particularly limited, and various alkali-soluble resins conventionally blended in photosensitive resin compositions can be used.
Hereinafter, a resin (A1) having a cardo structure, an acrylic resin (A2), and a novolak resin (A3) will be described as preferred specific examples of the alkali-soluble resin (A).

[Resin (A1) having 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 desired alkali solubility can be used. A cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting a first ring structure. The second ring structure and the third ring structure may be the same structure or different structures.
A representative example of the cardo skeleton is a skeleton in which two aromatic rings (eg, benzene rings) are bonded to the 9-position carbon atom of a fluorene ring.

（式（ａ－１）中、Ｘ^ａは、下記式（ａ－２）で表される基を示す。ｍ１は０以上２０以下の整数を示す。） The cardo resin (A1) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable.

(In the formula (a-1), X ^a represents a group represented by the following formula (a-2). m1 represents an integer of 0 or more and 20 or less.)

（式（ａ－２）中、Ｒ^ａ１は、それぞれ独立に水素原子、炭素原子数１以上６以下の炭化水素基、又はハロゲン原子を示し、Ｒ^ａ２は、それぞれ独立に水素原子又はメチル基を示し、Ｒ^ａ３は、それぞれ独立に直鎖又は分岐鎖のアルキレン基を示し、ｍ２は、０又は１を示しＷ^ａは、下記式（ａ－３）で表される基を示す。）

(In formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 each independently represents a hydrogen atom or a methyl group. , R ^a3 each independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^a represents a group represented by the following formula (a-3).)

（式（ａ－３）中の環Ａは、芳香族環と縮合していてもよく置換基を有していてもよい脂肪族環を示す。脂肪族環は、脂肪族炭化水素環であっても、脂肪族複素環であってもよい。）

(Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and may have a substituent. The aliphatic ring is an aliphatic hydrocarbon ring. may be 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, and an alkylene group having 1 to 6 carbon atoms. is particularly preferred, and ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl groups are most preferred.

Aliphatic rings for ring A in formula (a-3) include monocycloalkanes, bicycloalkanes, tricycloalkanes, tetracycloalkanes and the like.
Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring which may be condensed with the aliphatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferred.

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

The divalent group X ^a in formula (a-1) can be obtained by reacting a tetracarboxylic dianhydride that gives residue Z ^a with a diol compound represented by the following formula (a-2a) ( A1) Introduced into the cardo resin.

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 and m2 are as described for formula (a-2). Ring A in formula (a-2a) is as described for formula (a-3).

A diol compound represented by formula (a-2a) can be produced, for example, by the following method.
First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is, if necessary, replaced by a group represented by —R ^a3 —OH according to a conventional method, Glycidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).

Then, the epoxy compound represented by formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by formula (a-2a).
In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 and m2 are as described for formula (a-2). Ring A in formulas (a-2b) and (a-2c) is as described for formula (a-3).

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

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

In formula (a-1) above, R ^a0 is a hydrogen atom or a group represented by —CO—Y ^a —COOH. Here, Y ^a represents a residue obtained by removing the acid anhydride group (--CO--O--CO--) from the dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride. Examples include phthalic anhydride and glutaric anhydride.

In the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. and biphenyl ether tetracarboxylic dianhydride.
In the above formula (a-1), m1 represents an integer of 0 or more and 20 or less.

（式（ａ－４）中、Ｒ^ａ４、Ｒ^ａ５、及びＲ^ａ６は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍ３は、０以上１２以下の整数を示す。）

(In formula (a-4), R ^a4 , R ^a5 , and R ^a6 are each independently 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 is an integer from 0 to 12.)

The alkyl group that can be selected as R ^a4 in formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group within this range, the heat resistance of the resulting carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 4 or less, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. 1 or more and 3 or less are particularly preferable.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

R ^a4 in formula (a-4) is more preferably a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms independently from the viewpoint that a cardo resin having excellent heat resistance can be easily obtained. R ^a4 in formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, particularly preferably a hydrogen atom or a methyl group.
Plural R ^a4 groups in formula (a-4) are preferably the same group, since this facilitates the preparation of a highly pure tetracarboxylic dianhydride.

m3 in formula (a-4) represents an integer of 0 or more and 12 or less. By setting the value of m3 to 12 or less, purification of the tetracarboxylic dianhydride can be facilitated.
The upper limit of m3 is preferably 5, more preferably 3, from the viewpoint of facilitating purification of the tetracarboxylic dianhydride.
From the viewpoint of chemical stability of the tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, 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 R ^a5 and R ^a6 in formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a4 .
R ^a5 and R ^a6 each have a hydrogen atom or a carbon atom number of 1 or more and 10 or less (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, more preferably 1 or more and 5 or less; more preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less), 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″-tetra Carboxylic acid dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (also known as "norbornane- 2-spiro-2′-cyclohexanone-6′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride”), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-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-cyclooctanone-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 -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, norbornane-2-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 and the like.

The weight average molecular weight of the cardo resin (A1) is preferably 1,000 or more and 40,000 or less, more preferably 2,000 or more and 30,000 or less. By setting the amount within the above range, it is possible to obtain sufficient heat resistance and film strength while obtaining good developability.

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

As the acrylic resin (A2), a resin containing structural units derived from (meth)acrylic acid and/or structural units derived from other monomers such as (meth)acrylic acid esters can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylic acid ester is a compound represented by the following formula (a-5) and is not particularly limited as long as it does not interfere with the object of the present invention.

In formula (a-5) above, R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. Moreover, this organic group may be linear, branched, or cyclic.

Substituents other than the hydrocarbon group in the organic group of R ^a8 are not particularly limited as long as the effects of the present invention are not impaired, and include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, and a cyanato group. , isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkylthioether group, aryl ether group, arylthioether group, amino group (—NH ₂ , —NHR, —NRR′: R and R′ each independently represent a hydrocarbon group) and the like. A hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

R ^a8 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. Moreover, 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 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec -pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group and the like.

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

The compound represented by formula (a-5) is also preferably an epoxy group-containing unsaturated compound having an epoxy group in R ^a8 .
Suitable examples of epoxy group-containing unsaturated compounds represented by formula (a-5) include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6 , 7-Epoxyheptyl (meth)acrylate and other (meth)acrylic acid epoxyalkyl esters; α-ethyl acrylate, α-n-propyl acrylate, α-n-butyl acrylate, α-ethyl acrylate and α-alkylacrylic acid epoxyalkyl esters such as 6,7-epoxyheptyl acid; 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 resin after curing, and the like. These epoxy group-containing unsaturated compounds can be used singly or in combination of two or more.

Also, the acrylic resin (A2) may be a resin obtained by polymerizing a monomer other than the (meth)acrylic acid ester. Such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These monomers can be used alone or in combination of two or more.

(Meth)acrylamides 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, N-hydroxyethyl-N-methyl(meth)acrylamide and the like.

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

Allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; mentioned.

Vinyl ethers include 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, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether , vinyl naphthyl ether, vinyl aryl ether such as vinyl anthranyl ether;

Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl Acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy alkylstyrenes such as methylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Halostyrenes such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene;

(A3) The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin are not particularly limited as long as the object of the present invention is not impaired. (A3) The amount of structural units derived from (meth)acrylic acid in the acrylic resin is preferably 5% by mass or more and 50% by mass or less, and 10% by mass or more and 30% by mass or less, relative to the mass of the acrylic resin. is more preferred.

The weight average molecular weight of the acrylic resin (A2) is preferably 2000 or more and 50000 or less, more preferably 5000 or more and 30000 or less. By setting the amount within the above range, there is a tendency that the film-forming ability of the photosensitive resin composition and the developability after exposure are easily balanced.

[Novolac resin (A3)]
The alkali-soluble resin (A) may contain a novolak resin (A3). When the alkali-soluble resin (A) contains the novolac resin (A3), it is easy to form a cured film that is resistant to deformation by heating and has good heat resistance.

As the novolak resin (A3), various novolak resins conventionally blended in photosensitive resin compositions can be used. As the novolac resin (A3), a novolac resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst is preferred.

(Phenols)
Phenols used for producing the novolac resin (A3) include, for example, phenol; cresols such as o-cresol, m-cresol and p-cresol; 2,3-xylenol, 2,4-xylenol, 2 xylenols such as ,5-xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; 2-isopropyl Alkylphenols such as phenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol and 3,4,5 - trialkylphenols such as trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; alkylpolyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (any also has 1 to 4 carbon atoms.); α-naphthol; β-naphthol; hydroxydiphenyl; These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferred, and the combined use of m-cresol and p-cresol is more preferred. In this case, various properties such as heat resistance of the cured film formed using the photosensitive resin composition can be adjusted by adjusting the mixing ratio of both.
The mixing ratio of m-cresol and p-cresol is not particularly limited, but 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 such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a cured film having excellent heat resistance.

Also preferred is a novolac resin produced by using m-cresol and 2,3,5-trimethylphenol in combination. When such a novolac resin is used, it is particularly easy to obtain a photosensitive resin composition capable of forming a cured film that is not excessively flowable when heated during post-baking.
The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the molar ratio of m-cresol/2,3,5-trimethylphenol is preferably 70/30 or more and 95/5 or less.

(aldehydes)
Examples of aldehydes used in producing the novolak resin (A3) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(acid catalyst)
Examples of acid catalysts used in producing the novolac resin (A3) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluene. organic acids such as sulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

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

As the novolac resin (A3), at least two resins having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of resins having different weight average molecular weights, it is possible to balance the developability of the photosensitive resin composition and the heat resistance of the 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 40% by mass or more and 80% by mass or less with respect to the total mass of the solid content of the photosensitive resin composition. is more preferred. By setting it as said range, it is easy to obtain the photosensitive resin composition which is excellent in developability.

<(B) Crosslinking agent>
(Monofunctional (meth) acrylic monomer (B1))
The photosensitive resin composition contains a cross-linking agent (B), and the cross-linking agent (B) has an optionally substituted biphenyl skeleton or an optionally substituted terphenyl skeleton. It contains a monofunctional (meth)acrylic monomer (B1). The "(meth)acrylic monomer" is an acryloyl group and/or methacryloyl group monomer that can be derived from (meth)acrylic acid.

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

で表される基のうちのいずれかの基である。 In the formula above, R ^x is a hydrogen atom or a methyl group. BP is an optionally substituted biphenyl group, and specific skeletons are 1,1'-biphenyl-4-yl group, 1,1'-biphenyl-3-yl group, or 1,1 '-biphenyl-2-yl group, preferably 1,1'-biphenyl-2-yl group or 1,1'-biphenyl-4-yl group. TP is a terphenyl group which may have a substituent, and a specific skeleton is represented by the following formula:

Any one of the groups represented by

As the monofunctional (meth)acrylic monomer (B1), a monofunctional (meth)acrylic monomer (B1a) having an optionally substituted biphenyl skeleton is particularly preferred.

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

Preferred examples of the monofunctional (meth)acrylic monomer (B1a) include compounds represented by the following formula (B1-1).
CH ₂ ═CR ^b1 —CO—(OR ^b2 —) _t1 —X ^b1 —BP (B1-1)
(In the 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, and BP is an optionally substituted biphenyl group. and t1 is an integer of 0 or more and 10 or less, and when t1 is 0, X ^b1 is -O- or -NH-, and when t1 is an integer of 1 or more and 10 or less, X ^b1 is , a single bond, -O-, -NH-, -O-CO-*, -NH-CO-*, -O-CO-O-, and -NH-CO-O-* It is a linking group, and among the linking groups, the bond marked with * for the asymmetric linking group is the bond that bonds to BP.)

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

The number of carbon atoms in the alkylene group for R ^b2 is 1 or more and 4 or less, preferably 2 or 3. Examples of the alkylene group include linear or branched alkylene groups such as methylene group, ethylene group, trimethylene group, propylene group, and butane-1,2-diyl group. Among these, ethylene group, trimethylene group and propylene group are preferred.

t1 is preferably 0, 1 or 2.

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

The compound represented by the above formula (B1-1) is preferably B1-1-a, B1-1-cB1-1-e, B1-1-f, B1-1-i, B1-1-m, B1-1-a and B1-1-c are particularly preferred.

(Polyfunctional (meth) acrylic monomer (B2))
The photosensitive resin composition can contain a cross-linking agent (B) other than the above monofunctional (meth)acrylic monomer (B1). Examples of cross-linking agents (B) other than monofunctional (meth)acrylic monomers (B1) include polyfunctional (meth)acrylic monomers (B2).

（式（Ｂ２－１）中、Ｒ^ｂ３は、水素原子、又は炭素原子数１以上４以下のアルキル基であり、Ｒ^ｂ４は多価アルコールＲ^ｂ５（ＯＨ）_ｍのｍ個のヒドロキシ基のうちｔ２個のヒドロキシ基を式（Ｂ２－１）中のエステル結合に供したｔ２価の残基であり、ｍ及びｔ２はそれぞれ独立に２以上２０以下の整数であり、ｍはｔ２以上である。） Preferred examples of the polyfunctional (meth)acrylic monomer (B2) include polyfunctional (meth)acrylates represented by the following formula (B2-1).

(In the formula (B2-1), R ^b3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^b4 is a polyhydric alcohol R ^b5 (OH) _m among m hydroxy groups A t2-valent residue in which t2 hydroxy groups are subjected to an ester bond in formula (B2-1), m and t2 are each independently an integer of 2 or more and 20 or less, and m is t2 or more. )

Specific examples of the polyfunctional (meth)acrylic monomer represented by formula (B2-1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetramethylene. glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 , 6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate ) acrylate, glycerin 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) Acrylates, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4- (Meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate Acid diglycidyl ester di(meth)acrylate, epichlorohydrin-modified hexahydrophthalic acid di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (that is, tolylene diisocyanate, trimethylhexa reaction product of methylene diisocyanate or hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate), neopentyl glycol di(meth) hydroxypivalate, neopentyl glycol di(meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate ) Polyfunctional monomers such as (meth)acrylic acid ester methylenebis(meth)acrylamide such as acrylate, (meth)acrylamide methylene ether, condensates of polyhydric alcohol and N-methylol(meth)acrylamide, triacryl formal, etc. is mentioned. These polyfunctional monomers can be used singly or in combination of two or more.

Among the specific examples of the polyfunctional (meth)acrylate monomer represented by the above formula (B2-1), the tendency to increase the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition , polyfunctional monomers having a functionality of 3 or more are preferable, polyfunctional monomers having a functionality of 4 or more are more preferable, and polyfunctional monomers having a functionality of 5 or more are still more preferable. Particularly preferred are dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and mixtures thereof.

(B) The content of the crosslinking agent in the photosensitive resin composition is preferably 10% by mass or more and 60% by mass or less, and 15% by mass or more and 50% by mass or less with respect to the total mass of the solid content of the photosensitive resin composition. is more preferred. By setting the amount within the above range, there is a tendency that sensitivity, developability, and resolution are easily balanced.

Further, the content of the monofunctional (meth)acrylic monomer (B1) with respect to the total mass of the (B) cross-linking agent is 1% by mass or more and 100% by mass or less, and 3% by mass or more and 70% by mass of the total mass of the (B) cross-linking agent component. % by mass or less is preferable, and 5% by mass or more and 50% by mass or less is more preferable. When the content of the (meth)acrylic monomer (B1) is within the above range, the curing of the portion where the activation energy does not directly reach during the position-selective exposure of the photosensitive resin composition is promoted, resulting in a thick film, Specifically, for example, even in a mode in which a cured film having a thickness of 5 μm or more and 50 μm or less is formed, curing can be sufficiently progressed even in the vicinity of the substrate side which is farther from the exposure side.

In a more preferred embodiment, the (B) cross-linking agent contains 1% by mass or more and 99% by mass or less of a monofunctional (meth)acrylic monomer (B1) with respect to the total mass of the (B) cross-linking agent, and a polyfunctional ( It is preferable to contain 1% by mass or more and 99% by mass or less of meth)acrylic monomer (B2), 3% by mass or more and 50% by mass or less of (B1), and 50% by mass of polyfunctional (meth)acrylic monomer (B2). It is preferable to contain 97% by mass or less. hardens to For this reason, the taper angle of the patterned cured film formed through position-selective exposure and development can be easily set to a favorable angle close to vertical.

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

Specific examples of the photopolymerization initiator (C) include, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-( 2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methyl ethoxy)-2-methylphenyl]methanone O-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, ethanone, 1-[9-ethyl-6-(pyrrole -2-ylcarbonyl)-9H-carbazol-3-yl], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylamino methyl benzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5- di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3 -dimethyl-4-methoxybenzophenone, benzyl, 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-dimethyl Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro -4-phenoxyacetophenone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 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-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-( 3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-( 4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis -trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4 -bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine etc. These photopolymerization initiators can be used alone or in combination of two or more.

（Ｒ^ｃ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０以上４以下の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｃ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｃ３は、水素原子、又は炭素原子数１以上６以下のアルキル基である。） As the photopolymerization initiator (C), it is also preferable to use an oxime compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group,
n1 is an integer of 0 or more and 4 or less,
n2 is 0 or 1,
R ^c2 is an optionally substituted phenyl group or an optionally substituted carbazolyl group,
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 as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferred examples of R ^c1 being 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, and a substituent. optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy a phenylalkyl group optionally having substituents, a naphthyl group optionally having substituents, a naphthoxy group optionally having substituents, a naphthoyl group optionally having substituents, a substituent optionally substituted naphthoxycarbonyl group, optionally substituted naphthyloxy group, optionally substituted naphthylalkyl group, optionally substituted heterocyclyl group, amino group, 1 , or amino group, morpholin-1-yl group and piperazin-1-yl group substituted with two organic groups, halogen, nitro group and cyano group. When n1 is an integer of 2 or more and 4 or less, R ^c1 may be the same or different. In addition, the number of carbon atoms in the substituent does not include the number of carbon atoms in the substituent that the substituent further has.

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

When R ^c1 is an alkoxy group, it preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. Further, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples of R ^c1 being an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n -pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Further, when R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (--O--) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.

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

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 7 carbon atoms. Specific examples of when R ^c1 is a saturated aliphatic acyl group include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Noyl group, n-hexadecanoyl group and the like. Specific examples of when R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

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

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

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more of N, S, O, or such monocyclic rings are fused together or such monocyclic rings are fused with a benzene ring. is a heterocyclyl group. When the heterocyclyl group is a condensed ring, it has up to 3 rings. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. , saturated aliphatic acyl groups having 2 to 20 carbon atoms, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted 7 or more carbon atoms a phenylalkyl group of 20 or less, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and A heterocyclyl group and the like can be mentioned. Specific examples of these suitable organic groups are the same as R ^c1 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group and the like.

Substituents in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, alkyl groups 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 heterocyclyl group contained in R ^c1 further have substituents, the number of substituents is not limited as long as the object of the present invention is not hindered, but 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 have multiple substituents, the multiple substituents may be the same or different.

Among R ^c1 , an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and 1 A group selected from the group consisting of an alkoxy group having at least 6 carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable. .

Regarding the position at which R ^c1 is bonded to the phenyl group, regarding the phenyl group to which R ^c1 is bonded, the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is the 1st position, and the position of the methyl group is the 2nd position. In addition, the 4- or 5-position is preferred, and the 5-position is more preferred. Further, n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

R ^c2 is an optionally substituted phenyl group or an optionally substituted carbazolyl group. Further, when R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent of the phenyl group or carbazolyl group is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that a phenyl group or a carbazolyl group may have on a carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a carbon atom cycloalkyl group having 3 to 10 carbon atoms, cycloalkoxy group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbon atoms saturated aliphatic acyloxy groups having a number of 2 to 20, optionally substituted phenyl groups, optionally substituted phenoxy groups, optionally substituted phenylthio groups, substituted a benzoyl group optionally having a substituent, a phenoxycarbonyl group optionally having a substituent, a benzoyloxy group optionally having a substituent, a phenylalkyl group having 7 to 20 carbon atoms optionally having a substituent, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted optionally substituted naphthyloxy group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, optionally substituted heterocyclyl group, optionally substituted heterocyclylcarbonyl group, an amino group, an amino group substituted with one or two organic groups, a morpholin-1-yl group and 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 suitable substituents which the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms, cyclo groups having 3 to 10 carbon atoms, Alkyl group, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group , an optionally substituted phenoxycarbonyl group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, an optionally substituted naphthyl group, having a substituent a naphthoyl group optionally having substituents, a naphthoxycarbonyl group optionally having substituents, a naphthylalkyl group optionally having 11 to 20 carbon atoms, optionally having substituents, a heterocyclyl group optionally having substituents, and An optionally substituted heterocyclylcarbonyl group and the like are included. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the phenyl group or carbazolyl group may have include 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 substituted A phenylalkyl group optionally having a group, a naphthylalkyl group optionally having a substituent, a heterocyclyl group optionally having a substituent, and an amino group substituted with one or two organic groups , ^Rc1 .

In R ^c2 , when the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents of the phenyl group or carbazolyl group further have a substituent, examples of the substituent include alkyl having 1 to 6 carbon atoms. Alkoxy groups having 1 to 6 carbon atoms; saturated aliphatic acyl groups having 2 to 7 carbon atoms; alkoxycarbonyl groups having 2 to 7 carbon atoms; saturated aliphatic groups having 2 to 7 carbon atoms Acyloxy group; phenyl group; naphthyl group; benzoyl group; naphthoyl group; a benzoyl group substituted with a 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; morpholin-1-yl group; piperazine- 1-yl group; halogen; nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents of the phenyl group or carbazolyl group further have substituents, the number of the substituents is not limited as long as the objects of the present invention are not hindered. 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group and heterocyclyl group have multiple substituents, the multiple substituents may be the same or different.

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

（Ｒ^ｃ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０以上４以下の整数である。）

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

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

(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 as long as the object of the present invention is not impaired. Preferred examples of the case where R ^c4 in formula (c2) is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; saturated aliphatic acyl group; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; A benzoyl group substituted with a group selected from the group consisting of the following alkyl groups, morpholin-1-yl groups, piperazin-1-yl groups, and phenyl groups; alkylamino group; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group;

In R ^c4 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A benzoyl group; a nitro group is preferred, and a benzoyl group; a naphthoyl group; a 2-methylphenylcarbonyl group; a 4-(piperazin-1-yl)phenylcarbonyl group; and a 4-(phenyl)phenylcarbonyl group are more preferred.

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

R ^c5 in formula (c3) can be selected from various organic groups within a range that does not impede the object 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, and 2 carbon atoms. Alkoxycarbonyl groups of 20 or less, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted phenoxycarbonyl groups, optionally substituted a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group optionally having a substituent, a naphthoyl group optionally having a substituent, a naphthoxycarbonyl group optionally having a substituent, a substituent Examples include an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, and the like.

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

R ^c6 in formula (c3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of groups suitable for R ^c6 include alkyl groups having 1 to 20 carbon atoms, phenyl groups optionally having substituents, naphthyl groups optionally having substituents, and groups having substituents. and heterocyclyl groups. As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferred, and a 2-methylphenyl group is particularly preferred.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the substituent may be an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, alkoxy groups having at least 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, and the number of carbon atoms a monoalkylamino group having an alkyl group of 1 to 6, a dialkylamino group having an alkyl group of 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and A cyano group and the like can be mentioned. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have substituents, the number of substituents is not limited as long as the object of the present invention is not impaired, 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 have multiple substituents, the multiple substituents may be the same or different.

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

Particularly suitable compounds among the oxime ester compounds represented by formula (c1) include the following PI-1 to PI-42.

An oxime ester compound represented by the following formula (c4) is also preferable as the photopolymerization initiator (C).

（Ｒ^ｃ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ８及びＲ^ｃ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよく、Ｒ^ｃ１０は１価の有機基であり、Ｒ^ｃ１１は、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０以上４以下の整数であり、ｎ５は０又は１である。）

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are each an optionally substituted chain alkyl group, an optionally substituted cyclic organic or a hydrogen atom, R ^c8 and R ^c9 may be bonded to each other to form a ring, R ^c10 is a monovalent organic group, R ^c11 is a hydrogen atom, or has a substituent an alkyl group having 1 or more and 11 or less carbon atoms which may be substituted, or an aryl group which may have a substituent, n4 is an integer of 0 or more and 4 or less, and n5 is 0 or 1.)

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

（Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、Ｒ^ｃ１０、ｎ４、及びｎ５は、式（ｃ４）と同様である。）

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

In formulas (c4) and (c5), ^Rc7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by —(CO) _n5 — on the fluorene ring in formula (c4). In formula (c4), the bonding position of R ^c7 to the fluorene ring is not particularly limited. When the compound represented by formula (c4) has one or more R ^c7 , one of the one or more R ^c7 is a fluorene ring, because the compound represented by formula (c4) is easy to synthesize. It is preferable to bind to the 2-position in the middle. When R ^c7 is plural, the plural R ^c7 may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferred examples of R ^c7 being 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, and a substituent. optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy a phenylalkyl group optionally having substituents, a naphthyl group optionally having substituents, a naphthoxy group optionally having substituents, a naphthoyl group optionally having substituents, a substituent an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like.

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

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

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

When R ^c7 is a saturated aliphatic acyl group or saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples of R ^c7 being a saturated aliphatic acyl group include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanoyl group Noyl group, n-hexadecanoyl group and the like. Specific examples of R ^c7 being a saturated aliphatic acyloxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

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

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

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more of N, S, O, or such monocyclic rings are fused together or such monocyclic rings are fused with a benzene ring. is a heterocyclyl group. When the heterocyclyl group is a condensed ring, it has up to 3 rings. A heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 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, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted 7 to 20 carbon atoms The following phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthoyl groups, optionally substituted naphthylalkyl groups having 11 to 20 carbon atoms, and heterocyclyl and the like. Specific examples of these suitable organic groups are the same as R ^c7 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group and the like.

Examples of substituents when the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, alkyl groups 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 heterocyclyl group contained in R ^c7 further have substituents, the number of substituents is not limited as long as the object of the present invention is not impaired, but 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c7 have multiple substituents, the multiple substituents may be the same or different.

Among the groups described above, a nitro group or a group represented by R ^c12 --CO-- is preferred as R ^c7 because it tends to improve the sensitivity. R ^c12 is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of groups suitable for R ^c12 include alkyl groups having 1 to 20 carbon atoms, phenyl groups optionally having substituents, naphthyl groups optionally having substituents, and substituents heterocyclyl groups that may be Among these groups, a 2-methylphenyl group, a thiophen-2-yl group and an α-naphthyl group are particularly preferred as R ^c12 .
Further, when R ^c7 is a hydrogen atom, the transparency tends to be improved, which is preferable. When R ^c7 is a hydrogen atom and R ^c10 is a group represented by formula (c4a) or (c4b) described later, the transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 are each an optionally substituted chain alkyl group, an optionally substituted cyclic organic group, or a hydrogen atom. R ^c8 and R ^c9 may combine with each other to form a ring. Among these groups, chain alkyl groups which may have a substituent are preferable as R ^c8 and R ^c9 . When R ^c8 and R ^c9 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 R ^c8 and R ^c9 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable. Specific examples of R ^c8 and R ^c9 being chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups. , n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group. In addition, when R ^c8 and R ^c9 are alkyl groups, the alkyl group may contain an ether bond (--O--) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms in 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 in the substituent is not included in the number of carbon atoms in the chain alkyl group. A chain alkyl group having a substituent is preferably linear.
The substituents that the alkyl group may have are not particularly limited as long as they do not interfere with the object of the present invention. Suitable examples of substituents include cyano groups, halogen atoms, cyclic organic groups, and alkoxycarbonyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferred. Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclyl groups. Specific examples of the cycloalkyl group are the same as the preferred examples when R ^c7 is a cycloalkyl group. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups. Specific examples of the heterocyclyl group are the same as the preferred examples when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms in 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 substituents, the number of substituents 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 R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups. When R ^c8 and R ^c9 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as in the case where R ^c8 and R ^c9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is either a phenyl group or a group formed by combining multiple benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.

When R ^c8 and R ^c9 are an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, A tetracyclododecyl group, an adamantyl group, and the like can be mentioned.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl groups are 5- or 6-membered monocyclic rings containing one or more of N, S, O, or such monocyclic rings together, or such monocyclic rings and a benzene ring. is a fused heterocyclyl group. When the heterocyclyl group is a condensed ring, it has up to 3 rings. A heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.

R ^c8 and R ^c9 may combine with each other to form a ring. A group consisting of a ring formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 combine 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 combining R ^c8 and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and pyridine. ring, pyrazine ring, pyrimidine ring, and the like.

Examples of preferred groups among R ^c8 and R ^c9 described above include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, cyano group, halogen atom, halogenated alkyl group, cyclic organic group, or alkoxycarbonyl group.

The straight-chain alkylene group for A ¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. When ^A2 is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms in 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 groups that ^Rc8 and ^Rc9 have as substituents. When ^A2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that ^Rc8 and ^Rc9 have as substituents.

Preferred specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl; group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n -pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and cyanoalkyl groups such as 8-cyano-n-octyl group; 2-phenylethyl group, 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 groups. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy carbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n -Alkoxycarbonylalkyl groups such as heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n- pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n- butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Preferred groups among those described above for R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^c10 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups ^, saturated aliphatic acyloxy groups, substituents, and A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a substituent which may have benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthyloxy group, optionally substituted naphthylalkyl group, optionally substituted heterocyclyl group, substituted a heterocyclylcarbonyl group optionally having a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like. Specific examples of these groups are the same as the groups described for R ^c7 . R ^c10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ^c7 may have.

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

As R ^c10 , a group represented by —A ³ —CO—OA ⁴ is also preferable. ^A3 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. ^A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

When ^A3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ³ is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Preferred examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred specific examples of ^A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl. phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

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

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０以上４以下の整数であり、Ｒ^ｃ１３及びＲ^ｃ１４がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１以下８以下の整数であり、ｎ８は１以上５以下の整数であり、ｎ９は０以上（ｎ８＋３）以下の整数であり、Ｒ^ｃ１５は有機基である。） 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), R ^c13 and R ^c14 are each an organic group, n6 is an integer of 0 or more and 4 or less, and R ^c13 and R ^c14 are present at adjacent positions on the benzene ring. , R ^c13 and R ^c14 may combine with each other to form a ring, n7 is an integer of 1 or less and 8 or less, n8 is an integer of 1 or more and 5 or less, and n9 is 0 or more (n8+3) is an integer below, and R ^c15 is an organic group.)

Examples of organic groups for R ^c13 and R ^c14 in formula (c4a) are the same as 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 thereof 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 combine 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 naphthalen-1-yl and 1,2,3,4- A tetrahydronaphthalen-5-yl group and the like can be mentioned. In the above formula (c4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In formula (c4b) above, R ^c15 is an organic group. Examples of the organic group include the same organic groups as those described for R ^c7 . Among organic groups, alkyl groups are preferred. Alkyl groups may be straight or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. R ^c15 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.

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

In formula (c4), R ^c11 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. A phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed when R ^c11 is an alkyl group. In addition, when R ^c7 is an aryl group, the substituent which may be present is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, or the like.

In 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 preferable.

In the compound represented by formula (c4), the oxime group (>C=N-OH) contained in the compound represented by formula (c5) above is represented by >C=N-O-COR ^c11 . It is produced by a method that includes the step of converting to an oxime ester group. 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=N-O-COR ^c11 is performed by using the compound represented by the above formula (c5) and an acylating agent. is carried out by reacting
Examples of the acylating agent that provides the acyl group represented by —COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O and an acid halide represented by R ^c11 COHal (Hal is a halogen atom). be done.

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

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

In the photosensitive resin composition, the content of the photopolymerization initiator (C) is not particularly limited as long as the object of the present invention is not impaired, and the content of the photopolymerization initiator (C) is 0.1% by mass or more and 20% by mass or less is preferable, and 0.3% by mass or more and 10% by mass or less is more preferable with respect to the mass of the solid content.

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

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

(D) As the sensitizer, a compound having at least one substituent selected from the group consisting of an alkoxy group, a substituted carbonyloxy group 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 preferable.
The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have substituents other than alkoxy groups, substituted carbonyloxy groups, and oxo groups (=O). Examples of substituents include alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, alkoxyalkyl groups having 2 to 20 carbon atoms, and 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, a mercapto group, and the like.

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

A substituted carbonyloxy group is a group represented by -O-CO- ^Ad . ^Ad is not particularly limited as long as the sensitizer (D) has the desired sensitizing action, and may 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, and an aryloxy group having 6 to 10 carbon atoms. .

An aryl group or an aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as it does not interfere with the object 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, and 6 to 10 carbon atoms. an aryloxy group, an aliphatic acyl group having 2 to 7 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 mercapto group and the like can be mentioned.

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

In a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound substituted with one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O) , The number of rings constituting the condensed ring is not particularly limited as long as the desired sensitizing effect is 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.
As long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the single ring forming the condensed polycyclic ring may not necessarily be an aromatic ring.

Preferable examples of the condensed polycyclic ring contained in the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound include acenaphthylene ring, phenanthrene ring, anthracene ring, naphthacene ring, xanthene ring, and thio A xanthene ring is mentioned. Among these rings, anthracene ring, naphthacene ring and thioxanthene ring are preferred.

Specific examples of compounds containing an anthracene ring and preferably used as (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(isobutylcarbonyloxy)anthracene , 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(benzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)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(isopropylcarbonyl) oxy)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(benzoyloxy)anthracene, 2-methyl-9,10-bis(4 -methylbenzoyloxy)anthracene, 2-methyl-9,10-bis(2-naphthoyloxy)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(benzoyloxy)anthracene, 1-methyl-9,10-bis(4-methylbenzoyloxy)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, 2-ethyl-9,10-bis(4-ethyl-benzoyloxy)anthracene, 2-ethyl-9,10-bis(2-naphthoyloxy)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, 1-ethyl-9 , 10-bis(4-ethyl-benzoyloxy)anthracene, 1-ethyl-9,10-bis(2-naphthoyloxy)anthracene, 1-(t-butyl)-9,10-bis(n-propylcarbonyl oxy)anthracene, 1-(t-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 1-(t -butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-(t-butyl)-9,10- Bis(n-hexylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis(benzoyloxy)anthracene, 1-(t-butyl)-9,10-bis(4-(t-butyl) -benzoyloxy)anthracene, 1-(t-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-(t-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(t-butyl)- 9,10-bis(isobutylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(n- hexylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(benzoyloxy)anthracene, 2-(t-butyl)-9,10-bis(4-(t-butyl)-benzoyloxy) Anthracene, 2-(t-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, 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-(t-butyl)-benzoyloxy)anthracene, 2-pentyl-9,10-bis(2-naphthoyloxy)anthracene and the like.

Alternatively, an anthracene compound substituted with a rogen atom is also preferred as the (D) sensitizer. A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Specific examples of halogen-substituted anthracene compounds that are preferable as (D) sensitizers 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(benzoyloxy)anthracene, 2-chloro-9,10-bis(4-methylbenzoyloxy)anthracene, 2-chloro-9, 10-bis(2-naphthoyloxy)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(benzoyloxy)anthracene, 1-chloro-9,10-bis(4-methylbenzoyloxy)anthracene, 1-chloro-9,10-bis(2-naphthoyloxy)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(benzoyloxy)anthracene, 2-fluoro- 9,10-bis(4-methylbenzoyloxy)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, 1-fluoro-9,10-bis(benzoyloxy)anthracene, 1-fluoro-9,10-bis(4-methylbenzoyloxy)anthracene, 1 -fluoro-9,10-bis(2-naphthoyloxy)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-9,10-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene , 2-bromo-9,10-bis(benzoyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzoyloxy)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(benzoyloxy)anthracene , 1-bromo-9,10-bis(4-methylbenzoyloxy)anthracene, and 1-bromo-9,10-bis(2-naphthoyloxy)anthracene.

Furthermore, an anthracene compound substituted with an alkoxy group is also preferable as the (D) sensitizer.
Specific examples of compounds which are alkoxy-substituted anthracene compounds and are preferred as (D) sensitizers include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis(n- Propyloxy)anthracene, 9,10-bis(n-butyloxy)anthracene, 9,10-bis(n-pentyloxy)anthracene, 9,10-bis(isopentyloxyoxy)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-propyloxy)anthracene, 9-(n-butyloxy)anthracene, 9-(n-pentyloxy)anthracene, 9-(isopentyloxyoxy)anthracene, 9-(n-hexyl) oxy)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-propyloxy)anthracene, 2-methyl-9,10-bis(n-butyloxy)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-propyloxy)anthracene, 2-ethyl-9,10-bis(n-butyloxy)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-9,10-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-butyloxy)anthracene, 2-methyl-9 -(n-pentyloxy)anthracene, 2-methyl-9-(isopentyloxyoxy)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-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl -9-(n-propyloxy)anthracene, 2-ethyl-9-(n-butyloxy)anthracene, 2-ethyl-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxyoxy) 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-propyloxy)anthracene, 2- Chloro-9,10-bis(n-butyloxy)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 -propyloxy)anthracene, 2-bromo-9,10-bis(n-butyloxy)anthracene, 2-bromo-9,10-bis(n-pentyloxy)anthracene, 2-bromo-9,10-bis(iso pentyloxy)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-methoxyanthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9-(n -propyloxy)anthracene, 2-chloro-9-(n-butyloxy)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-propyloxy)anthracene, 2-bromo-9-(n-butyloxy)anthracene, 2- Bromo-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxyoxy)anthracene, 2-bromo-9-(n-hexyloxy)anthracene, 2-bromo-9-(n-heptyl oxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, 2-bromo-9-(2-ethylhexyloxy)anthracene and the like.

Among the anthracene compounds described above, 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, and 9 , 10-bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutylcarbonyloxy)anthracene , 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 are preferred.

Specific examples of the compound containing a naphthacene ring and suitably used as the (D) sensitizer include:
2-methyl-5,11-dioxo-6,12-bis(acetyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(propionyloxy)naphthacene, 2-methyl-5,11- dioxo-6,12-bis(n-propylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6, 12-bis(n-butylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis( n-pentylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n- heptylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(acetyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(propionyloxy)naphthacene, 2- ethyl-5,11-dioxo-6,12-bis(n-propylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(n-butylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis(n-pentylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6 , 12-bis(n-heptylbornyloxy) naphthacene compounds substituted with alkylcarbonyloxy groups such as naphthacene;
2-methyl-5,11-dioxo-6,12-bis(benzoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2-methyl-5 , 11-dioxo-6,12-bis(m-toluoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene, 2-methyl-5,11 -dioxo-6,12-bis(α-naphthoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene, 2-ethyl-5,11-dioxo -6,12-bis(benzoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12- bis(m-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis( aroyloxy group-substituted naphthacene compounds such as α-naphthoyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene;
2-methyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-methyl-5, 11-dioxo-6,12-bis(n-propyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 2-methyl-5,11- Dioxo-6,12-bis(n-butyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-pentyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-heptyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis(methoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis( n-propyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n- Butyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-pentyloxy carbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-heptyloxy alkoxycarbonyloxy group-substituted naphthacene compounds such as carbonyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene;
2-methyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-methyl -5,11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-methyl -5,11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene, 2-ethyl -5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5, Aroyloxycarbonyls such as 11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene Oxy group-substituted naphthacene compounds can be mentioned.

Among the above naphthacene ring-containing compounds, 5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 5,11- Dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(n-butylcarbonyl) oxy)naphthacene, 5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)naphthacene and 5,11-dioxo-6,12-bis(n-heptanoyloxy)naphthacene are preferred.
(A) In terms of compatibility with photopolymerizable compounds, 5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy) ) naphthacene, 5,11-dioxo-6,12-bis(n-butyryloxy)naphthacene, 5,11-dioxo-6,12-bis(n-valeryloxy)naphthacene, 5,11-dioxo-6,12-bis (Heptanoyloxy)naphthacene is preferred.

(D) Specific examples of compounds containing a thioxanthene ring suitably used as a sensitizer include thioxanthene-9-one, 2-methyl-9H-thioxanthene-9-one, 2-isopropyl-9H- thioxanthen-9-one, 1,4-dimethylthioxanthen-9-one, 3-methyl-9-oxo-9H-thioxanthen-2-yl acetate and the like.

The content of the sensitizer, which is the component (D), is preferably 5 parts by mass or more and 60 parts by mass or less with respect to the total 100 parts by mass of the photopolymerization initiator component (C) in the photosensitive resin composition, and 15 parts by mass. Part or more and 50 parts by mass or less is more preferable. When the photosensitive resin composition contains the sensitizer within the above range, the curing reaction by exposure proceeds uniformly, and it is easy to form a patterned cured film with particularly good edge angles.

<(E) Colorant>
Depending on the application, the photosensitive resin composition may be a substantially colorless and transparent composition that does not contain a coloring agent. On the other hand, in another application, the photosensitive resin composition may further contain (D) a colorant. The photosensitive resin composition contains, for example, a black pigment as a colorant (D) component, and is preferably used for forming a black matrix (or black bank) in a color filter of a display device, for example. Also, a chromatic colorant can be preferably used, for example, in the formation of a color filter for a display device.

The (D) coloring agent contained in the photosensitive resin composition is not particularly limited, but when the coloring agent is used as a light shielding agent, it is preferable to use a black pigment as the light shielding agent. Black pigments include carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, metal sulfates, metal carbonates, and the like. , organic and inorganic pigments. Among these, it is preferable to use carbon black, which has a high light-shielding property.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black which has excellent light shielding properties. Resin-coated carbon black may also be used.

Resin-coated carbon black has lower conductivity than carbon black without resin coating, so when used as a black matrix for a liquid crystal display element such as a liquid crystal display, there is little current leakage, and it is a highly reliable low-power. Power consumption displays can be manufactured.
Examples of black pigments other than carbon black include (D2a) perylene pigments and (D2b) lactam pigments. These pigments can be used in combination of two or more.

The (D2a) perylene-based pigment is not particularly limited as long as it is composed of a compound having a perylene skeleton and exhibits a black color.
(D2a) Specific examples of the perylene pigment include a perylene pigment represented by formula (d-1) below, a perylene pigment represented by formula (d-2) below, and a perylene pigment represented by formula (d-3) below. A perylene pigment represented by is mentioned. Commercially available products such as K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, and 34 can be preferably used as (D2a) perylene pigments.

式（ｄ－１）中、Ｒ^ｄ１及びＲ^ｄ２は、それぞれ独立に炭素原子数１以上３以下のアルキレン基を表し、Ｒ^ｄ３及びＲ^ｄ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In formula (d-1), R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 3 carbon atoms, R ^d3 and R ^d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or represents an acetyl group.

式（ｄ－２）中、Ｒ^ｄ５及びＲ^ｄ６は、それぞれ独立に、炭素原子数１以上７以下のアルキレン基を表す。

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

式（ｄ－３）中、Ｒ^ｄ７及びＲ^ｄ８は、それぞれ独立に、水素原子、炭素原子数１以上２２以下のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｄ７及びＲ^ｄ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (d-3), R ^d7 and R ^d8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and containing a heteroatom of N, O, S, or P; good too. When R ^d7 and R ^d8 are alkyl groups, the alkyl groups 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) are disclosed, for example, in JP-A-62-1753. , and can be synthesized using the method described in JP-B-63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials and subjected to a heat reaction in water or an organic solvent. The desired product can be obtained by reprecipitating the resulting crude product in sulfuric acid, or by recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

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

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

In formula (d-4), X ^d represents a double bond and is each independently an E or Z isomer as a geometric isomer, and R ^d9 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, bromine atom, chlorine atom, fluorine atom, carboxy group, or sulfo group; R ^d10 each independently represents a hydrogen atom, methyl group, or phenyl group; R ^d11 each independently represents a hydrogen atom , a methyl group, or a chlorine atom.
The compounds represented by formula (d-4) can be used alone or in combination of two or more.
R ^d9 is preferably bonded to the 6-position of the dihydroindolone ring, and R ^d11 is bonded to the 4-position of the dihydroindolone ring, from the viewpoint of facilitating the production of the compound represented by formula (d-4). preferably. From the same point of view, R ^d9 , R ^d10 and R ^d11 are preferably hydrogen atoms.
The compound represented by formula (d-4) has EE isomer, ZZ isomer, and EZ isomer as geometric isomers. may be a mixture of
The compound represented by formula (d-4) can be produced, for example, by the methods described in WO 2000/24736 and WO 2010/081624.

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

Further, in order to adjust the color tone of black pigments such as carbon black, organic pigments such as those shown below may be appropriately added as auxiliary pigments. Alternatively, without using a black pigment such as carbon black, it is possible to obtain black by combining a plurality of organic pigments as shown below, for example, by mixing three primary color materials.

Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists), specifically, the following color index (C .I.) numbered pigments are preferably used.

Examples of yellow pigments that can be suitably used include C.I. I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same and only the number is described.), 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 preferably used include C.I. I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same and only the number is described.), 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 preferably used include C.I. I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the number is described.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50 mentioned.

Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same 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 preferably used include C.I. I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and only the number is described.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64 , and 66.

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

A dispersant may be further used to uniformly disperse the above colorant in the photosensitive resin composition. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more. It is preferably used in the range of no more than 20 parts by mass and more preferably in the range of 20 parts by mass or more and 40 parts by mass or less.

The amount of the coloring agent to be used in the photosensitive resin composition may be appropriately determined according to the application of the photosensitive resin composition. 1 part by mass or more and 50 parts by mass or less is preferable, and 5 parts by mass or more and 30 parts by mass or less is more preferable. By setting the amount within the above range, the black matrix and each colored layer can be formed in the desired pattern, which is preferable.

In particular, when a black matrix (or black bank) is formed using a photosensitive resin composition, the light shielding in the photosensitive resin composition is such that the OD value per 1 μm of the black matrix film is 0.1 or more. It is preferable to adjust the amount of agent. If the OD value per 1 μm of the film in the black matrix is 0.1 or more, sufficient display contrast can be obtained when used for the black matrix of the display.

It is preferable to add the colorant to the photosensitive resin composition after dispersing the colorant at an appropriate concentration using a dispersant to form a dispersion.

<Solvent (S)>
The photosensitive resin composition may or may not contain a solvent (S). When the solvent (S) is included, 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 mono Ethyl 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, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly)alkylene glycol monoalkyl ethers such as monoethyl ether; 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 (Poly)alkylene glycol monoalkyl ether acetates such as acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid methyl, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, pyruvic acid other esters such as methyl, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, and amides such as N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

The photosensitive resin composition may be prepared by dispersing/dissolving each component in a solvent. If the aforementioned component (A) is liquid, no solvent may be used. When a solvent is included, the solvent used in the photosensitive resin composition includes, for example, 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, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, (Poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether; 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 (poly)alkylene glycol monoalkyl ether acetates such as monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. ketones; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N,N-dimethylformamide and N,N-dimethylacetamide. 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. Just adjust.

<(E) water repellent>
The photosensitive resin composition may further contain a water repellent. Formation of a water-repellent film having a pattern shape with a photosensitive resin composition is used, for example, in the fields of planographic printing plates, nozzle surfaces of inkjet heads, etc., because the printing quality is greatly improved by water-repellent or liquid-repellent properties. This is desired.

(E) The water repellent is not particularly limited, but preferably contains a fluorine-containing compound. For example, water repellents include cationic polymerizable perfluoroalkyl compositions and cationic polymerizable perfluoropolyether compositions. Specifically, the composition preferably contains an ink repellent agent having a side chain containing a group represented by the following formula (E-1) or a group represented by the following formula (E-2).
-CFXR ^f (E-1)
-(SiR ^e1 R ^e2 -O)n-SiR ^e3 R ^e4 R ^e5 (E-2)
In formula (1), X represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and R ^f is a carbon atom in which at least one hydrogen atom which may have an etheric oxygen atom is substituted with a fluorine atom. It represents a fluoroalkyl group of number 20 or less, or a fluorine atom.
In formula (2), R ^e1 , R ^e2 , R ^e3 and R ^e4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ^e5 is a hydrogen atom or a C 1-10 It represents an organic group, and n represents an integer of 1-200.
Further, a condensate containing a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having a cationic polymerizable group can be exemplified. As an example, for example, the following formula CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si(OCH ₃ ) ₃
(In the formula, n is an integer of 0 or more and 7 or less.)
Compounds represented by and the like. If n exceeds the above range, the compatibility in the photosensitive resin composition is lowered, making it difficult to impart uniform water repellency to the entire coating film.

In the photosensitive resin composition, the blending ratio of the water repellent is not particularly limited, but it is preferably 20 parts by mass or less with respect to the total 100 parts by mass of the components other than the solvent in the photosensitive resin composition. It is preferably 0.05 parts by mass or more and 10 parts by mass or less. When the water repellent agent is used in an amount within the above range, the alkali-soluble resin (A) and the water repellent agent are well compatible, and the cured film has good hardness and good water repellency. It is easy to achieve well-balanced edge angle characteristics of the cured film.

<Other ingredients>
If necessary, the photosensitive resin composition may contain other various additives. Specific examples include dispersing aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like.

Thermal polymerization inhibitors used in the photosensitive resin composition include, for example, hydroquinone and hydroquinone monoethyl ether. Examples of antifoaming agents include silicone-based and fluorine-based compounds, and surfactants include anionic, cationic, and nonionic compounds.

[Method for preparing photosensitive resin composition]
The photosensitive resin composition is prepared by mixing all of the above components with a stirrer. In addition, when the prepared photosensitive resin composition does not contain an insoluble component such as a pigment, it may be filtered using a filter so that the photosensitive resin composition becomes uniform.

<<Method of Forming Cured Film>>
The method for producing a cured film includes a step of applying a photosensitive resin composition on a substrate to form a photosensitive resin layer (hereinafter also simply referred to as a “resin layer forming step”), and a position-selective formation of the resin layer. (hereinafter simply referred to as “exposure step”), and a step of developing the exposed photosensitive resin layer with a developer to form a pattern (hereinafter simply referred to as “development step”).

The substrate (substrate or support) can be selected according to various uses, and examples thereof include quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, and metals such as Ni, Cu, Cr, and Fe. Substrates, paper, SOG (Spin On Glass), polymer substrates such as polyester films, polycarbonate films, and polyimide films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulation There are no particular restrictions on the substrate, such as a flexible substrate, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, or the like. Furthermore, in the case of forming a laminate structure on a substrate, for example, any layer which is already formed on the substrate and which is a substructure is also included in the concept of the base material to which the photosensitive resin layer is applied. Also, the shape of the substrate is not particularly limited, and may be plate-like or roll-like. The substrate may further have, for example, unevenness on the surface according to various patterns. Moreover, as the base material, a light-transmitting or non-light-transmitting base material can be selected.

First, in the resin layer forming step, for example, a contact transfer coating device such as a roll coater, a reverse coater, a bar coater, a spinner (rotary coating device), a dispenser, an inkjet, or a spray is applied onto a substrate on which a cured product is to be formed. , Screen printing, applying a photosensitive resin composition using a non-contact coating device such as a curtain flow coater, if necessary, drying (pre-baking) to remove the solvent to form a photosensitive resin layer. can.

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. Although there is no particular upper limit, it is, for example, 50 μm or less, preferably 20 μm or less. As described above, the photosensitive resin composition accelerates curing even in areas where the active energy does not reach directly during exposure. Even in this mode, the curing can be sufficiently progressed in the vicinity of the substrate side which is farther from the exposure side.

For the sake of convenience, "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 capable of curing the photosensitive resin composition, and if necessary, heat treatment can also be performed together.

Light sources for exposure are not particularly limited, and examples thereof include high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, carbon arc lamps, and LEDs. Using such a light source, the coating film is irradiated with 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-rays, j-rays, k-rays, or other radiation or electromagnetic waves can be applied to expose the coating film. The exposure of the coating film may be position-selectively performed through a negative mask. Although the exposure amount varies depending on the composition of the curable composition, it is preferably 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 200 mJ/cm ^{2 or more and 1200 mJ/cm 2} or more. ² or less is more preferable. The exposure illuminance varies depending on the composition of the photosensitive resin composition, but is preferably in the range of 1 mW/cm ² or more and 50 mW/cm ² or less.
The temperature for heating is not particularly limited, and is preferably 180° C. or higher and 280° C. or lower, more preferably 200° C. or higher and 260° C. or lower, and particularly preferably 220° C. or higher and 250° C. or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

The step of curing the photosensitive resin layer is performed by position-selective exposure, and the position-selectively exposed photosensitive resin layer is developed to obtain a patterned cured film.
The aforementioned curable compositions are not overly soluble in developer after exposure. Therefore, by using the curable composition described above, it is possible to form a well-shaped patterned cured product in which the exposed portions are convex portions and the unexposed portions are concave portions.

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

Then, if necessary, the cured product after exposure or the patterned cured product after development may be post-baked to further proceed with heat curing. The post-baking temperature is preferably 150° C. or higher and 270° C. or lower.

≪Curified product≫
The cured product is obtained by curing the curable composition described above. Therefore, the cured product can 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 made of the above cured product, it can have the above fine fine pattern.

The cured product may be used as a bank formed in a shape that partitions the substrate surface into a plurality of sections for forming dots.
A dot indicates the minimum area in which light can be modulated in the optical element. In organic EL devices, quantum dot displays, TFT arrays, and thin-film solar cells, 1 dot = 1 pixel for black-and-white display, and for example, 3 dots (R (red), G (green), B (blue), etc.) = 1 pixel.

Since the cured product is formed from a photosensitive resin composition having excellent patterning properties,
When used for optical elements (particularly, organic EL elements, quantum dot displays, TFT arrays, or thin-film solar cells produced by the inkjet method), the openings are uniformly coated with ink, and dots can be formed with high accuracy.

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

An example in which the cured product is used as a bank and dots are formed in the opening of the bank by an inkjet method to obtain an optical element will be described below, but the invention is not limited to this.

A method of manufacturing a quantum dot display, which is an example of an optical element, using banks formed on a substrate (for example, banks formed in a grid pattern when viewed from above) will be described.

Here, the banks on the substrate are formed so that the openings match the dot pattern of the quantum dot display to be manufactured.

Also, the substrate is a translucent substrate such as glass on which a translucent electrode such as ITO is deposited by sputtering or the like. This translucent electrode may be patterned as required.

A predetermined amount of ink is injected into the opening by dropping ink from an inkjet head into the opening surrounded by the bank. As the ink, known inks for quantum dot displays (e.g. materials for hole injection layer, hole transport layer, quantum dot layer, hole blocking layer and electron injection layer) can be used according to the function of the dots. , etc.) are appropriately selected and used.

Then, depending on the type of ink used, for example, drying and/or heating are performed to remove the solvent or cure the ink, thereby forming a desired dot layer adjacent to the bank. After that, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by a vapor deposition method or the like to obtain a quantum dot display.

The quantum dot display may be a blue light conversion type quantum dot display. In this case, banks are formed in a lattice pattern in plan view along the outline of each dot on a translucent substrate such as glass. Next, a nanoparticle solution that converts blue light to green light, a nanoparticle solution that converts blue light to red light, and, if necessary, a blue color ink are applied and dried by an inkjet method inside the openings for forming dots. to create a module. A display with excellent color reproducibility can be obtained by using a light source emitting blue as a backlight and using the module as a substitute for a color filter.

By using the bank made of the cured product according to the present invention, it is possible to uniformly apply the ink to the openings partitioned by the cured product (bank) with high pattern accuracy in the manufacturing process, thereby forming with high accuracy. An optical element (organic EL element, quantum dot display, TFT array or thin-film solar cell) having dots formed thereon can be obtained.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited to these Examples.

In Examples 1 to 23 and Comparative Examples 1 to 5 shown below, resins (a-1-1) and (a-1- 2) and (a-2-1) were used.

First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72 g of acrylic acid were placed in a 500 ml four-necked flask. 0 g of the solution was charged and dissolved by heating at 90° C. to 100° C. while blowing air at a rate of 25 ml/min. Next, the solution was gradually heated to 120° C. while the solution remained cloudy, and dissolved completely. At this point, the solution gradually became transparent and viscous, but the stirring was continued. During this time, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target. Then, it was cooled to room temperature to obtain a 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 dissolved, followed by 80.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. were mixed, and the temperature was gradually raised to 110° C. to 115° C. for 4 hours to react. After confirming the disappearance of the acid anhydride, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to give resin (a-1-1) (mass average molecular weight: 3400) was obtained. Disappearance of acid anhydride was confirmed by IR spectrum.

Production of resin (a-1-1) except that 80.5 g of biphenyltetracarboxylic dianhydride in the production of resin (a-1-1) was changed to 59.7 g of pyromellitic dianhydride. A resin (a-1-2) was obtained in the same manner. The weight average molecular weight was 2,500.

（アクリル系樹脂ａ－２－１の上記式中、各単位の右下の数字は、アルカリ可溶性樹脂中の各単位の含有量（質量％）を意味する。）
上記アルカリ可溶性樹脂の重量平均分子量は、７０００であった。

(In the above formula of acrylic resin a-2-1, the lower right number of each unit means the content (% by mass) of each unit in the alkali-soluble resin.)
The weight average molecular weight of the alkali-soluble resin was 7,000.

In each of the examples and comparative examples, dipentaerythritol hexaacrylate (b-2-1) was used as the cross-linking agent (B) and the polyfunctional (meth)acrylic monomer (B2).

Furthermore, compounds represented by the following formulas (b-1-1) to (b-1-4) were used as monofunctional (meth)acrylic monomers as the cross-linking agent (B) in the amounts shown in Table 1. .

In each example and comparative example, compounds c1 and c2 represented by the following formula were used as the photopolymerization initiator (C).

In addition, 2-isopropylthioxanthone (compound d1: 2-isopropyl-9H-thioxanthen-9-one) was used as the sensitizer (D) in each of the examples and comparative examples.

Furthermore, in each of Examples 1 to 18, 22 to 26 and Comparative Examples 1 to 4, the amount of the colorant as shown in Table 1 (the amount of the colorant component in each dispersion converted to a numerical value) was As (E), carbon black dispersion (27% by mass of furnace black in PGMEA solvent) (e1), or 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.

In each example and comparative example, the active agent (f1: BYK310) as the additive (F) and (f3) a fluorosurfactant (perfluorobutylethyl methacrylate, polyethylene glycol methacrylate, and a configuration derived from n-butyl methacrylate A copolymer containing units, mass average molecular weight: 20000) was added, and N-phenyl-3-aminopropyltrimethoxysilane (f2) was added as an additive.

All of these activators (f1), (f3) and additive (f2) were added in the examples. However, in the photosensitive resin composition, these activators and additives are not essential components, and evaluation results similar to those of the examples disclosed herein were obtained even with the same composition except that they were not blended. there is

In each example and comparative example, 3-methoxybutyl acetate (g1) and propylene glycol monomethyl ether acetate (g2) were used as solvents in a ratio of 15/85 (mass ratio).

[Examples 1 to 26 and Comparative Examples 1 to 5]
Alkali-soluble resin (A), crosslinking agent (B), photopolymerization initiator (C), sensitizer (D), colorant (E), additive (E) and The solvent (G) was uniformly mixed with a stirrer at room temperature (25° C.±2° C.) to obtain a photosensitive resin composition of each example and comparative example. In Examples 19 to 21 and Comparative Example 5, the colorant (E) was not blended, and a transparent resin composition was used.

[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 prebaked at 100 ° C. for 120 seconds to form a coating film. bottom. Next, using a proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap is set to 50 μm, and ultraviolet rays are applied to the coating film through a negative mask having a line pattern with a width of 20 μm. irradiated. The exposure amount was 200 mJ/cm ² . After exposure, the coating film was developed with a 0.04 mass % KOH aqueous solution at 26° C. for 50 seconds, and 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 was observed with an optical microscope to evaluate the straightness of the pattern. The straightness of the pattern was evaluated as "good" when there was no rattling at the edge of the line, and as "bad" when there was rattling.

(taper angle)
A taper angle was evaluated for a line pattern formed with an exposure amount of 200 mJ/cm ² . The taper angle was measured as the bonding angle between the pattern and the substrate with a scanning electron microscope. Table 1 shows the measured taper angles. It means that the closer the taper angle is to 90°, the closer the cross-sectional shape of the pattern is to a desired rectangular shape. If the taper angle is considerably smaller than 90°, the cross-sectional shape of the pattern is not a desired rectangular shape. The cross-sectional shape of the line pattern was determined based on the following criteria based on the measurement result of the taper angle. The results are shown in Table 1 together.
A: The taper angle is 80° or more and 90° or less.
○: The taper angle is 70° or more and less than 80°.
Δ: The taper angle is 50° or more and less than 70°.
x: 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 prebaked at 100 ° C. for 120 seconds to form a coating film. bottom. Then, using a proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Corporation), the photosensitive resin layer was exposed with an exposure amount of 200 mJ/cm ² and an exposure gap of 50 μm. A cured film was formed by post-baking the exposed photosensitive resin layer at 230° C. for 30 minutes. The thickness of the formed light shielding film was 10 μm. The OD value per 10 μm of the light-shielding film thus formed was measured using a transmittance meter (D-200II, manufactured by GretagMacbeth), and the OD value per 1 μm was calculated using an approximate curve. Table 1 shows the measurement results of the OD value.
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. It was found that a cured film having 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 containing no colorant are all 0.01/μm, and have high transmittance. It was found that a cured film was formed.

Claims (9)

an alkali-soluble resin (A);
a cross-linking agent (B);
a photoinitiator (C);
A photosensitive resin composition comprising
As the cross-linking agent (B), a monofunctional (meth)acrylic monomer (B1a) represented by the following formula (B1-1) and a polyfunctional (meth)acrylic monomer (B2) having a functionality of two or more are included. ,
Curing formed by exposing the photosensitive resin composition at an exposure amount of 200 mJ/cm 2 , developing with 0.04% by mass KOH at 26° C. after the exposure, and post-baking at 230° C. for 30 minutes after the ^development A photosensitive resin composition, wherein the taper angle of the film is 70° or more and 90° or less.
CH ₂ ═CR ^b1 —CO—(OR ^b2 —) _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 an unsubstituted biphenyl group, n1 is 0 or 1 , When n1 is 0, X ^b1 is -O- or -NH-.) 2. The photosensitive resin composition according to claim 1 , wherein the alkali-soluble resin (A) contains a resin having a cardo structure. The photosensitive resin composition according to claim 1 or 2 , wherein the content of the monofunctional (meth)acrylic monomer (B1a) is 5% by mass or more and 50% by mass or less with respect to the total mass of the crosslinking agent (B). thing. 4. The photosensitive resin composition according to any one of claims 1 to 3 , further comprising a sensitizer (D). 5. The photosensitive resin composition according to any one of claims 1 to 4 , further comprising a coloring agent (E). 6. The photosensitive resin composition according to claim 5 , wherein the coloring agent (E) is a black pigment. The photosensitive resin composition according to any one of claims 1 to 6 , further comprising a water repellent (F). Coating the photosensitive resin composition according to any one of claims 1 to 7 on a substrate to form a photosensitive resin layer;
position-selectively exposing the photosensitive resin layer;
developing the exposed photosensitive resin layer with a developer;
A method for producing a patterned cured film, comprising: A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7 .