JP7313136B2 - Photosensitive resin composition, method for producing patterned cured film, and patterned 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 patterned cured film.

For example, in a display device such as a liquid crystal display device, a large number of insulating films, light-transmitting members such as spacers, and light-shielding members such as a black matrix are used. Such members are often formed as patterned films. In order to form a patterned film, a photosensitive resin composition that gives a cured film by exposure is widely used. A patterned cured film can be formed by developing such a photosensitive resin composition after position-selectively exposing it.

For example, as a photosensitive resin composition capable of forming a transparent cured film, a composition containing a resin, a polymerizable compound, a polymerization initiator having a specific structure, and a solvent has been proposed (Patent Document 1). Specifically, Examples of Patent Document 1 disclose a photosensitive resin composition containing a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, a polymerization initiator represented by one of the following formulas, and a mixed solvent composed of 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-ethoxyethyl propionate, and 3-methoxybutyl acetate.

JP 2012-58728 A

By the way, photosensitive resin compositions in general are often required to be capable of forming a patterned cured film having excellent straightness and adhesion to a substrate and having a favorable cross-sectional shape. However, when using a conventionally known photosensitive resin composition such as the photosensitive resin composition described in Patent Document 1, it is often impossible to form a patterned cured film that is excellent in straightness and adhesion to a substrate and has a good cross-sectional shape.

The present invention has been made in view of the above problems, and aims to provide a photosensitive resin composition capable of forming a patterned cured film having excellent straightness and adhesion to a substrate and having a good cross-sectional shape, a method for producing a patterned cured film using the photosensitive resin composition, and a patterned cured film that can be produced by the production method.

The present inventors have found that the above problems can be solved by combining a photopolymerization initiator (C-I), which is an oxime ester compound having a specific structure containing a nitrated carbazole ring, and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-II), in a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), and have completed the present invention. More specifically, the present invention provides the following.

（式（Ｃ１）中、Ｘ^０１は、下記式（Ｃ１－１）：

で表される構造において、芳香族環上に結合する水素原子のうち、ｔ２＋ｔ３個の水素原子を除いた基であり、Ｘ^０２及びＸ^０３は、それぞれ独立に１価の有機基であり、Ｘ^０４及びＸ^０５は、それぞれ独立に水素原子、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、ｔ０～ｔ３は、それぞれ独立に、０又は１であり、ｔ２及びｔ３の少なくとも一方は１であり、
式（Ｃ１－１）中、Ｘ^０６は、カルバゾール環中の窒素原子にＣ－Ｎ結合で結合する１価の有機基であり、ｔ４及びｔ５は、それぞれ独立に０又は１であり、ｔ４及びｔ５の少なくとも一方は１である。）
で表される光重合開始剤（Ｃ－Ｉ）と、光重合開始剤（Ｃ－Ｉ）以外の他の光重合開始剤（Ｃ－ＩＩ）とを含み、
光重合開始剤（Ｃ）の質量における、前記光重合開始剤（Ｃ－Ｉ）の質量の比率が、２０質量％以上９５質量％以下である、感光性樹脂組成物である。 A first aspect of the present invention is a photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), wherein the photopolymerization initiator (C) is represented by the following formula (C1):

(In formula (C1), X ⁰¹ is the following formula (C1-1):

wherein t2+t3 hydrogen atoms are removed from among the hydrogen atoms bonded to the aromatic ring, X ⁰² and X ⁰³ are each independently a monovalent organic group, X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, t0 to t3 are each independently 0 or 1, and t2 and at least one of t3 is 1;
In formula (C1-1), ^X06 is a monovalent organic group bonded to the nitrogen atom in the carbazole ring via a C—N bond, t4 and t5 are each independently 0 or 1, and at least one of t4 and t5 is 1. )
Including a photopolymerization initiator (C-I) represented by and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I),
The photosensitive resin composition, wherein the mass ratio of the photopolymerization initiator (C-I) to the mass of the photopolymerization initiator (C) is 20% by mass or more and 95% by mass or less.

A second aspect of the present invention is
Coating the photosensitive resin composition according to the first aspect on a substrate to form a coating film;
position-selectively exposing the coating film;
Developing the exposed coating film;
A method for producing a patterned cured film, comprising:

A third aspect of the present invention is a patterned cured film comprising a cured product of the photosensitive resin composition according to the first aspect.

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a patterned cured film having excellent straightness and adhesion to a substrate and having a good cross-sectional shape, a method for producing a patterned cured film using the photosensitive resin composition, and a patterned cured film that can be produced by the production method.

It is a figure which shows typically the cross-sectional shape of the pattern width direction of the cured film formed using the photosensitive resin composition provided with the cross-sectional shape of forward taper. It is a figure which shows typically the pattern width direction cross-sectional shape of the cured film formed using the photosensitive resin composition provided with reverse taper cross-sectional shape.

<<Photosensitive resin composition>>
The photosensitive resin composition contains an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C).
The photosensitive resin composition includes, as a photopolymerization initiator (C), a photopolymerization initiator (C-I) represented by the formula (C1) described later and another photopolymerization initiator (C-I) other than the photopolymerization initiator (C-II) in combination. The mass ratio of the photopolymerization initiator (CI) to the mass of the photopolymerization initiator (C) is 20% by mass or more and 95% by mass or less.
The photosensitive resin composition contains a predetermined amount of the photopolymerization initiator (C-I) and the photopolymerization initiator (C-II) in combination, so that the photosensitive resin composition can be used to form a patterned cured film having excellent straightness and adhesion to the substrate and having a good cross-sectional shape.

The essential or optional components contained in the photosensitive resin composition are described below.

<Alkali-soluble resin (A)>
The photosensitive resin composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) is not particularly limited, and can be appropriately selected from alkali-soluble resins conventionally blended in various photosensitive resin compositions.
Here, in the present specification, the alkali-soluble resin (A) refers to a resin having functional groups (for example, phenolic hydroxyl group, carboxy group, sulfonic acid group, etc.) that impart alkali solubility in the molecule.

Resins suitable as the alkali-soluble resin (A) include a resin (a-1) having a cardo structure (hereinafter also referred to as "cardo resin (a-1)").
When using the resin (a-1) having a cardo structure as the alkali-soluble resin, it is easy to obtain a photosensitive resin composition having excellent resolution, and to form a cured film that is difficult to flow excessively by heating using the photosensitive resin composition. Therefore, it is easy to form a cured film having a good shape.

[Resin (a-1) having cardo structure]
As the resin (a-1) having a cardo skeleton, a resin having a cardo skeleton in its structure and having a predetermined 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 have 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.

The cardo resin (a-1) 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 formula (a-1), X ^a represents a group represented by formula (a-2) below. m1 represents an integer of 0 or more and 20 or less.

In the above formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, 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).

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

Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and which may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Aliphatic rings 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 the formula (a-1) is introduced into the cardo resin (a-1) by reacting a tetracarboxylic dianhydride that gives the residue Z ^a with a diol compound represented by the following formula (a-2a).

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, a hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is optionally substituted with a group represented by -R ^a3 -OH according to a conventional method, and then glycidylized 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, 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 the tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
In the above formula (a-1), m 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 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 represents an integer of 0 to 12.)

The alkyl group that can be selected as R ^a4 in formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group within this range, the heat resistance of the obtained 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, even more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less, in order to easily obtain a cardo resin having excellent heat resistance.
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 are preferably a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms (preferably from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4, particularly preferably from 1 to 3), and particularly preferably a hydrogen atom or a methyl group, because the purification of the tetracarboxylic dianhydride is easy.

Examples of the tetracarboxylic dianhydride represented by formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride"), Methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-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''-tetra Carboxylic acid 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 acid dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid acid 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 (a-1) is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 10,000. By setting the amount within the above range, it is possible to obtain sufficient heat resistance and mechanical strength for a cured film formed using the photosensitive resin composition while obtaining good developability.

[Novolac resin (a-2)]
It is also preferable that the alkali-soluble resin (A) contains the novolak resin (a-2) from the viewpoint of easily forming a cured film that does not flow excessively when heated.
As the novolak resin (a-2), various novolak resins conventionally blended in photosensitive resin compositions can be used. As the novolac resin (a-2), those 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 are preferred.

(Phenols)
Phenols used for producing the novolak resin (a-2) include, for example, phenol; cresols such as o-cresol, m-cresol and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; Alkylphenols such as propylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglicinol; (all alkyl groups have from 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 having excellent heat resistance.
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 novolac resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(acid catalyst)
The acid catalyst used in producing the novolak resin (a-2) includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and p-toluenesulfonic 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 novolak resin (a-2) is preferably 2000 as a lower limit, more preferably 5000, particularly preferably 10000, further preferably 15000, most preferably 20000, and more preferably 50000 as an upper limit, and more preferably 45000 as an upper limit, from the viewpoint of heat resistance of a cured film formed using a photosensitive resin composition. 0000 is more preferred and 35000 is most preferred.

As the novolac resin (a-2), at least two kinds of resins having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of different weight average molecular weights, the developability of the photosensitive resin composition and the heat resistance of the cured film formed using the photosensitive resin composition can be balanced.

[Modified epoxy resin (a-3)]
The alkali-soluble resin (A) may contain a polybasic acid anhydride (a-3c) adduct (a-3) of a reaction product of an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b). Such an adduct is also referred to as "modified epoxy resin (a-3)".
In the specification and claims of the present application, a compound that corresponds to the above definition and does not correspond to the resin (a-1) having a cardo structure is referred to as a modified epoxy resin (a-3).

The epoxy compound (a-3a), unsaturated group-containing carboxylic acid (a-3b), and polybasic acid anhydride (a-3c) are described below.

<Epoxy compound (a-3a)>
The epoxy compound (a-3a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound containing no aromatic group, preferably an aromatic epoxy compound having an aromatic group.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a polyfunctional epoxy compound having a functionality of two or more, and is preferably a polyfunctional epoxy compound.

Specific examples of the epoxy compound (a-3a) include bifunctional epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AD-type epoxy resin, naphthalene-type epoxy resin, and biphenyl-type epoxy resin; glycidyl ester-type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidylamine-type epoxy resins such as aminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglycinol triglycidyl ether, trihydroxybiphenyltriglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1 , 3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; mentioned.

As the epoxy compound (a-3a), an epoxy compound having a biphenyl skeleton is preferable.
The epoxy compound having a biphenyl skeleton preferably has at least one biphenyl skeleton represented by the following formula (a-3a-1) in its main chain.
The epoxy compound having a biphenyl skeleton is preferably a polyfunctional epoxy compound having two or more epoxy groups.
By using an epoxy compound having a biphenyl skeleton, it is easy to obtain a resin composition which is excellent in balance between sensitivity and developability and capable of forming a cured film having excellent adhesion to a substrate.

（式（ａ－３ａ－１）中、Ｒ^ａ７は、それぞれ独立に、水素原子、炭素原子数１以上１２以下のアルキル基、ハロゲン原子、又は置換基を有してもよいフェニル基であり、ｊは１以上４以下の整数である。）

(In formula (a-3a-1), each R ^a7 is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group, and j is an integer of 1 to 4.)

When R ^a7 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group and sec-octyl group. Chill, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl groups.

When R ^a7 is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When R ^a7 is an optionally substituted phenyl group, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1.
Examples of substituents include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aliphatic acyl groups having 2 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups.

（式（ａ－３ａ－２）中、Ｒ^ａ７及びｊは、式（ａ－３ａ－１）と同様であり、ｋは括弧内の構成単位の平均繰り返し数であって０以上１０以下である。） The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (a-3a-2).

(In formula (a-3a-2), R ^a7 and j are the same as in formula (a-3a-1), and k is the average number of repetitions of the constituent units in parentheses and is 0 or more and 10 or less.)

（式（ａ－３ａ－３）中、ｋは、式（ａ－３ａ－２）と同様である。） Among the epoxy compounds represented by the formula (a-3a-2), compounds represented by the following formula (a-3a-3) are preferable because they are particularly easy to obtain a photosensitive resin composition having an excellent balance between sensitivity and developability.

(In formula (a-3a-3), k is the same as in formula (a-3a-2).)

(Unsaturated group-containing carboxylic acid (a-3b))
In preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) is reacted with the unsaturated group-containing carboxylic acid (a-3b).
The unsaturated group-containing carboxylic acid (a-3b) is preferably a monocarboxylic acid containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, α-cyanocinnamic acid, and cinnamic acid. Also, the unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more.

The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferred reaction method, for example, an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid (a-3b) are reacted in an organic solvent at a reaction temperature of 50° C. or higher and 150° C. or higher for several hours or more and several tens of hours or less using a tertiary amine such as triethylamine or benzylethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, or triphenylphosphine. mentioned.

In the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), the ratio of the amounts of both used in the reaction is generally preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, particularly preferably 1:0.9 to 1:1.1, as the ratio of the epoxy equivalent of the epoxy compound (a-3a) to the carboxylic acid equivalent of the unsaturated group-containing carboxylic acid (a-3b).
When the ratio of the amount of the epoxy compound (a-3a) used to the amount of the unsaturated group-containing carboxylic acid (a-3b) used is 1:0.5 to 1:2 in terms of the above equivalent ratio, the crosslinking efficiency tends to improve, which is preferable.

(Polybasic acid anhydride (a-3c))
Polybasic acid anhydrides (a-3c) are anhydrides of carboxylic acids having two or more carboxyl groups.
The polybasic acid anhydride (a-3c) is not particularly limited, but for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydro Phthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, a compound represented by the following formula (a-3c-1), and a compound represented by the following formula (a-3c-2). Also, the polybasic acid anhydride (a-3c) may be used alone or in combination of two or more.

（式（ａ－３ｃ－２）中、Ｒ^ａ８は、炭素原子数１以上１０以下の置換基を有してもよいアルキレン基を示す。）

(In formula (a-3c-2), R ^a8 represents an optionally substituted alkylene group having 1 to 10 carbon atoms.)

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings, since a photosensitive resin composition having an excellent balance between sensitivity and developability can be easily obtained. Further, the polybasic acid anhydride (a-3c) more preferably contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2).

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.
The ratio of the amount used is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2, in terms of the number of moles of OH groups in the component after the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) and the acid anhydride group of the polybasic acid anhydride (a-3c). By setting it as the said range, it is easy to obtain the photosensitive resin composition with favorable developability.

The acid value of the modified epoxy resin (a-3) is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 110 mgKOH/g or less, in terms of resin solid content. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility in a developer can be obtained, and by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained and surface properties can be improved.

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1000 or more and 40000 or less, more preferably 2000 or more and 30000 or less. When the weight average molecular weight is 1000 or more, it is easy to form a cured film having excellent heat resistance and strength. Moreover, when it is 40,000 or less, it is easy to obtain a photosensitive resin composition exhibiting sufficient solubility in a developer.

[Acrylic resin (a-4)]
The acrylic resin (a-4) is also preferred as a component constituting the alkali-soluble resin (A).
As the acrylic resin (a-4), those 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 represented by the following formula (a-4-1) and is not particularly limited as long as it does not interfere with the object of the present invention.

In formula (a-4-1) above, R ^a9 is a hydrogen atom or a methyl group, and R ^a10 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.

Ｒ ^ａ１０の有機基中の炭化水素基以外の置換基としては、本発明の効果が損なわれない限り特に限定されず、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シアノ基、イソシアノ基、シアナト基、イソシアナト基、チオシアナト基、イソチオシアナト基、シリル基、シラノール基、アルコキシ基、アルコキシカルボニル基、カルバモイル基、チオカルバモイル基、ニトロ基、ニトロソ基、カルボキシ基、カルボキシラート基、アシル基、アシルオキシ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、ヒドロキシイミノ基、アルキルエーテル基、アルキルチオエーテル基、アリールエーテル基、アリールチオエーテル基、アミノ基（－ＮＨ _２ 、－ＮＨＲ、－ＮＲＲ'：Ｒ及びＲ'はそれぞれ独立に炭化水素基を示す）等が挙げられる。 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.

Moreover, the organic group as R ^a10 may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, or an oxetanyl group.
An acyl group having an unsaturated double bond such as an acryloyloxy group or a methacryloyloxy group can be produced, for example, by reacting at least part of the epoxy group in the acrylic resin (a-4) containing a structural unit having an epoxy group with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

R ^a10 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, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isonyl, Nyl group, n-decyl group, isodecyl group and the like can be mentioned.

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 cyclopentyl group and cyclohexyl group, and polycyclic alicyclic groups such as adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group and tetracyclododecyl group.

Specific examples of the compound represented by formula (a-4-1) when the compound represented by formula (a-4-1) has a chain group having an epoxy group as R ^a10 include (meth)acrylic acid epoxyalkyl esters such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate.

The compound represented by formula (a-4-1) may also be an alicyclic epoxy group-containing (meth)acrylic acid ester. The alicyclic group that constitutes the alicyclic epoxy group may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group etc. are mentioned as a polycyclic alicyclic group.

Specific examples of the case where the compound represented by formula (a-4-1) is an alicyclic epoxy group-containing (meth)acrylic acid ester include compounds represented by the following formulas (a-4-1a) to (a-4-1o). Among these, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferable, and compounds represented by the following formulas (a-4-1a) to (a-4-1c) are more preferable in order to achieve appropriate developability.

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^a22 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t represents an integer of 0 to 10. R ^a21 is preferably a linear or branched alkylene group such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group and hexamethylene group. R ^a22 is preferably, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, or -CH ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

Further, the acrylic resin (a-4) may be 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; allyloxyethanol;

Vinyl ethers include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl aryl ether such as ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, 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 methoxyacetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; Halostyrenes such as styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene;

The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the acrylic resin (a-4) are not particularly limited as long as they do not hinder the object of the present invention. The amount of structural units derived from (meth)acrylic acid in the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less, relative to the mass of the acrylic resin (a-4).

When the acrylic resin (a-4) has a structural unit having an unsaturated double bond, the amount of the structural unit having an unsaturated double bond in the acrylic resin (a-4) is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or more, and particularly preferably 1% by mass or more and 20% by mass or less.
When the acrylic resin (a-4) contains a structural unit having an unsaturated double bond in an amount within the above range, the acrylic resin can be incorporated into the cross-linking reaction in the resist film to make it uniform, which is effective in improving the heat resistance and mechanical properties of the column spacer.

The weight average molecular weight of the acrylic resin (a-4) is preferably 2000 or more and 50000 or less, more preferably 3000 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.

The content of the alkali-soluble resin (A) is preferably 20% by mass or more and 85% by mass or less, more preferably 25% by mass or more and 75% by mass or less, relative to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later (total solid content). By setting it as said range, it is easy to obtain the photosensitive resin composition which is excellent in developability.

<Photopolymerizable Monomer (B)>
As the photopolymerizable monomer (B), a monomer having an ethylenically unsaturated group can be preferably used. The monomers having ethylenically unsaturated groups include monofunctional monomers and polyfunctional monomers.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride. , crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(meth) acryloyloxy-2-hydroxypropyl phthalate rate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative half (meth) acrylate, and the like. These monofunctional monomers can be used singly or in combination of two or more.

On the other hand, polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene 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-hexaneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol). Thritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, 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, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (that is, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate or the like and 2-hydroxyethyl (meth) acrylate), Examples include polyfunctional monomers such as methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensates of polyhydric alcohols and N-methylol(meth)acrylamide, and triacrylformal. These polyfunctional monomers can be used singly or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, trifunctional or higher polyfunctional monomers are preferable, tetrafunctional or higher polyfunctional monomers are more preferred, and pentafunctional or higher polyfunctional monomers are further preferred, from the viewpoint of increasing the adhesion of the photosensitive resin composition to the substrate and the strength of the photosensitive resin composition after curing.

The content of the photopolymerizable monomer (B) in the photosensitive resin composition is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, relative to the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described later (total solid content). By setting the amount within the above range, there is a tendency that sensitivity, developability, and resolution are easily balanced.

<Photoinitiator (C)>
The photosensitive resin composition includes a photopolymerization initiator (C-I) represented by the following formula (C1) as a photopolymerization initiator (C), and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I). The mass ratio of the photopolymerization initiator (CI) to the mass of the photopolymerization initiator (C) is 20% by mass or more and 95% by mass or less.
As described above, the photosensitive resin composition contains a combination of the photopolymerization initiator (C-I) and the photopolymerization initiator (C-II) in an amount within the predetermined range described above, so that the photosensitive resin composition can be used to form a patterned cured film having excellent straightness and adhesion to the substrate, and having a good cross-sectional shape.
The mass ratio of the photopolymerization initiator (CI) to the mass of the photopolymerization initiator (C) is more preferably 25% by mass or more and 90% by mass or less, and further preferably 30% by mass or more and 85% by mass or less.

[Photopolymerization initiator (CI)]
The photopolymerization initiator (CI) is an oxime ester compound represented by the following formula (C1).

で表される構造において、芳香族環上に結合する水素原子のうち、ｔ２＋ｔ３個の水素原子を除いた基である。Ｘ^０２及びＸ^０３は、それぞれ独立に１価の有機基である。Ｘ^０４及びＸ^０５は、それぞれ独立に水素原子、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る。ｔ０～ｔ３は、それぞれ独立に、０又は１である。ｔ２及びｔ３の少なくとも一方は１である。
式（Ｃ１－１）中、Ｘ^０６は、カルバゾール環中の窒素原子にＣ－Ｎ結合で結合する１価の有機基である。ｔ４及びｔ５は、それぞれ独立に０又は１であり、ｔ４及びｔ５の少なくとも一方は１である。 In formula (C1), X ⁰¹ is the following formula (C1-1):

In the structure represented by , it is a group obtained by removing t2+t3 hydrogen atoms from the hydrogen atoms bonded to the aromatic ring. X ⁰² and X ⁰³ are each independently a monovalent organic group. X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. t0 to t3 are each independently 0 or 1; At least one of t2 and t3 is 1.
In formula (C1-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring via a CN bond. t4 and t5 are each independently 0 or 1, and at least one of t4 and t5 is 1;

In formula (C1-1), X ⁰⁶ is a monovalent organic group bonded to the nitrogen atom in the carbazole ring via a CN bond. The monovalent organic group may contain heteroatoms such as O, S, N, P, Si, and halogen atoms. The number of carbon atoms in the organic group as X ⁰⁶ is not particularly limited. The number of carbon atoms in the organic group as X ⁰⁶ is, for example, preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and particularly preferably 1 or more and 20 or less.

Preferred examples of organic groups as X ⁰⁶ include alkyl groups, alkenyl groups, alkynyl groups, aliphatic cyclic hydrocarbon groups, aryl groups, aliphatic heterocyclic groups, heteroaryl groups, aliphatic acyl groups, aromatic acyl groups, and combinations of these groups. Preferred examples of combinations of these groups include aralkyl groups and cycloalkylalkyl groups.

When the organic group as X ⁰⁶ is an alkyl group, alkenyl group, or alkynyl group, these groups may be linear or branched. When the organic group as X ⁰⁶ is an aliphatic acyl group, the portion other than the carbonyl group in the aliphatic acyl group may be linear, branched, cyclic, or a combination of these structures.

The organic group as X ⁰⁶ may have a substituent. Ｘ ^０６としての有機基が有していてもよい置換基の例としては、炭素原子数１以上２０以下のアルキル基、炭素原子数１以上２０以下のアルコキシ基、炭素原子数３以上１０以下のシクロアルキル基、炭素原子数３以上１０以下のシクロアルコキシ基、炭素原子数２以上２０以下の飽和脂肪族アシル基、炭素原子数２以上２０以下のアルコキシカルボニル基、炭素原子数２以上２０以下の飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいフェニルチオ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよい炭素原子数７以上２０以下のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよい炭素原子数１１以上２０以下のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、アミノ基、１、又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基、ハロゲン、ニトロ基、及びシアノ基等が挙げられる。

Among the above groups for X ⁰⁶ , an alkyl group, an aryl group, and an aralkyl group are preferred in view of the ease of synthesis and availability of the photopolymerization initiator (C-I).

X⁰⁶is an alkyl group, specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n- Examples include undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups.

Preferred examples of X ⁰⁶ being an aryl group include a phenyl group, naphthalen-1-yl group, naphthalen-2-yl group, 2-phenylphenyl group, 3-phenylphenyl group and 4-phenylphenyl group.

Preferred examples of X ⁰⁶ being an aralkyl group include benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, naphthalen-1-ylmethyl and naphthalen-2-ylmethyl groups.

Among the specific examples of X ⁰⁶ explained above, a methyl group, an ethyl group, a phenyl group, a naphthalen-1-yl group and a naphthalen-2-yl group are preferable, and an ethyl group and a phenyl group are more preferable.

X ⁰¹ is not particularly limited as long as it is a group obtained by removing t2+t3 hydrogen atoms among the hydrogen atoms bonded to the aromatic ring in the structure represented by the above formula (C1-1). As the group represented by the above formula (C1-1), monovalent or divalent groups represented by the following formulas (C1-1a) to (C1-1c) are preferable.

In formulas (C1-1a) to (C1-c), t4, t5 and ^X06 are the same as in formula (C1-1). X ⁰⁷ is a divalent organic group attached to the nitrogen atom in the carbazole ring via a C—N bond. X ⁰⁷ is a divalent organic group containing an aromatic ring. Of the two bonds that X ⁰⁷ has, the other of the bonds that bond to the carbazole ring in formulas (C1-1a) and (C1-1c) bonds to the aromatic ring in X ⁰⁷ .
X ⁰⁷ corresponds to a divalent group obtained by removing one hydrogen atom bonded to the aromatic ring from the above-mentioned monovalent organic group containing an aromatic ring as X ⁰⁶ .

Taking formula (C1-1a) as an example, preferable specific examples of X ⁰⁷ are described below. A divalent group corresponding to X ⁰⁷ in the structure below is also preferred as X ⁰⁷ in formula (C1-1c).

In formulas (C1-1a) to (C1-1c), the bonding position of the nitro group on the carbazole ring is not particularly limited.
Preferred examples of the group represented by the formula (C1-1a), the group represented by the formula (C1-1b), and the group represented by the formula (C1-1c) include a group represented by the formula (C1-1aa), a group represented by the formula (C1-1ba), and a group represented by the formula (C1-1ca), respectively, because the compound represented by the formula (C1) is easily synthesized and available.

In formula (C1), X ⁰² and X ⁰³ are each independently a monovalent organic group. Ｘ ^０２及びＸ ^０３のとしての好適な有機基の例としては、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、アルコキシカルボニル基、飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、１、又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基等が挙げられる。

When X ⁰² and X ⁰³ are alkyl groups, 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. Moreover, when X ⁰² and X ⁰³ are alkyl groups, they may be linear or branched. Specific examples of X ⁰² and X ⁰³ being alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 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-o cyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group and the like. In addition, when X ⁰² and X ⁰³ 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 X ⁰² and X ⁰³ are alkoxy groups, 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. Moreover, when X ⁰² and X ⁰³ are alkoxy groups, they may be linear or branched. Ｘ ^０２及びＸ ^０３がアルコキシ基である場合の具体例としては、メトキシ基、エトキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、イソブチルオキシ基、ｓｅｃ－ブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ｓｅｃ－ペンチルオキシ基、ｔｅｒｔ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、ｎ－ヘプチルオキシ基、ｎ－オクチルオキシ基、イソオクチルオキシ基、ｓｅｃ－オクチルオキシ基、ｔｅｒｔ－オクチルオキシ基、ｎ－ノニルオキシ基、イソノニルオキシ基、ｎ－デシルオキシ基、及びイソデシルオキシ基等が挙げられる。 Moreover, when X ⁰² and X ⁰³ are alkoxy groups, the alkoxy groups 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 X ⁰² and X ⁰³ are 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. Specific examples of X ⁰² and X ⁰³ being cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Specific examples of X ⁰² and X ⁰³ being cycloalkoxy groups include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy groups.

When X ⁰² and X ⁰³ are saturated aliphatic acyl groups or saturated aliphatic acyloxy groups, the number of carbon atoms in the saturated aliphatic acyl groups or saturated aliphatic acyloxy groups is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples of when R ^c7 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group and n-tridecanyl group. Noyl group, n-tetradecanoyl group, n-pentadecanoyl group, n-hexadecanoyl group and the like. Ｘ ^０２及びＸ ^０３が飽和脂肪族アシルオキシ基である場合の具体例としては、アセチルオキシ基、プロパノイルオキシ基、ｎ－ブタノイルオキシ基、２－メチルプロパノイルオキシ基、ｎ－ペンタノイルオキシ基、２，２－ジメチルプロパノイルオキシ基、ｎ－ヘキサノイルオキシ基、ｎ－ヘプタノイルオキシ基、ｎ－オクタノイルオキシ基、ｎ－ノナノイルオキシ基、ｎ－デカノイルオキシ基、ｎ－ウンデカノイルオキシ基、ｎ－ドデカノイルオキシ基、ｎ－トリデカノイルオキシ基、ｎ－テトラデカノイルオキシ基、ｎ－ペンタデカノイルオキシ基、及びｎ－ヘキサデカノイルオキシ基等が挙げられる。

When X ⁰² and X ⁰³ are alkoxycarbonyl groups, 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. Ｘ ^０２及びＸ ^０３がアルコキシカルボニル基である場合の具体例としては、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ｎ－ブチルオキシカルボニル基、イソブチルオキシカルボニル基、ｓｅｃ－ブチルオキシカルボニル基、ｔｅｒｔ－ブチルオキシカルボニル基、ｎ－ペンチルオキシカルボニル基、イソペンチルオキシカルボニル基、ｓｅｃ－ペンチルオキシカルボニル基、ｔｅｒｔ－ペンチルオキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、ｎ－ヘプチルオキシカルボニル基、ｎ－オクチルオキシカルボニル基、イソオクチルオキシカルボニル基、ｓｅｃ－オクチルオキシカルボニル基、ｔｅｒｔ－オクチルオキシカルボニル基、ｎ－ノニルオキシカルボニル基、イソノニルオキシカルボニル基、ｎ－デシルオキシカルボニル基、及びイソデシルオキシカルボニル基等が挙げられる。

When X ⁰² and X ⁰³ are phenylalkyl groups, 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 X ⁰² and X ⁰³ are naphthylalkyl groups, 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 X ⁰² and X ⁰³ being phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl groups. Specific examples of when X ⁰² and X ⁰³ are naphthylalkyl groups include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group and 2-(β-naphthyl)ethyl group. When X ⁰² and X ⁰³ are a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or naphthyl group.

When X ⁰² and X ⁰³ are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more of N, S, and O, or a heterocyclyl group in which such monocyclic rings are condensed with each other or such monocyclic rings and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the condensed ring may have up to 3 monocyclic 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, tetrahydrofuran and the like. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When X ⁰² and X ⁰³ are a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when X ⁰² and X ⁰³ are a heterocyclyl group.

Ｘ ^０２及びＸ ^０３が１又は２の有機基で置換されたアミノ基である場合、有機基の好適な例は、炭素原子数１以上２０以下のアルキル基、炭素原子数３以上１０以下のシクロアルキル基、炭素原子数２以上２１以下の飽和脂肪族アシル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよい炭素原子数７以上２０以下のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよい炭素原子数１１以上２０以下のナフチルアルキル基、及びヘテロシクリル基等が挙げられる。 Specific examples of these suitable organic groups are the same as X ⁰² and X ⁰³ . 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 and acetylamino group. amino 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, and β-naphthoylamino group.

X⁰²and X⁰³Examples of substituents when the phenyl group, naphthyl group, and heterocyclyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and a monoalkylamino group having 1 to 6 carbon atoms. A dialkylamino group having an alkyl group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like can be mentioned.

When these substituents are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, an ether bond (- O-) may be included.

When the phenyl group, naphthyl group, and heterocyclyl group contained in X ⁰² and X ⁰³ 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 X ⁰² and X ⁰³ have multiple substituents, the multiple substituents may be the same or different.

X ⁰² and X ⁰³ are 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 as described above as the substituents that the phenyl group may have.

Among the organic groups, X ⁰² and X ⁰³ are preferably an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or an optionally substituted phenylthioalkyl group on the aromatic ring. 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. 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 X ⁰² and X ⁰³ , a group represented by -A ¹ -CO-OA ² is also preferable. A ¹ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. ^A2 is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ¹ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ¹ 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 ² include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Preferred specific examples of ^A4 include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, and β-naphthylmethyl group.

-A¹-CO-OA²Preferable specific examples of the group represented by, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 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 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（Ｃ１ａ）及び（Ｃ１ｂ）中、Ｘ^０８及びＸ^０９はそれぞれ有機基である。ｔ６は０以上４以下の整数である。Ｘ^０８及びＸ^０９がベンゼン環上の隣接する位置に存在する場合、Ｘ^０８及びＸ^０９が互いに結合して環を形成してもよい。ｔ７は１以上８以下の整数である。ｔ８は１以上５以下の整数である。ｔ９は０以上（ｔ８＋３）以下の整数である。Ｘ^０１０は有機基である。 X ⁰² and X ⁰³ have been described above, and X ⁰² and X ⁰³ are preferably groups represented by the following formula (C1a) or (C1b).

In formulas (C1a) and (C1b), X ⁰⁸ and X ⁰⁹ are each organic groups. t6 is an integer of 0 or more and 4 or less. When X ⁰⁸ and X ⁰⁹ are present at adjacent positions on the benzene ring, X ⁰⁸ and X ⁰⁹ may combine with each other to form a ring. t7 is an integer of 1 or more and 8 or less. t8 is an integer of 1 or more and 5 or less. t9 is an integer from 0 to (t8+3). X ⁰¹⁰ is an organic group.

Examples of organic groups for X ⁰⁸ and X ⁰⁹ in formula (C1a) are the same as for X ⁰² and X ⁰³ . X ⁰⁸ is preferably an alkyl group or a phenyl group. When X ⁰⁸ 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. Thus, X ⁰⁸ is most preferably a methyl group. When X ⁰⁸ and X ⁰⁹ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by formula (C1a) in which X ⁰⁸ and X ⁰⁹ form a ring include naphthalen-1-yl group and 1,2,3,4-tetrahydronaphthalen-5-yl group. In the above formula (C1a), t6 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In formula (C1b) above, X ⁰¹⁰ is an organic group. Examples of the organic group include groups similar to the organic groups described for X ⁰² and X ⁰³ . 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. X ⁰¹⁰ 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 formula (C1b), t8 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 formula (C1b), t9 is 0 or more and (t8+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 formula (C1b), t7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (C1), X ⁰⁴ and X ⁰⁵ are each independently 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 substituents which may be possessed when X ⁰⁴ and X ⁰⁵ are alkyl groups. In addition, when X ⁰⁴ and X ⁰⁵ are aryl groups, the substituents which may be present are preferably exemplified by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom.

In formula (C1), X ⁰⁴ and X ⁰⁵ are 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, etc. Among these, a methyl group or a phenyl group is more preferable.

As described above, X ⁰¹ is preferably a group represented by formula (C1-1aa), a group represented by formula (C1-1ba), or a group represented by formula (C1-1ca).
Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1aa) include the following compounds.

Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1ba) include the following compounds.

Preferred specific examples of the oxime ester compound represented by formula (C1) when X ⁰¹ is a group represented by formula (C1-1ca) include the following compounds.

<Photoinitiator (C-II)>
The photosensitive resin composition contains, as the photopolymerization initiator (C), the photopolymerization initiator (C-II) described above and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I).
The other photopolymerization initiator (C-II) is not particularly limited as long as it is a photopolymerization initiator that does not correspond to the photopolymerization initiator (C-I).

Preferable examples of the photopolymerization initiator (C-II) include oxime ester compounds having a structure that does not correspond to the above formula (C1); )-2-diethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and other α-aminoketone compounds; 1-phenyl-2-hydroxy-2- α-hydroxyketone-based photopolymerization initiators such as methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl methyl ketal; benzophenone-based photopolymerization initiators such as methyl ylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4′-methyldiphenylsulfide, and 4,4′-bisdiethylaminobenzophenone; -phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl) )-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine, 2-[4-(4-methoxystyryl)phenyl]-4,6-bis(trichloromethyl)-1,3 , Triazine-based photopolymerization initiators such as 5-triazine; carbazole-based photopolymerization initiators; 2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl )-4,4,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole photopolymerization initiators; Benzimidazoline-based photopolymerization initiators such as those described above are exemplified.

The photosensitive resin composition preferably contains an oxime ester compound and/or an α-aminoketone-based compound as the photopolymerization initiator (C-II), and more preferably contains an oxime ester compound and an α-aminoketone-based compound in combination, since the desired effect can be easily obtained.

As the oxime ester compound as the photopolymerization initiator (C-II), an oxime ester compound represented by the following formula (C2) is particularly preferred.

のいずれか１つで表される基である。Ｒ^ｃ３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る。
式（Ｃ２－１）中、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る。ＡはＳ又はＯである。ｎ２は、０以上４以下の整数である。
式（Ｃ２－２）中、Ｒ^ｃ５及びＲ^ｃ６は、それぞれ独立に１価の有機基である。
式（Ｃ２－３）中、Ｒ^ｃ７は、水素原子、ニトロ基又は１価の有機基である。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、又は水素原子である。Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよい。ｎ３は０以上４以下の整数である。 In formula (C2), R ^c1 is a monovalent organic group. R ^c2 is represented by the following formulas (C2-1) to (C2-3):

is a group represented by any one of R ^c3 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group.
In formula (C2-1), R ^c4 is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups. A is S or O; n2 is an integer of 0 or more and 4 or less.
In formula (C2-2), R ^c5 and R ^c6 are each independently a monovalent organic group.
In formula (C2-3), 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 group, or a hydrogen atom. R ^c8 and R ^c9 may combine with each other to form a ring. n3 is an integer of 0 or more and 4 or less.

The monovalent organic group as R ^c1 in formula (C2) is the same as the monovalent organic group described above for X ⁰² and X ⁰³ in formula (C1).
The monovalent organic group as R ^c1 is preferably a group represented by the following formula (C2a) or (C2b).

In formulas (C2a) and (C2b), R ^c10 and R ^c11 are each a monovalent organic group. n4 is an integer of 0 or more and 4 or less. When R ^c10 and R ^c11 are present at adjacent positions on the benzene ring, R ^c10 and R ^c11 may combine with each other to form a ring. n5 is an integer of 1 or less and 8 or less. n6 is an integer of 1 or more and 5 or less. n7 is an integer of 0 or more and (n6+3) or less. R ^c12 is a monovalent organic group.

R ^c10 , R ^c11 and n4 in formula (C2a) are the same as X ⁰⁸ , X ⁰⁹ and t6 in formula (C1a) described above for formula (C1). R ^c12 , n5, n6, and n7 in formula (C2b) are the same as X ⁰¹⁰ , t7, t8, and t9 in formula (C1b) described above for formula (C1).

The group represented by formula (C2-1), the group represented by formula (C2-2), and the group represented by formula (C2-3) for R ^c2 will be described below.

The group represented by formula (C2-1) is a monovalent organic group having the following structure.

When R ^c4 in formula (C2-1) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired.式（Ｃ２－１）においてＲ ^ｃ４が有機基である場合の好適な例としては、炭素原子数１以上６以下のアルキル基；炭素原子数１以上６以下のアルコキシ基；炭素原子数２以上７以下の飽和脂肪族アシル基；炭素原子数２以上７以下のアルコキシカルボニル基；炭素原子数２以上７以下の飽和脂肪族アシルオキシ基；フェニル基；ナフチル基；ベンゾイル基；ナフトイル基；炭素原子数１以上６以下のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；炭素原子数１以上６以下のアルキル基を有するモノアルキルアミノ基；炭素原子数１以上６以下のアルキル基を有するジアルキルアミノ基；モルホリン－１－イル基；ピペラジン－１－イル基；ハロゲン；ニトロ基；シアノ基が挙げられる。

Among R ^c4 , a benzoyl group; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a nitro group is preferred; a benzoyl group; a naphthoyl group;

In formula (C2-1), n2 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 n2 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.

The group represented by formula (C2-2) is a monovalent organic group having the following structure.

R ^c5 in formula (C2-2) can be selected from various organic groups as long as the objects of the present invention are not impaired. Ｒ ^ｃ５の好適な例としては、炭素原子数１以上２０以下のアルキル基、炭素原子数３以上１０以下のシクロアルキル基、炭素原子数２以上２０以下の飽和脂肪族アシル基、炭素原子数２以上２０以下のアルコキシカルボニル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよい炭素原子数７以上２０以下のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよい炭素原子数１１以上２０以下のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び置換基を有してもよいヘテロシクリルカルボニル基等が挙げられる。

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 (C2-2) 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 an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclyl group. As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

Ｒ ^ｃ５ 、又はＲ ^ｃ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基がさらに置換基を有する場合の置換基としては、炭素原子数１以上６以下のアルキル基、炭素原子数１以上６以下のアルコキシ基、炭素原子数２以上７以下の飽和脂肪族アシル基、炭素原子数２以上７以下のアルコキシカルボニル基、炭素原子数２以上７以下の飽和脂肪族アシルオキシ基、炭素原子数１以上６以下のアルキル基を有するモノアルキルアミノ基、炭素原子数１以上６以下のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン、ニトロ基、及びシアノ基等が挙げられる。 When the phenyl group, naphthyl group, and heterocyclyl group contained in 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, but is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c5 or R ^c6 have multiple substituents, the multiple substituents may be the same or different.

The group represented by formula (C2-3) is a monovalent organic group having the following structure.

In formula (C2-3), 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 group, or a hydrogen atom. R ^c8 and R ^c9 may combine with each other to form a ring. n3 is an integer of 0 or more and 4 or less.

In formula (C2-3), R ^c7 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) _n1 — on the fluorene ring in formula (C2-3). In formula (C2-3), the bonding position of R ^c7 to the fluorene ring is not particularly limited. When the compound represented by the formula (C2-3) has one or more R ^c7 , one of the one or more R ^c7 is preferably bound to the 2-position in the fluorene ring, because the compound represented by the formula (C2-3) is easy to synthesize. 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. Ｒ ^ｃ７が有機基である場合の好適な例としては、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、飽和脂肪族アシルオキシ基、アルコキシカルボニル基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、１、又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基等が挙げられる。

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, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n -nonyl group, isononyl group, n-decyl group, isodecyl group and the like. Further, 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. In addition, 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, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, se c-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. 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. Specific examples of R ^c7 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 ^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 when R ^c7 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group and n-tridecanyl group. Noyl group, n-tetradecanoyl group, n-pentadecanoyl group, n-hexadecanoyl group and the like. Ｒ ^ｃ７が飽和脂肪族アシルオキシ基である場合の具体例としては、アセチルオキシ基、プロパノイルオキシ基、ｎ－ブタノイルオキシ基、２－メチルプロパノイルオキシ基、ｎ－ペンタノイルオキシ基、２，２－ジメチルプロパノイルオキシ基、ｎ－ヘキサノイルオキシ基、ｎ－ヘプタノイルオキシ基、ｎ－オクタノイルオキシ基、ｎ－ノナノイルオキシ基、ｎ－デカノイルオキシ基、ｎ－ウンデカノイルオキシ基、ｎ－ドデカノイルオキシ基、ｎ－トリデカノイルオキシ基、ｎ－テトラデカノイルオキシ基、ｎ－ペンタデカノイルオキシ基、及びｎ－ヘキサデカノイルオキシ基等が挙げられる。

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. Ｒ ^ｃ７がアルコキシカルボニル基である場合の具体例としては、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ｎ－ブチルオキシカルボニル基、イソブチルオキシカルボニル基、ｓｅｃ－ブチルオキシカルボニル基、ｔｅｒｔ－ブチルオキシカルボニル基、ｎ－ペンチルオキシカルボニル基、イソペンチルオキシカルボニル基、ｓｅｃ－ペンチルオキシカルボニル基、ｔｅｒｔ－ペンチルオキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、ｎ－ヘプチルオキシカルボニル基、ｎ－オクチルオキシカルボニル基、イソオクチルオキシカルボニル基、ｓｅｃ－オクチルオキシカルボニル基、ｔｅｒｔ－オクチルオキシカルボニル基、ｎ－ノニルオキシカルボニル基、イソノニルオキシカルボニル基、ｎ－デシルオキシカルボニル基、及びイソデシルオキシカルボニル基等が挙げられる。

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 R ^c7 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 ^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 a heterocyclyl group in which such monocyclic rings are fused together or such monocyclic rings and a benzene ring are condensed. 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, tetrahydrofuran and the like. 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.

Ｒ ^ｃ７が１又は２の有機基で置換されたアミノ基である場合、有機基の好適な例は、炭素原子数１以上２０以下のアルキル基、炭素原子数３以上１０以下のシクロアルキル基、炭素原子数２以上２１以下の飽和脂肪族アシル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよい炭素原子数７以上２０以下のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよい炭素原子数１１以上２０以下のナフチルアルキル基、及びヘテロシクリル基等が挙げられる。 Specific examples of these suitable organic groups are the same as for 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 and acetylamino group. amino 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, and β-naphthoylamino group.

Ｒ ^ｃ７に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基がさらに置換基を有する場合の置換基としては、炭素原子数１以上６以下のアルキル基、炭素原子数１以上６以下のアルコキシ基、炭素原子数２以上７以下の飽和脂肪族アシル基、炭素原子数２以上７以下のアルコキシカルボニル基、炭素原子数２以上７以下の飽和脂肪族アシルオキシ基、炭素原子数１以上６以下のアルキル基を有するモノアルキルアミノ基、炭素原子数１以上６以下のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン、ニトロ基、及びシアノ基等が挙げられる。 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 an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclyl group. Among these groups, 2-methylphenyl group, thiophen-2-yl group and α-naphthyl group are particularly preferred as R ^c12 .

In formula (C2-3), 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 preferably 1 or more and 6 or less. Specific examples of R ^c8 and R ^c9 being chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, and tert. -octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group and the like. 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 substituted chain alkyl groups, the chain alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. 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 preferably a phenyl group, a group formed by combining multiple benzene rings via carbon-carbon bonds, or a group formed by condensing multiple benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. 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, tetracyclododecyl, and adamantyl groups.

When R ^c8 and R ^c9 are a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more of N, S, and O, or a heterocyclyl group in which such monocyclic rings are condensed with each other or such a monocyclic ring and a benzene ring are condensed. 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, tetrahydrofuran and the like.

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 the ring optionally condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine ring, pyrazine ring, and pyrimidine ring.

Examples of preferred groups among R ^c8 and R ^c9 described above include groups represented by the formula -A ⁰¹ -A ⁰² . In the formula, A ⁰¹ is a linear alkylene group, and A ⁰² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in the linear alkylene group of A ⁰¹ is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² 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 A ⁰² 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 A ⁰² 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 A ⁰² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^c8 and R ^c9 have as substituents. When A ⁰² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R ^c8 and R ^c9 have as substituents.

R.^c8and R^c9Preferred specific examples of are alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; , 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7-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- cyanoalkyl groups such as n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; hexyl-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; , 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group and alkoxycarbonylalkyl groups such as 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 3,3,4,4,5,5,5 Examples thereof include halogenated alkyl groups such as -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-heptafluoro-n-pentyl group. is.

Among the oxime ester compounds represented by formula (C2), compounds in which R ^c1 is a group represented by formula (C2a), R ^c10 is a methyl group, and R ^c2 is a group represented by formula (C2-1) are preferred. Such an oxime ester compound is specifically a compound represented by the following formula (C2-I).

In formula (C2-I), R ^c3 is the same as R ^c3 in formula (C2). In formula (C2-II), R ^c4 , A and n2 are the same as R ^c4 , A and n2 in formula (C2-1). In formula (C2-I), R ^c11 and n4 are the same as R ^c11 and n4 in formula (C2a).

Among the oxime ester compounds represented by formula (C2), compounds in which R ^c3 is represented by formula (C2-3) are also preferable. Such an oxime ester compound is specifically a compound represented by the following formula (C2-II).

In formula (C2-II), R ^c1 and R ^c3 are the same as R ^c1 and R ^c3 in formula (C2). In formula (C2-II), R ^c7 and R ^c are the same as R ^c1 and R ^c3 in formula (C2).

Preferable specific examples of the oxime ester compound represented by formula (C2-I) include the following compounds.

Preferable specific examples of the oxime ester compound represented by formula (C2-II) include the following compounds.

The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, relative to the total mass of the solid content of the photosensitive resin composition. By setting the content of the photopolymerization initiator (C) within the above range, it is possible to obtain a photosensitive resin composition that has good curability and is less likely to cause defects in pattern shape.

As described above, the photosensitive resin composition contains a photopolymerization initiator (C-I) represented by the following formula (C1) as a photopolymerization initiator (C), and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I). The mass ratio of the photopolymerization initiator (C-I) in the mass of the photopolymerization initiator (C) is 20% by mass or more and 95% by mass or less, more preferably 25% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 85% by mass or less.

When the photopolymerization initiator (C-II) contains an α-aminoketone compound, the ratio of the mass of the α-aminoketone compound to the mass of the photopolymerization initiator (C-II) is not particularly limited. When the photopolymerization initiator (C-II) contains an α-aminoketone compound, the mass ratio of the α-aminoketone compound in the mass of the photopolymerization initiator (C-II) is preferably 5% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and further preferably 20% by mass or more and 40% by mass or less.

When the photopolymerization initiator (C-II) contains an oxime ester compound other than the photopolymerization initiator (C-I) in combination with an α-aminoketone compound, the ratio of the total mass of the oxime ester compound and the α-aminoketone compound in the mass of the photopolymerization initiator (C-II) is not particularly limited. The total ratio of the mass of the oxime ester compound and the mass of the α-aminoketone compound in the mass of the photopolymerization initiator (C-II) is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

When the photopolymerization initiator (C-II) contains an oxime ester compound other than the photopolymerization initiator (C-I) in combination with an α-aminoketone compound, the mass of the oxime ester compound and the α-aminoketone compound. The ratio of the mass of the α-aminoketone compound to the total mass is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and particularly preferably 20% by mass or more and 40% by mass or less.

<Colorant (D)>
The photosensitive resin composition may further contain a coloring agent (D). Since the photosensitive resin composition contains the coloring agent (D), it is preferably used, for example, for forming a color filter for a liquid crystal display. Further, the photosensitive resin composition contains a light-shielding agent (D1) as a coloring agent (D), and is preferably used for forming a black matrix in a color filter of a display device, for example.

The coloring agent (D) contained in the photosensitive resin composition is not particularly limited, but for example, it is preferable to use compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colourists), specifically, those having the following Color Index (C.I.) numbers.

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, 10 4, 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, 1 75, 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.

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.) 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 , 114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,192,193,194,202,206,20 7, 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.

Moreover, when providing a light-shielding property to the photosensitive resin composition, it is preferable that the photosensitive resin composition contains a black pigment as a light-shielding agent (D1). A photosensitive resin composition containing a black pigment is suitably used to form a black matrix or black column spacer in a liquid crystal display panel, or to form a bank for partitioning a light-emitting layer in an organic EL device.

Examples of black pigments include carbon black, perylene-based pigments, lactam-based pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, metal oxides such as silver, composite oxides, metal sulfides, metal sulfates, metal carbonates, and various organic and inorganic pigments. Among these black pigments, carbon black is preferable because it is easily available and can easily form a cured film having excellent light-shielding properties and high electric resistance.
The hue of the black pigment is not limited to black, which is an achromatic color in color theory, and may be purplish black, bluish black, or reddish black.

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 of a liquid crystal display element such as a liquid crystal display, there is little current leakage, and a highly reliable and low power consumption display can be manufactured.

As the carbon black, carbon black that has been subjected to a treatment for introducing acidic groups is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity according to Bronsted's definition. Specific examples of acidic groups include a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like. The acidic groups introduced into carbon black may form a salt. The cation that forms a salt with an acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of cations include various metal ions, cations of nitrogen-containing compounds, ammonium ions, etc. Alkali metal ions such as sodium ions, potassium ions and lithium ions, and ammonium ions are preferred.

Among the carbon blacks that have been subjected to a treatment for introducing acidic groups as described above, carbon blacks having one or more functional groups selected from the group consisting of carboxylic acid groups, carboxylic acid groups, sulfonic acid groups, and sulfonic acid groups are preferable from the viewpoint of achieving high resistance of a light-shielding cured film formed using a photosensitive resin composition.

The method for introducing acidic groups into carbon black is not particularly limited. Examples of methods for introducing acidic groups include the following methods.
1) A method of introducing sulfonic acid groups into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using a sulfite, hydrogen sulfite, or the like.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protective group with carbon black having a hydroxyl group.
5) A method of subjecting carbon black to a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group, followed by deprotection.

Among these methods, method 2) is preferable because the treatment for introducing an acidic group is easy and safe. The organic compound having an amino group and an acidic group used in method 2) is preferably a compound in which an amino group and an acidic group are bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of acidic groups introduced into carbon black is preferably 1 mmol or more and 200 mmol or less, more preferably 5 mmol or more and 100 mmol or less, relative to 100 g of carbon black.

Carbon black into which acidic groups have been introduced may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. The coating treatment with the resin does not particularly affect the dielectric constant of the light-shielding cured film formed using the photosensitive resin composition. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallylphthalate resins, glyptal resins, epoxy resins, alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone. Thermoplastic resins such as Tong. The coating amount of the resin with respect to the carbon black is preferably 1% by mass or more and 30% by mass or less with respect to the total mass of the carbon black and the resin.

Perylene-based pigments can also be preferably used as black pigments. Specific examples of perylene pigments include perylene pigments represented by formula (d-1) below, perylene pigments represented by formula (d-2) below, and perylene pigments represented by formula (d-3) below. 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 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, and R ^d3 and R ^d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or 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 or an alkyl group having 1 to 22 carbon atoms, which may contain a heteroatom of N, O, S or P. 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) can be synthesized using the methods described in, for example, JP-A-62-1753 and 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 heating 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 perylene pigment well in the photosensitive resin composition, the average particle size of the perylene pigment is preferably 10 nm or more and 1000 nm or less.

A lactam-based pigment can also be included as a light-shielding agent. Examples of 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, R ^d9 is each independently a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, R ^d10 is each independently a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 is each independently 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 preferably bonded to the 4-position of the dihydroindolone ring, because the compound represented by formula (d-4) can be easily produced. 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, ZZ, and EZ isomers as geometric isomers, and may be any of these single compounds or a mixture of these geometric isomers.
The compound represented by formula (d-4) can be produced, for example, by the methods described in WO2000/24736 and WO2010/081624.

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

Furthermore, fine particles containing a silver-tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as black pigments. The AgSn alloy fine particles may contain AgSn alloy as a main component, and may contain other metal components such as Ni, Pd, and Au.
The average particle size of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x for obtaining a chemically stable AgSn alloy is 1 ≤ x ≤ 10, and the range of x for obtaining chemical stability and blackness at the same time is 3 ≤ x ≤ 4.
Here, when the mass ratio of Ag in the AgSn alloy is obtained within the above range of x,
Ag/AgSn=0.4762 when x=1
When x=3, 3Ag/Ag3Sn=0.7317
When x=4, 4·Ag/Ag4Sn=0.7843
When x=10, 10Ag/Ag10Sn=0.9008
becomes.
Therefore, this AgSn alloy becomes chemically stable when it contains 47.6% by mass or more and 90% by mass or less of Ag, and when it contains 73.17% by mass or more and 78.43% by mass or less of Ag, chemical stability and blackness can be effectively obtained with respect to the amount of Ag.

This AgSn alloy fine particle can be produced using a normal fine particle synthesis method. Examples of fine particle synthesis methods include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

Although the AgSn alloy fine particles have a high insulating property, depending on the application of the photosensitive resin composition, the surface thereof may be covered with an insulating film in order to further improve the insulating property. A metal oxide or an organic polymer compound is suitable as a material for such an insulating film.
As metal oxides, metal oxides having insulating properties such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), and the like are preferably used.
As the organic polymer compound, insulating resins such as polyimide, polyether, polyacrylate, and polyamine compounds are preferably used.

The film thickness of the insulating film is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, in order to sufficiently improve the surface insulation of the AgSn alloy fine particles.
The insulating film can be easily formed by surface modification technology or surface coating technology. In particular, use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform thickness can be formed at a relatively low temperature.

As the black pigment, the above-described perylene-based pigment, lactam-based pigment, and AgSn alloy fine particles may be used alone, or may be used in combination.
In addition, the black pigment may contain pigments of hues such as red, blue, green, and yellow for the purpose of adjusting color tone. Colorants having hues other than the black pigment can be appropriately selected from known colorants. For example, the various pigments described above can be used as dyes having hues other than the black pigment. The amount of the coloring matter having a hue other than the black pigment is preferably 15% by mass or less, more preferably 10% by mass or less, relative to the total mass of the black pigment.

A black composition containing a combination of two or more black or chromatic pigments and/or dyes can be used together with the black pigment described above or in place of the black pigment.
The content of carbon black in the black composition is preferably 3% by mass or less. By using a black composition having a carbon black content of 3% by mass or less, it is easy to suppress the generation of floating matter and development residues after development.
The content of carbon black in the black composition is more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0% by mass.

The hues of the pigments and dyes contained in the black composition are not particularly limited. The black composition may contain black pigments and/or dyes. The black composition may be a combination of multiple black colorants. In this case, as the black colorant, for example, perylene black, aniline black, black azo compound, and the like can be used.
The black composition may contain a combination of two or more pigments and/or dyes having hues other than black so that the composition exhibits a black color.

Since the black hue can be finely adjusted and the generation of floating matter and development residue after development can be easily suppressed, the black composition is preferably a combination of multiple types of chromatic colorants rather than a colorant consisting of a single type of colorant.

The black composition is preferably a combination of two or more organic pigments selected from, for example, five organic pigments of blue, purple, yellow, red, and orange.
By combining two or more organic pigments out of the above five organic pigments, a pseudo-blackened hue can be expressed. Here, "pseudo-black" is ideally chromatically black, but any hue that is acceptable in the application of a black film formed using a black composition is acceptable.

The ratio (mass ratio) of the organic pigments of each hue in the black composition exhibiting pseudo black is preferably (blue organic pigment) / (yellow organic pigment + orange organic pigment) / (red organic pigment + purple organic pigment) = (30% by mass or more and 60% by mass or less) / (0% by mass or more and 50% by mass or less) / (5% by mass or more and 70% by mass or less).

As the above five organic pigments, conventionally known ones can be used.
As a blue organic pigment, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, and C.I. I. Pigment Blue 60 may be mentioned.
As a purple organic pigment, C.I. I. Pigment Violet 19, and C.I. I. Pigment Violet 23 may be mentioned.
As a yellow organic pigment, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180, and C.I. I. Pigment Yellow 181 may be mentioned.
As an orange organic pigment, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 69, C.I. I. Pigment Orange 71, and C.I. I. Pigment Orange 73 may be mentioned.
As a red organic pigment, C.I. I. Pigment Red 122, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179, C.I. I. Pigment Red 242, C.I. I. Pigment Red 224, C.I. I. Pigment Red 254, C.I. I. Pigment Red 256, C.I. I. Pigment Red 264, and C.I. I. Pigment Red 272 may be mentioned.

Among them, the blue organic pigment is C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 15:6 is at least one selected from the group consisting of C.I. I. Pigment Violet 23 and the yellow organic pigment is C.I. I. Pigment Yellow 83 and/or C.I. I. Pigment Yellow 139, and the orange organic pigment is C.I. I. Pigment Orange 43 and/or C.I. I. Pigment Orange 64 and the red organic pigment is C.I. I. Pigment Red 254 and/or C.I. I. Pigment Red 256, is preferred.
By using these organic pigments in combination, it is easy to form a black cured film having a good black hue and excellent optical density (OD value).
be.

In order to obtain a pseudo-black black composition, it is preferable to combine at least one selected from blue organic pigments, yellow organic pigments, and orange organic pigments, and these organic pigments are more preferably combined with at least one organic pigment selected from red organic pigments and purple organic pigments.
Specific combinations of pigments belonging to organic pigments of each color include, for example,
・C. I. Pigment Blue 15:4 and C.I. I. Pigment Yellow 139 and C.I. I. Combination with Pigment Red 254,
・C. I. Pigment Blue 15:6 and C.I. I. Pigment Orange 64 and C.I. I. combination with Pigment Violet 23,
・C. I. Pigment Blue 15:4 or 15:3 and C.I. I. Pigment Yellow 83 and C.I. I. Pigment Violet 23 and C.I. I. in combination with Pigment Red 254, and
・C. I. Pigment Blue 15:6 and C.I. I. Pigment Violet 23 and C.I. I. A combination with Pigment Red 256 is preferred.

A dispersant may be further used to uniformly disperse the coloring agent (D) 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 (D), it is preferable to use an acrylic resin-based dispersant as the dispersant.
In some cases, corrosive gas originating from the dispersant is generated from the cured film. Therefore, it is also a preferred embodiment that the pigment is dispersed without using a dispersant.

In addition, in the photosensitive resin composition, a pigment and a dye may be used in combination. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the photosensitive resin composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
Further, these dyes can be dispersed in an organic solvent or the like by forming a lake (chlorination) and used as the colorant (D).
In addition to these dyes, for example, the dyes described in JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. can be preferably used.

The amount of the coloring agent (D) used in the photosensitive resin composition can be appropriately selected within a range that does not hinder the object of the present invention. Typically, the amount of the coloring agent (D) used is preferably 2% by mass or more and 75% by mass or less, more preferably 3% by mass or more and 70% by mass or less, relative to the total mass of the solid content of the photosensitive resin composition.

In particular, when forming a black matrix using a photosensitive resin composition, it is preferable to adjust the amount of the light shielding agent in the photosensitive resin composition so that the OD value per 1 μm of the black matrix film is 4 or more. If the OD value per 1 μm of film in the black matrix is 4 or more, sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display.

When a pigment is used as the colorant (D), the pigment is preferably dispersed in the presence or absence of a dispersant at an appropriate concentration to form a dispersion, and then added to the photosensitive resin composition.
In this specification, the amount of the pigment used can be defined as a value including the present dispersant.

<Sensitizer (E)>
The photosensitive resin composition may contain a sensitizer (E) together with the above photopolymerization initiator. Since the photosensitive resin composition contains the sensitizer (E), it can be cured satisfactorily even when using a light source with low irradiation energy such as LED exposure.

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

The sensitizer (E) is preferably 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). 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 a substituent other than an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O). Examples of such substituents include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, and an aromatic group having 7 to 11 carbon atoms. group acyl groups (aroyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, mercapto groups, 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, n-octyloxy, 2-ethylhexyl, n-nonyloxy, and n-decyloxy groups.

A substituted carbonyloxy group is a group represented by —O—CO—A ^e . A ^e is not particularly limited as long as the sensitizer (E) 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 the substituent include an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, 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.

When A ^e is an alkyl group or an alkoxy group, these groups may be linear or branched.
Suitable examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl groups.
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, n-hexyloxy, n-heptyloxy, n-octyloxy, and 2-ethylhexyloxy groups.

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.

Suitable 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 thioxanthene ring. Among these rings, anthracene ring, naphthacene ring and thioxanthene ring are preferred.

Specific examples of compounds containing an anthracene ring and suitable for use as the sensitizer (E) 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, and 9,10-bis(isobutylcarbonyloxy)anthracene. Cene, 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(isopropylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-methyl-9,10-bis(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 Cene, 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-methylbenzoyl) oxy)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-butyl carbonyloxy)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 -(tert-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy) ) anthracene, 1-(tert-butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 1-(t-butyl)-9,10-bis(4-(tert-butyl)-benzoyloxy)anthracene, 1-(tert-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-(tert- butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-(tert-butyl)-9,10-bis(benzoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(4-(t-butyl)-benzoyloxy)anthracene, 2-(tert-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-pentyl-9,10-bis (n-propylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2 -pentyl-9,10-bis(benzoyloxy)anthracene, 2-pentyl-9,10-bis(4-(tert-butyl)-benzoyloxy)anthracene, and 2-pentyl-9,10-bis(2-naphthoyloxy)anthracene.

Halogen-substituted anthracene compounds are also preferred as sensitizers (E). A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Specific examples of halogen-substituted anthracene compounds preferred as the sensitizer (E) 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 Cene, 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- xylcarbonyloxy)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-9,1 0-bis(benzoyloxy)anthracene, 1-bromo-9,10-bis(4-methylbenzoyloxy)anthracene, 1-bromo-9,10-bis(2-naphthoyloxy)anthracene and the like.

Anthracene compounds substituted with alkoxy groups are also preferred as sensitizers (E).
Specific examples of alkoxy-substituted anthracene compounds that are preferable as the sensitizer (E) 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, 9,1 0-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-hexyloxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy)anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,10-bis(n-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-9,1 0-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(isopentyloxy)anthracene, 2-bromo-9,10-bis(n-hexyloxy)anthracene, 2-bromo-9,10-bis(n-heptyloxy)anthracene, 2-bromo-9,10-bis(n-octyloxy)anthracene, 2-bromo-9,10-bis(2-ethylhexyloxy)anthracene, 2-chloro-9-methoxyanthracene, 2-chloro-9-ethoxyanthracene Cene, 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 thracene, 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, 2-bromo-9-(2-ethylhexyloxy)anthracene and the like.

Among the anthracene compounds described above, from the viewpoint of ease of production and performance as a sensitizer (E), Thracene, 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 sensitizer (E) 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 Xo-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-heptylbonyloxy)naphthacene and other alkylcarbonyloxy group-substituted naphthacene compounds;
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(α-naphthoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene and the like yloxy group-substituted naphthacene compound;
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 Cene, 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-pentyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-heptyloxycarbonyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6,12-bis(n-o alkoxycarbonyloxy group-substituted naphthacene compounds such as ctyloxycarbonyloxy)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-5,11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6, Examples thereof include aroyloxycarbonyloxy group-substituted naphthacene compounds such as 12-bis(β-naphthyloxycarbonyloxy)naphthacene.

Among the above compounds containing a naphthacene ring, 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-butylcarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)naphthacene and 5,11-dioxo-6,12-bis(n-heptanoyloxy)naphthacene are preferred.

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

The content of the sensitizer (E) is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 15 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the photopolymerization initiator (C) in the photosensitive resin composition. 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.

<Organic solvent (S)>
The photosensitive resin composition may typically contain an organic solvent (S) for the purpose of adjusting coatability. Examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono (Poly)alkylene glycol monoalkyl ethers such as methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; monoalkyl ether acetates; 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 and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Other esters such as n-propyl, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent (S) used can be appropriately determined according to the application of the photosensitive resin composition. As an example of the amount of the organic solvent (S) to be used, there is an amount such that the solid content concentration of the photosensitive resin composition is in the range of 1% by mass or more and 50% by mass or less.

<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 uniformly mixing desired amounts of each of the above components. 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 for producing patterned cured film>>
By using the photosensitive resin composition described above, it is possible to form a patterned cured film which is excellent in linearity and adhesion to a substrate, and which has a favorable cross-sectional shape.
Specifically, the above-described photosensitive resin composition is applied on a substrate to form a coating film;
position-selectively exposing the coating film;
developing the exposed coating film;
A patterned cured film is produced by the method comprising:

The method of applying the photosensitive resin composition onto the substrate is not particularly limited. Typically, a photosensitive resin composition is applied onto a substrate using a contact transfer coating device such as a roll coater, a reverse coater, and a bar coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater.

The coating film is then dried as necessary. A drying method is not particularly limited. Examples of the drying method include (1) a method of drying on a hot plate at a temperature of 80° C. to 120° C., preferably 90° C. to 100° C. for 60 seconds to 120 seconds, (2) a method of leaving at room temperature for several hours to several days, and (3) a method of placing in a hot air heater or an infrared heater for several tens of minutes to several hours to remove the solvent.

Then, the coating film is position-selectively exposed according to the shape of the pattern of the cured film. Typically, the coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Although the energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, it is preferably about 10 mJ/cm ² or more and 2000 mJ/cm ² or less.

Then, the exposed coating film is developed with a developer to form a patterned cured film. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

After development, if necessary, the patterned cured film may be post-baked at a temperature of about 200° C. or higher and 250° C. or lower.

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

[Examples 1 to 28 and Comparative Examples 1 to 13]
A cardo resin synthesized according to the following method was used as the alkali-soluble resin (A) (component (A)) in the examples and comparative examples.
First, 235 g of a bisphenol fluorene type epoxy resin (epoxy equivalent: 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were placed in a 500 mL four-necked flask, and heated and dissolved at 90 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 was still cloudy and dissolved completely. At this time, 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 value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-obtained bisphenol fluorene type epoxy acrylate and dissolved, and then 80.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and reacted at 110 to 115° C. for 4 hours while gradually raising the temperature. After confirming the disappearance of the acid anhydride groups, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain a cardo resin. Disappearance of acid anhydride groups was confirmed by IR spectrum.

Dipentaerythritol hexaacrylate was used as the photopolymerizable monomer (B) (component (B)) in Examples and Comparative Examples.

In the examples and comparative examples, the compounds described below were used as the photopolymerization initiator (C) (component (C)). In the examples and comparative examples, the following CI1 and CI2 were used as the photopolymerization initiator (CI), which is the oxime ester compound represented by the above formula (C1).

In Examples and Comparative Examples, the following CII1 to CII5 were used as oxime ester compounds as photopolymerization initiators (C-II) other than photopolymerization initiator (C-I).

In Examples and Comparative Examples, the following CII6 was used as an aminoketone compound as a photopolymerization initiator (C-II).
CII6: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one

In the examples and comparative examples, the following D1 and D2 were used as the colorant (D) (component (D)). The amount of the colorant (D) described in Table 1 below is not the amount of the dispersion, but the amount of solid content (amount of pigment and dispersant) in the dispersion.
D1: Carbon black dispersion (carbon black content 20% by mass, dispersant content 5% by mass)
D2: Organic pigment mixed dispersion (C.I. Pigment Blue 15:6/C.I. Pigment Violet 23/C.I. Pigment Red 256=40% by mass/20% by mass/40% by mass, solid content concentration 15% by mass)

Alkali-soluble resin (A), photopolymerizable monomer (B), photopolymerization initiator (C) of the type shown in Table 1, coloring agent (D) of the type shown in Table 1, 0.2 parts by weight of silane coupling agent ((3-phenylaminopropyl)trimethoxysilane), and 0.5 parts by weight of surfactant were uniformly dissolved and dispersed in the organic solvent (S) so that the solid content concentration was 15% by weight, respectively, in the amounts shown in Table 1, respectively. A flexible resin composition was obtained. As the organic solvent (S), a mixed solvent containing 15% by mass of 3-methoxybutyl acetate and 85% by mass of propylene glycol monomethyl ether acetate was used.

The photosensitive resin composition of each example and comparative example was applied onto a glass substrate (100 mm×100 mm) using a spin coater and prebaked at 90° C. for 120 seconds to form a coating film having a thickness of 1.0 μm. Next, using a proximity exposure apparatus (product name: TME-150RTO, manufactured by Topcon Corporation), the coating film was irradiated with ultraviolet rays through a negative mask having a line pattern of 6 μm in width with an exposure gap of 50 μm. The exposure amount was set in three stages of 20, 40, and 60 mJ/cm ² . The exposed coating film was developed with a 0.04 mass % KOH aqueous solution at 26° C. for 40 seconds, and then post-baked at 230° C. for 30 minutes to form a line pattern.

<Straightness evaluation>
The unevenness of the edges of the formed line pattern was observed with an optical microscope to evaluate the straightness of the pattern. The case where there was no rattling was evaluated as "good", and the case where there was rattling was evaluated as "bad".

<Adhesion evaluation>
The presence or absence of peeling of the formed line pattern was observed with an optical microscope to evaluate the pattern adhesion. A case where peeling was not observed was evaluated as "good", and a case where peeling was observed was evaluated as "poor".

<Taper angle>
As shown in FIG. 1, the taper angle was evaluated by measuring the angle θ between the substrate 90a and the side surface of the line portion 10 in the cross section of the line portion 10 in the width direction of the line pattern formed by exposure of 40 mJ/cm ² .
In the case of a trapezoidal shape as shown in FIG. 1, θ is more than 0 degrees and less than 90 degrees, which is a forward tapered shape. In the case of an inverted trapezoidal shape as shown in FIG. 2, θ is greater than 90 degrees and less than 180 degrees, which is an inverted tapered shape.
In FIGS. 1 and 2, the surface where the substrate 90a and the line portion 10 of the cured product pattern of the photosensitive resin composition are in contact is defined as a reference surface, and the angle formed by the line parallel to the reference surface and the side surface of the line is expressed as θ, which is the same as θ above.
The taper angle (pattern cross-sectional shape) was evaluated according to the following criteria.
◎: measurement angle θ is 70 degrees or more and 85 degrees or less ○: measurement angle θ is 86 degrees or more and 90 degrees or less △: measurement angle θ is 91 degrees or more and 100 degrees or less ×: measurement angle θ is 101 degrees or more XX: measurement angle θ is 69 degrees or less

The technical significance of the taper angle θ will be supplemented below. The taper angle θ is desirably 90 degrees in order to ensure fidelity to the mask pattern.
When incorporating a black matrix formed using a photosensitive resin composition into an image display panel, liquid crystal may be arranged in contact with the black matrix. The molecular orientation of liquid crystals is controlled by voltage. Controlling this molecular orientation drastically changes the light transmittance in an optical system including a polarizing plate. As a result, characters, images, etc. are displayed on the image display panel.
When the liquid crystal is arranged in contact with the black matrix, the liquid crystal alignment behavior differs from that of the pattern flat portion (corresponding to the above-mentioned line portion or space portion) at the pattern boundary portion of the black matrix due to the influence of the boundary step. As an optical phenomenon, even if the light transmittance is 0% in the pattern flat portion, the light beam is transmitted at the pattern boundary portion, and is observed as light bleeding or light leakage at the pattern boundary portion, which is not suitable for an image display panel or an image display device.
This light bleeding phenomenon is remarkable when the taper angle θ of the black matrix pattern exceeds 90 degrees, and is reduced when the line taper angle θ is 90 degrees or less. When a driving test is performed as an image display panel and an image display device, a taper angle θ of 85 degrees or less is particularly suitable. If the angle is less than 70 degrees, the light transmission area becomes narrow (corresponding to narrowing of the space portion other than the line portion 10 in FIG. 1), and the amount of light decreases.
Therefore, for liquid crystal display panels and liquid crystal display devices, the line taper angle θ is preferably 90 degrees or less, and most preferably 70 degrees or more and 85 degrees or less.

According to Table 1, the patterned cured film formed using the photosensitive resin composition of the example containing the alkali-soluble resin (A), the photopolymerizable monomer (B), the photopolymerization initiator (C-I), which is an oxime ester compound having the structure represented by the above formula (C1), and the photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I) at predetermined ratios, has excellent linearity and adhesion to the substrate, and has a good cross-sectional shape. I understand.
On the other hand, the patterned cured film formed using the photosensitive resin composition of the comparative example containing only one of the photopolymerization initiator (C-I) and the photopolymerization initiator (C-II), or the photopolymerization initiator (C-I) and the photopolymerization initiator (C-II) at a predetermined ratio, could not achieve both good straightness and good adhesion to the substrate, and had a poor cross-sectional shape.

Claims (6)

A photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), wherein the photopolymerization initiator (C) has the following formula (C1):
(In formula (C1), X ⁰¹ is the following formula (C1-1a):
X ⁰² and X ⁰³ are each independently a monovalent organic group; X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group; t0 to t3 are each independently 0 or 1; is 0 and
In formula (C1-1a), X ⁰⁷ is a divalent organic group that binds to a nitrogen atom in a carbazole ring via a C—N bond, X ⁰⁷ is a divalent organic group containing an aromatic ring, of the two bonds possessed by X ⁰⁷ , the other of the bonds that bind to the carbazole ring in formula (C1-1a) is bonded to the aromatic ring in X ⁰⁷ , and t4 and t5 are each independently 0 or 1 and at least one of t4 and t5 is 1;
The monovalent organic groups for X ⁰² and X ⁰³ are an alkyl group, a cycloalkyl group, and a phenyl group which may have a substituent. )
and a photopolymerization initiator (C-I) represented by and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I),
The photopolymerization initiator (C-II) is an oxime ester compound,
The oxime ester compound has the following formula (C2):
(In formula (C2), R ^c1 is a monovalent organic group, and R ^c2 is represented by the following formula (C2-3):
is a group represented by R ^c3 is a hydrogen atom or an optionally substituted alkyl group having 1 to 11 carbon atoms,
式（Ｃ２－３）中、Ｒ ^ｃ７は、ニトロ基又はＲ ^ｃ１２ －ＣＯ－で表される基（式中、Ｒ ^ｃ１２は、２－メチルフェニル基、チオフェン－２－イル基、又はα－ナフチル基である。）であり、Ｒ ^ｃ８及びＲ ^ｃ９は、それぞれ、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、２－メトキシエチル基、２－シアノエチル基、２－フェニルエチル基、２－シクロヘキシルエチル基、２－メトキシカルボニルエチル基、２－クロロエチル基、２－ブロモエチル基、３，３，３－トリフルオロプロピル基、及び３，３，４，４，５，５，５－ヘプタフルオロ－ｎ－ペンチル基であり、ｎ３は０以上４以下の整数であり、
n1 in the formula (C2) is 0 or 1,
The R ^c1 is represented by the following formula (C2b):
(In the formula (C2b), n5 is an integer of 1 or less and 8 or less, n6 is an integer of 1 or more and 5 or less, n7 is an integer of 0 or more and (n6+3) or less, R ^c12 is a monovalent organic group ,
The monovalent organic group as R ^c12 is the same as X ⁰² and X ⁰³ in formula (C1). )
is a group represented by
A photosensitive resin composition, wherein the mass ratio of the photopolymerization initiator (C-I) to the mass of the photopolymerization initiator (C) is 20% by mass or more and 95% by mass or less. The photopolymerization initiator (C) further contains an aminoketone-based compound as the photopolymerization initiator (C-II),
The aminoketone compound is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butan-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one, and 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one selected from the group consisting of one or more, the photosensitive resin composition according to claim 1. Furthermore, the photosensitive resin composition of Claim 1 or 2 containing a coloring agent (D). The photosensitive resin composition according to claim 3, wherein the coloring agent (D) is a light shielding agent (D1). Forming a coating film by applying the photosensitive resin composition according to any one of claims 1 to 4 on a substrate;
position-selectively exposing the coating film;
developing the exposed coating film;
A method for producing a patterned cured film, comprising: A patterned cured film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 4.

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