JP2020086317A - Photosensitive resin composition, production method of patterned cured film, and patterned cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a patterned cured film having excellent straightness and adhesion to a substrate and having a good cross-sectional shape, and patterning using the photosensitive resin composition. To provide a method for producing a cured film, and a patterned cured film that can be produced by the production method. In a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), a specific structure containing a nitrated carbazole ring. Of the oxime ester compound (C-I) and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-II) are used in combination. [Selection diagram] None

Description

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, many insulating films, translucent members such as spacers, and light-shielding members such as 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 the photosensitive resin composition by exposing the photosensitive resin composition in a position-selective manner.

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, in the example of Patent Document 1, a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, and a polymerization initiation represented by any of the following formulas Disclosed is a photosensitive resin composition containing an agent and a mixed solvent of 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate.

JP2012-58728A

By the way, it is often required that a photosensitive resin composition as a whole be capable of forming a patterned cured film having excellent straightness and adhesion to a substrate and having a good cross-sectional shape. However, when a conventionally known photosensitive resin composition such as the photosensitive resin composition described in Patent Document 1 is used, it is patterned to have excellent straightness and adhesion to a substrate and a good cross-sectional shape. Often, a cured film cannot be formed.

The present invention has been made in view of the above problems, and is 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. And 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 identified a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), which contains a nitrated carbazole ring. By using a photopolymerization initiator (C-I) which is an oxime ester compound having a structure of and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-II) in combination, They have found that they can solve the problems 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 containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C), which is a photopolymerization initiator ( C) is the following formula (C1):

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

In the structure represented by, a hydrogen atom bonded to the aromatic ring, excluding t2+t3 hydrogen atoms, X ⁰² and X ⁰³ are each independently a monovalent organic group, ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and 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 by a C—N bond, t4 and t5 are each independently 0 or 1, and t4 and At least one of t5 is 1. )
A photopolymerization initiator (C-I) represented by and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I),
The photosensitive resin composition is such that the ratio of the mass 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 second aspect of the present invention is
Forming a coating film by coating the photosensitive resin composition according to the first aspect on a substrate;
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 made of a cured product of the photosensitive resin composition according to the first aspect.

According to the present invention, 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, and the photosensitive resin composition, It is possible to provide a method for producing a patterned cured film to be used, 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 a forward taper. 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 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 a photopolymerization initiator (C) other than the photopolymerization initiator (C-I) represented by the formula (C1) described below as the photopolymerization initiator (C). It contains in combination with a photopolymerization initiator (C-II). The ratio of the mass 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.
When the photosensitive resin composition contains a predetermined amount of the photopolymerization initiator (C-I) and the photopolymerization initiator (C-II) in combination, the photosensitive resin composition is used to move straight ahead. Further, it is possible to form a patterned cured film having excellent adhesion to a substrate and having a good cross-sectional shape.

The essential or optional components contained in the photosensitive resin composition will be 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 the alkali-soluble resins that have been conventionally blended in various photosensitive resin compositions.
Here, in the present specification, the alkali-soluble resin (A) refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) that imparts alkali solubility in the molecule.

Examples of the resin 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 the resin (a-1) having a cardo structure is used as the alkali-soluble resin, it is easy to obtain a photosensitive resin composition having excellent resolution, and a cured film that hardly flows when heated by using the photosensitive resin composition is formed. Easy to form. Therefore, it is easy to form a cured film having a good shape.

[Resin (a-1) having a 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. The cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom forming the first ring structure. The second annular structure and the third annular structure may have the same structure or different structures.
A representative example of the cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the carbon atom at the 9-position of the fluorene ring.

The cardo resin (a-1) is not particularly limited, and a conventionally known resin can be used. Among them, the resin represented by the following formula (a-1) is preferable.

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

In the formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group. R ^a3 independently represents a linear or branched alkylene group, m 2 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, and an alkylene group having 1 to 6 carbon atoms. Is particularly preferable, and an ethane-1,2-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group are the most preferable.

Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle.
Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like.
Specific examples thereof 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 an aromatic hydrocarbon ring or an aromatic heterocycle, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

The following groups are mentioned as a suitable example of the divalent group represented by Formula (a-3).

The divalent group X ^a in the formula (a-1) is a cardo group by reacting a tetracarboxylic acid dianhydride giving ^a residue Z ^a with a diol compound represented by the following formula (a-2a). It is introduced into the resin (a-1).

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

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.
First, after replacing the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with a group represented by -R ^a3 -OH, if necessary, according to a conventional method, Glycidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).
Then, the epoxy compound represented by the formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (a-2a).
In formula (a-2b) and formula (a-2c), R ^a1 , R ^a3 , and m2 are as described for formula (a-2). The 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 the formula (a-2b) include the following diol compounds.

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

In the formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include a tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. And biphenyl ether tetracarboxylic acid dianhydride.
In addition, 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. , M3 represents an integer of 0 or more and 12 or less.)

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 included 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 is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 4 or less, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. It is particularly preferably 1 or more and 3 or less.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

As R ^a4 in the formula (a-4), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferably each independently from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. 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, and particularly preferably a hydrogen atom or a methyl group.
It is preferable that the plurality of R ^a4 in the formula (a-4) are the same group because the preparation of high-purity tetracarboxylic dianhydride is easy.

M3 in Formula (a-4) shows the integer of 0-12. By setting the value of m3 to 12 or less, the purification of the tetracarboxylic dianhydride can be facilitated.
From the viewpoint of easy purification of the tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, and more preferably 3.
From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2.
2 or 3 is particularly preferable for m3 in the formula (a-4).

The alkyl group having 1 to 10 carbon atoms which can be selected as R ^a5 and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms which can be selected as R ^a4. ..
R ^a5 and R ^a6 are each a hydrogen atom or a carbon atom number of 1 or more and 10 or less (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less), because purification of the tetracarboxylic dianhydride is easy. It is more preferably 1 or more and 4 or less, particularly preferably 1 or more and 3 or less), and particularly preferably a hydrogen atom or a methyl group.

Examples of the tetracarboxylic acid dianhydride represented by the formula (a-4) include, for example, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″, 6,6"-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6" -Tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetra Carboxylic 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 acid dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride , Norbornane-2-spiro-α-cyclononanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone -Α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2' '-Norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5' ',6,6''-Tetracarboxylic dianhydride, norbol Nan-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α- Cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α' -Spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2' '-Norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-norbornane-5,5 ″,6,6″-Tetracarboxylic acid dianhydride and the like can be mentioned.

The cardo resin (a-1) has a weight average molecular weight of preferably 1,000 or more and 40,000 or less, more preferably 1,500 or more and 30,000 or less, and further preferably 2,000 or more and 10,000 or less. Within the above range, sufficient heat resistance and mechanical strength can be obtained for the cured film formed using the photosensitive resin composition while obtaining good developability.

[Novolak resin (a-2)]
It is also preferable that the alkali-soluble resin (A) contains the novolac resin (a-2) from the viewpoint of easily forming a cured film that does not flow excessively by heating.
As the novolac resin (a-2), various novolac resins conventionally blended in the photosensitive resin composition can be used. As the novolac resin (a-2), those obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as “phenols”) and an aldehyde with an acid catalyst are preferable.

(Phenols)
Examples of the phenols used when producing the novolac resin (a-2) include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol. , 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols; 2 -Alkylphenols such as isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol, and 3,4 , Trialkylphenols such as 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglysinol; alkyl polyhydric phenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (Each alkyl group has 1 to 4 carbon atoms.); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol together. 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 the 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.

A novolac resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. 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 is 70/30 or more and 95/5 or less in terms of a molar ratio of m-cresol/2,3,5-trimethylphenol. Is preferred.

(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)
Examples of the acid catalyst used in producing the novolac resin (a-2) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and Examples thereof include organic acids such as paratoluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more kinds.

(Molecular weight)
The polystyrene-equivalent weight average molecular weight (Mw; hereinafter also simply referred to as "weight average molecular weight") of the novolac resin (a-2) is from the viewpoint of heat resistance of a cured film formed using the photosensitive resin composition. , The lower limit is preferably 2000, more preferably 5000, particularly preferably 10,000, further preferably 15,000, most preferably 20,000, and the upper limit is preferably 50,000, more preferably 45,000, further preferably 40,000, most preferably 35,000.

As the novolak resin (a-2), it is possible to use a combination of at least two resins having different polystyrene-equivalent weight average molecular weights. By using those having different weight average molecular weights in a combination of large and small, it is possible to balance the developability of the photosensitive resin composition with the heat resistance of the cured film formed using the photosensitive resin composition.

[Modified epoxy resin (a-3)]
The alkali-soluble resin (A) is 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). May be included. Such an adduct is also referred to as "modified epoxy resin (a-3)".
In addition, in the specification and claims of the present application, a compound which corresponds to the above definition and which does not correspond to the resin (a-1) having a cardo structure is referred to as a modified epoxy resin (a-3). ).

Hereinafter, the epoxy compound (a-3a), the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c) will be described.

<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 not containing an aromatic group. Well, an aromatic epoxy compound having an aromatic group is preferable.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a bifunctional or higher functional polyfunctional epoxy compound, and a polyfunctional epoxy compound is preferable.

Specific examples of the epoxy compound (a-3a) include 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. Functional epoxy resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylenediamine, tetraglycidyl bisaminomethylcyclohexane Glycidylamine type epoxy resin; Heterocyclic epoxy resin such as triglycidyl isocyanurate; Phlorogricinol triglycidyl ether, trihydroxybiphenyl triglycidyl 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-functional epoxy resins such as 2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetrafunctional epoxy resins such as tetraglycidoxy biphenyl.

Moreover, 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 the 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 has an excellent balance between sensitivity and developability and which can form 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), R ^a7 is each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, j is an integer of 1 or more and 4 or less.)

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, sec-octyl group, tert- Examples include octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, and n-dodecyl group.

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 a phenyl group which may have a substituent, 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 the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group. 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, but examples thereof include an epoxy compound represented by the following formula (a-3a-2). be able to.

(In formula (a-3a-2), R ^a7 and j are the same as those in formula (a-3a-1), and k is the average number of repeating structural 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), it is particularly easy to obtain a photosensitive resin composition having a good balance between sensitivity and developability. Compounds are preferred.

(In the formula (a-3a-3), k is the same as the 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).
As the unsaturated group-containing carboxylic acid (a-3b), a monocarboxylic acid having a reactive unsaturated double bond such as an acryl group or a methacryl group in the molecule is preferable. Examples of the unsaturated group-containing carboxylic acid include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyanocinnamic acid, cinnamic acid and the like. In addition, the unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more kinds.

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), a tertiary amine such as triethylamine, benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, The reaction is carried out in an organic solvent at a reaction temperature of 50° C. or higher and 150° C. or higher for several hours to several tens of hours using a quaternary ammonium salt such as tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine or triphenylphosphine as a catalyst. There is a method.

The ratio of the amounts of both used in the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) is such that the epoxy equivalent of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid ( The ratio of a-3b) to the carboxylic acid equivalent is usually 1:0.5 to 1:2, preferably 1:0.8 to 1:1.25, more preferably 1:0.9 to 1:1. .1 is particularly preferred.
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 the above equivalent ratio, the crosslinking efficiency is Is preferred, which is preferable.

(Polybasic acid anhydride (a-3c))
The polybasic acid anhydride (a-3c) is a carboxylic acid anhydride having two or more carboxyl groups.
The polybasic acid anhydride (a-3c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride. Phthalic acid, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexa Hydrophthalic 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). The polybasic acid anhydrides (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 alkylene group having 1 to 10 carbon atoms which may have a substituent.)

As the polybasic acid anhydride (a-3c), a compound having two or more benzene rings is preferable because it is easy to obtain a photosensitive resin composition having an excellent balance between sensitivity and developability. The polybasic acid anhydride (a-3c) 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). Is more preferable.

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.
In addition, the usage ratio is such that the molar number of OH groups in the component after the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) and the polybasic acid anhydride (a-3c). The equivalent ratio of the acid anhydride group of 1) is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. Within the above range, it is easy to obtain a photosensitive resin composition having good 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. When the acid value of the resin is 10 mgKOH/g or more, sufficient solubility in the developing solution can be obtained, and when the acid value is 150 mgKOH/g or less, sufficient curability can be obtained and surface property is improved. Can be good.

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1,000 or more and 40,000 or less, more preferably 2,000 or more and 30,000 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. Further, when it is 40,000 or less, it is easy to obtain a photosensitive resin composition exhibiting sufficient solubility in a developing solution.

[Acrylic resin (a-4)]
Acrylic resin (a-4) is also preferable as a component constituting the alkali-soluble resin (A).
As the acrylic resin (a-4), a resin containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from another monomer such as (meth)acrylic acid ester 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 impair the object of the present invention.

In the above formula (a-4-1), 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 a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

The substituent other than the hydrocarbon group in the organic group of R ^a10 is not particularly limited as long as the effects of the present invention are not impaired, and a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group. , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkyl thioether group, aryl ether group, aryl thioether group, amino group (-NH ₂ , -NHR, —NRR′: R and R′ each independently represent a hydrocarbon group) and the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the above-mentioned 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.
The acyl group having an unsaturated double bond, such as an acryloyloxy group or a methacryloyloxy group, is, for example, at least a part of the epoxy group in the acrylic resin (a-4) containing a structural unit having an epoxy group. It can be produced by reacting 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. When these groups include 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 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-octyl group, n-nonyl group, isononyl group, n-decyl group, An isodecyl group etc. are 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 a cyclopentyl group, and a monocyclic alicyclic group such as a cyclohexyl group or Examples thereof include 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 the formula (a-4-1) when the compound represented by the formula (a-4-1) has a chain group having an epoxy group as R ^a10 include: Examples of (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. ..

Further, the compound represented by the formula (a-4-1) may be an alicyclic epoxy group-containing (meth)acrylic acid ester. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

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

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, and R ^a22 represents 2 having 1 to 10 carbon atoms. Represents a valent hydrocarbon group, and t represents an integer of 0 or more and 10 or less. As R ^a21 , a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. Examples of R ^a22 include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

Further, the acrylic resin (a-4) may be a polymer of a monomer other than the (meth)acrylic acid ester. Examples of such a monomer 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 kinds.

Examples of (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 can be mentioned.

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; and anhydrides of these dicarboxylic acids.

As the allyl compound, allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate; allyloxyethanol; Can be mentioned.

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

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

Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromo styrene, Halostyrenes such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene; and the like.

In the acrylic resin (a-4), the amount of the structural unit derived from (meth)acrylic acid and the amount of the structural unit derived from another monomer are not particularly limited as long as the object of the present invention is not impaired. The amount of the structural unit derived from (meth)acrylic acid in the acrylic resin (a-4) is preferably 5% by mass or more and 50% by mass or less with respect to the mass of the acrylic resin (a-4). More preferably, it is not less than 30% by mass and not more than 30% by mass.

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 1% by mass or more. 50 mass% or less is preferable, 1 mass% or more and 30 mass% or more is more preferable, and 1 mass% or more and 20 mass% or less is particularly preferable.
Since the acrylic resin (a-4) contains the 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 be uniformized, and thus the column spacer. It is effective in improving the heat resistance and mechanical properties of.

The weight average molecular weight of the acrylic resin (a-4) is preferably 2,000 or more and 50,000 or less, and more preferably 3,000 or more and 30,000 or less. Within the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

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

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

Examples of 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-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic 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, 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, a phthalic acid derivative half (meth)acrylate, and the like. These monofunctional monomers may be used alone or in combination of two or more.

On the other hand, as the polyfunctional monomer, 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-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol 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 poly Glycidyl ether poly(meth)acrylate, urethane (meth)acrylate (that is, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate and the like and 2-bidroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, Examples thereof include polyfunctional monomers such as (meth)acrylamide methylene ether, a condensation product of polyhydric alcohol and N-methylol(meth)acrylamide, and triacrylformal. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a trifunctional or higher polyfunctional monomer 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. Is preferable, a polyfunctional monomer having 4 or more functional groups is more preferable, and a polyfunctional monomer having 5 or more functional groups is further preferable.

The content of the photopolymerizable monomer (B) in the photosensitive resin composition is 1% by mass or more based on the mass (total solid content) of the photosensitive resin composition excluding the mass of the organic solvent (S) described below. 50 mass% or less is preferable, and 5 mass% or more and 40 mass% or less is more preferable. Within the above range, the sensitivity, developability and resolution tend to be easily balanced.

<Photopolymerization initiator (C)>
The photosensitive resin composition contains a photopolymerization initiator (C-I) represented by the following formula (C1) as a photopolymerization initiator (C), and a light other than the photopolymerization initiator (C-I). And a polymerization initiator (C-II). The ratio of the mass 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.
As described above, the photosensitive resin composition contains the photopolymerization initiator (C-I) and the photopolymerization initiator (C-II) in an amount within the above-mentioned predetermined range in combination, whereby the photosensitive resin composition The composition can be used to form a patterned cured film having excellent straightness and adhesion to a substrate and having a good cross-sectional shape.
The mass ratio of the photopolymerization initiator (C-I) 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 (C-I)]
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 alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. t0 to t3 are 0 or 1 independently of each other. 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 by a C—N 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 by a C—N bond. The monovalent organic group may contain O, S, N, P, Si, and a hetero atom such as a halogen atom. The number of carbon atoms of the organic group as X ⁰⁶ is not particularly limited. The number of carbon atoms of 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.

Preferable examples of the organic group as X ⁰⁶ include an alkyl group, an alkenyl group, an alkynyl group, an aliphatic cyclic hydrocarbon group, an aryl group, an aliphatic heterocyclic group, a heteroaryl group, an aliphatic acyl group and an aromatic acyl group. Groups and combinations of these groups. Preferable examples of the combination of these groups include an aralkyl group, a cycloalkylalkyl group and the like.

When the organic group as X ⁰⁶ is an alkyl group, an alkenyl group or an 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, or cyclic. Alternatively, a combination of these structures may be used.

The organic group as X ⁰⁶ may have a substituent. Examples of the substituent which the organic group as X ⁰⁶ may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. Cycloalkyl group, cycloalkoxy group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms Saturated aliphatic acyloxy group, phenyl group which may have a substituent, phenoxy group which may have a substituent, phenylthio group which may have a substituent, benzoyl group which may have a substituent, A phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent Naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthoyl group An oxy group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 1 Or an amino group substituted with an organic group of 2, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like.

Among the above groups as X ⁰⁶ , an alkyl group, an aryl group, and an aralkyl group are preferable from the viewpoint of the ease of synthesis and availability of the photopolymerization initiator (CI).

Specific examples of the case where X ⁰⁶ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an 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-undecyl group Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group. ..

Preferable examples when X ⁰⁶ is an aryl group include a phenyl group, a naphthalene-1-yl group, a naphthalen-2-yl group, a 2-phenylphenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group. Is mentioned.

Preferable examples when X ⁰⁶ is an aralkyl group include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a naphthalen-1-ylmethyl group, and a naphthalene-2. And -ylmethyl group.

Among the specific examples of X ⁰⁶ described 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 from the hydrogen atoms bonded to the aromatic ring in the structure represented by the formula (C1-1). As the group represented by the 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 X ⁰⁶ are the same as in formula (C1-1). X ⁰⁷ is a divalent organic group bonded to the nitrogen atom in the carbazole ring by a C—N bond. X ⁰⁷ is a divalent organic group containing an aromatic ring. Two coupling hands, the other bonds of bond that binds to the carbazole ring in Formula (C1-1a) and formula (C1-1c) that X ⁰⁷ has ^is bonded to the aromatic ring in ^{X 07.}
In addition, 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, preferred specific examples of X ⁰⁷ are described below. The divalent group corresponding to X ⁰⁷ in the following structure is also preferable as X ⁰⁷ in the 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.
From the viewpoint of easy synthesis and availability of the compound represented by the formula (C1), the group represented by the formula (C1-1a), the group represented by (C1-1b), and the formula (C1-1c). As preferred examples of the group represented by the formula (), 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). Is mentioned.

In formula (C1), X ⁰² and X ⁰³ are each independently a monovalent organic group. Examples of suitable organic groups as X ⁰² and X ⁰³ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent which may have a substituent. Benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, substituted A naphthoxycarbonyl group which may have a group, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a substituent A heterocyclylcarbonyl group which may have 1 or 2, an amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, a piperazin-1-yl group and the like.

When X ⁰² and X ⁰³ are an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When X ⁰² and X ⁰³ are alkyl groups, they may be linear or branched. When X ⁰² and X ⁰³ are alkyl groups, specific examples thereof 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-octyl group, n-nonyl group, Examples thereof include isononyl group, n-decyl group, and isodecyl group. When X ⁰² and X ⁰³ are alkyl groups, the alkyl groups may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When X ⁰² and X ⁰³ are an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When X ⁰² and X ⁰³ are alkoxy groups, they may be linear or branched. Specific examples of the case where X ⁰² and X ⁰³ are alkoxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group. Group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec- Examples thereof include an octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. Further, when X ⁰² and X ⁰³ are an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When X ⁰² and X ⁰³ are a cycloalkyl group or a cycloalkoxy group, the cycloalkyl group or the cycloalkoxy group preferably has 3 or more and 10 or less carbon atoms, and more preferably has 3 or more and 6 or less carbon atoms. Specific examples of the case where X ⁰² and X ⁰³ are cycloalkyl groups include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. When X ⁰² and X ⁰³ are cycloalkoxy groups, specific examples thereof include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. ..

When X ⁰² and X ⁰³ are a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the saturated aliphatic acyl group or the saturated aliphatic acyloxy group preferably has 2 or more and 21 or less carbon atoms, and 2 or more and 7 or less. More preferable. When R ^c7 is a saturated aliphatic acyl group, specific examples thereof include 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, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca group Examples thereof include a noyl group and an n-hexadecanoyl group. When X ⁰² and X ⁰³ are saturated aliphatic acyloxy groups, specific examples thereof include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group. , 2,2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group Group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

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, and more preferably 2 or more and 7 or less. When X ⁰² and X ⁰³ are alkoxycarbonyl groups, specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n- Heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group Group, an isodecyloxycarbonyl group, and the like.

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, and 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. When X ⁰² and X ⁰³ are phenylalkyl groups, specific examples include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. When X ⁰² and X ⁰³ are naphthylalkyl groups, specific examples thereof include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. Is mentioned. 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 the naphthyl group.

When X ⁰² and X ⁰³ are a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and O, such monocycles, or such monocycle and a benzene ring. And is a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of monocycles constituting the condensed ring is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. The heterocyclic ring constituting the heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

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

When X ⁰² and X ⁰³ are amino groups substituted with 1 or 2 organic groups, preferred examples of the organic groups include alkyl groups having 1 to 20 carbon atoms, cyclo groups having 3 to 10 carbon atoms. Alkyl group, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted carbon atom number 7 to 20 phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms , And a heterocyclyl group. Specific examples of these suitable organic groups are the same as X ⁰² and X ⁰³ . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in X ⁰² and X ⁰³ each further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Alkoxy group, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 1 to 6 carbon atoms A monoalkylamino group having an alkyl group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. Can be mentioned.

These substituents are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, saturated aliphatic acyl groups having 2 to 7 carbon atoms, and 2 to 7 carbon atoms. Alkoxycarbonyl group, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and dialkylamino having an alkyl group having 1 to 6 carbon atoms When it is a group, an ether bond (—O—) may be contained in the carbon chain of these substituents.

When the phenyl group, naphthyl group, and heterocyclyl group contained in X ⁰² and X ⁰³ further have a substituent, the number of the substituents is not limited as long as the object of the present invention is not impaired, but 1 or more and 4 or less. Is preferred. When the phenyl group, naphthyl group, and heterocyclyl group contained in X ⁰² and X ⁰³ have a plurality of substituents, the plurality of substituents may be the same or different.

As X ⁰² and X ⁰³ , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is as described above as the substituent that the phenyl group may have.

Among the organic groups, as X ⁰² and X ⁰³ , an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, which may have a substituent on the aromatic ring A good phenylthioalkyl group is preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. preferable. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of 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 of 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. Of the cycloalkylalkyl groups, the cyclopentylethyl group is preferred. The number of carbon atoms of 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 preferable.

Further, as X ⁰² and X ⁰³ , a group represented by —A ¹ —CO—O—A ² is also preferable. A ¹ is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. A ² 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, and is 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.

Preferable examples of A ² include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferable specific examples of A ⁴ include 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. Group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Specific preferred examples of the group represented by -A ¹ -CO-O-A ² include 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 group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, and 3-phenoxycarbonyl-n-propyl group.

式（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。 Although X ⁰² and X ⁰³ have been described above, a group represented by the following formula (C1a) or (C1b) is preferable as X ⁰² and X ⁰³ .

In formulas (C1a) and (C1b), X ⁰⁸ and X ⁰⁹ are organic groups, respectively. 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 of 0 or more and (t8+3) or less. X ⁰¹⁰ is an organic group.

Examples of the organic group for X ⁰⁸ and X ^{09 in} formula (C1a) are the same as X ⁰² and X ⁰³ . As X ⁰⁸ , an alkyl group or a phenyl group is preferable. When X ⁰⁸ is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, it is most preferable that X ⁰⁸ is a methyl group. When X ⁰⁸ and X ⁰⁹ are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (C1a), in which X ⁰⁸ and X ⁰⁹ form a ring, include naphthalen-1-yl group and 1,2,3,4-tetrahydro. Examples thereof include naphthalen-5-yl group. In the above formula (C1a), t6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (C1b), 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 the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 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. Preferred examples of X ⁰¹⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and among these, a methyl group is more preferred.

In the above 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 an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (C1b), t7 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (C1), X ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. is there. Preferable examples of the substituent that X ⁰⁴ and X ⁰⁵ may have when X ⁰⁴ and X ⁰⁵ are alkyl groups include a phenyl group and a naphthyl group. Further, when X ⁰⁴ and X ⁰⁵ are aryl groups, the substituent that may be possessed is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, or the like. Are preferably exemplified.

In formula (C1), as X ⁰⁴ and X ⁰⁵ , hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like can be mentioned. It is preferably exemplified, and 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).
When X ⁰¹ is a group represented by the formula (C1-1aa), suitable examples of the oxime ester compound represented by the formula (C1) include the following compounds.

When X ⁰¹ is a group represented by the formula (C1-1ba), the following compounds can be given as preferred specific examples of the oxime ester compound represented by the formula (C1).

When X ⁰¹ is a group represented by the formula (C1-1ca), the following compounds can be given as preferred specific examples of the oxime ester compound represented by the formula (C1).

<Photopolymerization initiator (C-II)>
The photosensitive resin composition contains, as the photopolymerization initiator (C), a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-II) together with the above-mentioned photopolymerization initiator (C-II). )including.
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 (CI).

Suitable examples of the photopolymerization initiator (C-II) include oxime ester compounds having a structure not corresponding to the above formula (C1); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane. -1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butane-1. -One, 2-(4-methylbenzyl)-2-diethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl Α-aminoketone compounds such as -1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one and 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl- Α-Hydroxyketone photoinitiators such as (2-hydroxy-2-propyl)ketone and 1-hydroxycyclohexylphenyl ketone; benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzyl methyl ketal Photopolymerization initiator; benzophenone such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4'-methyldiphenyl sulfide, 4,4'-bisdiethylaminobenzophenone -Based photopolymerization initiators; thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-s-triazine, 2- Phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-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 initiator such as 5-triazine; carbazole-based photopolymerization initiator; 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)- 1,2′-biimidazole, 2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole, 2, 2'-bis(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' -Biimidazole-based photopolymerization initiators such as tetraphenyl-1,2'-biimidazole; benzimidazoline-based photopolymerization initiators represented by the following formulas and the like are exemplified.

The photosensitive resin composition preferably contains an oxime ester compound and/or an α-aminoketone compound as the photopolymerization initiator (C-II) because the desired effect is easily obtained, and the oxime ester compound and α It is more preferable to include a combination of aminoketone compounds.

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

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 the 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 alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
In formula (C2-1), R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group. A is S or O. 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 a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to 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 the formula (C2) is the same as the monovalent organic group described above for X ⁰² and X ⁰³ in the 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 the formula (C2a) are respectively the same as X ⁰⁸ , X ⁰⁹ , and t6 in the formula (C1a) described above for the formula (C1). R ^c12 , n5, n6, and n7 in the formula (C2b) are respectively the same as X ⁰¹⁰ , t7, t8, and t9 in the formula (C1b) described above for the formula (C1).

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

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

When R ^c4 in the 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. When R ^c4 in the formula (C2-1) is an organic group, preferable examples thereof include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and 2 to 7 carbon atoms. The following saturated aliphatic acyl groups; alkoxycarbonyl groups having 2 to 7 carbon atoms; saturated aliphatic acyloxy groups having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; 1 carbon atom A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 6 or less, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; an alkyl group having 1 to 6 carbon atoms A monoalkylamino group having; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; a cyano group.

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

In the 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. If n2 is 1, the binding position of R ^c4, to the bond to the phenyl group R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

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

R ^c5 in the formula (C2-2) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 carbon atoms. 20 or less alkoxycarbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent which may have a substituent. A phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms which may have, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

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 it does not hinder the object of the present invention, and can be selected from various organic groups. Specific examples of the group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. And optionally includes a heterocyclyl group. As R ^c6 , a phenyl group which may have a substituent is more preferable among these groups, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c5 or R ^c6 further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Alkoxy group, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 1 to 6 carbon atoms Monoalkylamino group having the following alkyl group, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, etc. Is mentioned. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c5 or R ^c6 further have a substituent, the number of the substituents is not limited as long as the object of the present invention is not impaired, but 1 or more and 4 The following are preferred. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c5 or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

The group represented by the 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 a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to 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 the formula (C2-3). In formula (C2-3), the bonding position of R ^c7 with respect to the fluorene ring is not particularly limited. When the compound represented by the formula (C2-3) has one or more ^{R c7,} since such that the synthesis of the compound represented by the formula (C2-3) is easy, of 1 or more ^{R c7} It is preferred that one is attached at the 2-position in the fluorene ring. If R ^c7 is more, a plurality of R ^c7 is independently in may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as the object of the present invention is not ^{impaired, and} is appropriately selected from various organic groups. Preferable examples of R ^c7 being an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent. Optionally phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy Group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted There may be mentioned a heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group and the like.

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

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

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of the case where R ^c7 is 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 the case where R ^c7 is 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 a saturated aliphatic acyloxy group, the saturated aliphatic acyl group or saturated aliphatic acyloxy group preferably has 2 or more and 21 or less carbon atoms, and more preferably has 2 or more and 7 or less carbon atoms. When R ^c7 is a saturated aliphatic acyl group, specific examples thereof include 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, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca group Examples thereof include a noyl group and an n-hexadecanoyl group. When R ^c7 is a saturated aliphatic acyloxy group, specific examples thereof include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

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, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^c7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the phenylalkyl group preferably has 7 or more and 20 or less carbon atoms, and more preferably has 7 or more and 10 or less carbon atoms. 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 when R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. When R ^c7 is a naphthylalkyl group, specific examples thereof 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 the naphthyl group.

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

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

When R ^c7 is an amino group substituted with an organic group having 1 or 2, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a carbon atom having 7 to 20 which may have a substituent The following phenylalkyl groups, naphthyl groups which may have a substituent, naphthoyl groups which may have a substituent, naphthylalkyl groups which may have a substituent and have 11 to 20 carbon atoms, and heterocyclyl. Groups and the like. Specific examples of these suitable organic groups are the same as R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituents is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c7 is preferably a nitro group or a group represented by R ^c12 —CO— because the sensitivity tends to improve. 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 as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. And optionally include a heterocyclyl group. Of these groups, R ^c12 is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.

In formula (C2-3), R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, R ^c8 and R ^c9 are preferably chain alkyl groups which may have a substituent. When R ^c8 and R ^c9 are chain alkyl groups 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 chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. preferable. When R ^c8 and R ^c9 are chain alkyl groups, specific examples thereof 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-octyl group, n-nonyl group Group, an isononyl group, an n-decyl group, an isodecyl group and the like. Moreover, when R ^c8 and R ^c9 are alkyl groups, the alkyl groups may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. .. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferable examples when R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. 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, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The preferred number of substituents depends 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. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c8 and R ^c9 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as when R ^c8 and R ^c9 are chain alkyl groups.

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

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but 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 group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

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

R ^c8 and R ^c9 may be bonded to each other to form a ring. The group consisting of the ring formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 are bonded to each other to form a cycloalkylidene group, the ring forming the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and 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 condensed with one or more other rings. Examples of the ring which may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring and a pyridine ring. And a ring, a pyrazine ring, a pyrimidine ring and the like.

Among the groups described above among R ^c8 and R ^c9 , examples of suitable groups 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 of the linear alkylene group of A ⁰¹ is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ⁰² is an alkoxy group, the alkoxy group may be linear or branched, and is 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, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. 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, and is preferably linear. When A ⁰² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups which R ^c8 and R ^c9 have as a substituent. When A ⁰² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group which R ^c8 and R ^c9 have as a substituent.

Preferable specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n -Cyanoalkyl groups such as pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group Group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, and other phenyl groups Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy Carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy Carbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxy group Alkoxycarbonylalkyl groups such as cycarbonyl-n-heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5- Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4- Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-tri Fluoropropyl group and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

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

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

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

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

Wherein ^{(C2-II), R c1} and ^{where R c3} is the same in ^{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).

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

Specific preferred examples of the oxime ester compound represented by the 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, and 0.5% by mass or more and 20% by mass or less with respect to the total mass of the solid content of the photosensitive resin composition. More preferable. By setting the content of the photopolymerization initiator (C) within the above range, it is possible to obtain a photosensitive resin composition which has good curability and is less likely to cause defective pattern shape.

As described above, the photosensitive resin composition has a photopolymerization initiator (C) other than the photopolymerization initiator (C-I) represented by the following formula (C1) as the photopolymerization initiator (C). Other photopolymerization initiator (C-II). The ratio of the mass 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, more preferably 25% by mass or more and 90% by mass or less, and 30 More preferably, it is not less than mass% and not more than 85 mass %.

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 ratio of the mass of the α-aminoketone compound to the mass of the photopolymerization initiator (C-II) is from 5% by mass to 100% by mass. % Or less is preferable, 10% by mass or more and 50% by mass or less is more preferable, and 20% by mass or more and 40% by mass or less is further preferable.

When the photopolymerization initiator (C-II) contains a combination of an oxime ester compound other than the photopolymerization initiator (C-I) and an α-aminoketone compound, the mass of the photopolymerization initiator (C-II). In, the total ratio of the mass of the oxime ester compound and the mass of the α-aminoketone compound 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, and 80% by mass. % Or more, more preferably 90% by mass or more, still more preferably 100% by mass.

When the photopolymerization initiator (C-II) contains a combination of an oxime ester compound other than the photopolymerization initiator (C-I) and 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 of the compound is preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 45 mass% or less, and 20 mass% or more and 40 mass% or less. Is particularly preferable.

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

The colorant (D) contained in the photosensitive resin composition is not particularly limited, but is classified into Pigment in the color index (CI; Issued by The Society of Dyers and Colorists), for example. It is preferable to use a compound having the following color index (C.I.) number.

Examples of suitable yellow pigments include C.I. I. Pigment Yellow 1 (hereinafter, “C.I. Pigment Yellow” is the same, and only the numbers are described.) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53. , 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116. , 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180. , And 185.

Examples of suitable orange pigments include C.I. I. Pigment Orange 1 (hereinafter, “C.I. Pigment Orange” is the same, and only the numbers are 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 suitable purple pigments include C.I. I. Pigment Violet 1 (hereinafter, “C.I. Pigment Violet” is the same, and only the number will be described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50. Can be mentioned.

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

Examples of suitable blue pigments include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the numbers are described.) 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64. , And 66.

Examples of pigments having 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, a green pigment, 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 the like, C.I. I. Pigment Black 1, C.I. I. Pigment Black 7 and other black pigments.

Further, in the case of imparting light shielding properties to the photosensitive resin composition, it is preferable that the photosensitive resin composition contains a black pigment as the light shielding agent (D1). The photosensitive resin composition containing a black pigment is suitably used for forming a black matrix or a black column spacer in a liquid crystal display panel and forming a bank for partitioning a light emitting layer in an organic EL element.

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

As the carbon black, known carbon black such as channel black, furnace black, thermal black, lamp black and the like can be used, but it is preferable to use channel black having excellent light-shielding properties. Alternatively, resin-coated carbon black may be used.

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a black matrix of a liquid crystal display device such as a liquid crystal display, there is little leakage of current and high reliability. It is possible to manufacture a display with low power consumption.

As the carbon black, carbon black that has been subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity according to Bronsted's definition. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group and the like. The acidic group 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 it does not hinder the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions are preferable.

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

The method of introducing an acidic group into carbon black is not particularly limited. Examples of the method of introducing an acidic group include the following methods.
1) A method of introducing a sulfonic acid group 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 sulfite, hydrogen sulfite or the like.
2) A method of diazo coupling carbon black with an organic compound having an amino group and an acidic group.
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 protecting group with carbon black having a hydroxyl group.
5) A method in which a Friedel-Crafts reaction is performed on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group, and then deprotection is performed.

Among these methods, the method 2) is preferable because the acidic group introduction treatment is easy and safe. The organic compound having an amino group and an acidic group used in the 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 aminobenzene sulfonic 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, and more preferably 5 mmol or more and 100 mmol or less with respect to 100 g of carbon black.

The carbon black introduced with an acidic group may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance can be easily formed. Note that the coating treatment with the resin does not cause any adverse effect on 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 phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, thermosetting resins such as alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, and poly Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylene sulfone, polyarylate and polyetheretherketone. The coating amount of the resin on the carbon black is preferably 1% by mass or more and 30% by mass or less based on the total of the mass of the carbon black and the mass of the resin.

Further, as the black pigment, a perylene pigment can also be preferably used. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d-1), a perylene-based pigment represented by the following formula (d-2), and a perylene-based pigment represented by the following formula (d-3). Perylene pigments. Among commercially available products, product names K0084 and K0086 manufactured by BASF and pigment blacks 21, 30, 31, 32, 33, 34 and the like can be preferably used as the perylene-based pigment.

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 represents an acetyl group.

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

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

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

In formula (d-3), R ^d7 and R ^d8 each independently represent a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and containing a hetero atom of N, O, S, or P. Good. When R ^d7 and R ^d8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) are described in, for example, JP-A No. 62-1753. It can be synthesized using the method described in JP-B-63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the target product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

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

Further, a lactam pigment can be included as the 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 each is a geometric isomer, which is independently an E-form or a Z-form, and R ^d9 is independently a hydrogen atom, a methyl group, a nitro group, or methoxy. A group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, R ^d10's each independently represent a hydrogen atom, a methyl group, or a phenyl group, and R ^d11's each independently represent a hydrogen atom. , Methyl group or chlorine atom.
The compound represented by the formula (d-4) can be used alone or in combination of two or more kinds.
From the ^viewpoint of easy production of the compound represented by the formula (d-4), R ^d9 is preferably bonded to the 6-position of the dihydroindolone ring, and R ^d11 is bonded to the 4-position of the dihydroindolone ring. Preferably. From the same viewpoint, R ^d9 , R ^d10 , and R ^d11 are preferably hydrogen atoms.
The compound represented by the formula (d-4) has EE isomers, ZZ isomers, and EZ isomers as geometric isomers, but may be a single compound of any of these isomers, or geometric isomers of these isomers. May be a mixture of.
The compound represented by the formula (d-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

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

Further, 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 a black pigment. The AgSn alloy fine particles only need to contain an AgSn alloy as a main component, and may contain Ni, Pd, Au or the like as another metal component.
The average particle diameter 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 in which a chemically stable AgSn alloy is obtained is 1≦x≦10, and the range of x in which chemical stability and blackness are simultaneously obtained is 3≦x≦4.
Here, when the mass ratio of Ag in the AgSn alloy is calculated in the range of x,
When x=1, Ag/AgSn=0.4762
When x=3, 3·Ag/Ag3Sn=0.7317
When x=4, 4·Ag/Ag4Sn=0.7843
When x=10, 10·Ag/Ag10Sn=0.908
Becomes
Therefore, this AgSn alloy becomes chemically stable when Ag is contained in an amount of 47.6% by mass or more and 90% by mass or less, and Ag is contained in an amount of 73.17% by mass or more and 78.43% by mass or less. Chemical stability and blackness can be effectively obtained with respect to the amount.

The AgSn alloy fine particles can be produced by using an ordinary fine particle synthesis method. Examples of the fine particle synthesis method 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.

The AgSn alloy fine particles have a high insulating property, but the surface may be covered with an insulating film in order to further improve the insulating property depending on the use of the photosensitive resin composition. As a material of such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, a metal oxide having an insulating property, for example, silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), or the like is preferably used. Be done.
Further, as the organic polymer compound, a resin having an insulating property, for example, polyimide, polyether, polyacrylate, polyamine compound or the like is preferably used.

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

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

A black composition containing two or more kinds of black or chromatic pigments and/or dyes in combination can be used together with the above-described black pigment 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 substances and development residues after development.
The content of carbon black in the black composition is more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0% by mass.

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

Since it is possible to finely adjust the hue of black and it is easy to suppress the generation of floating matters and development residues after development, the black composition has a plurality of types than a colorant composed of a single type of colorant. The combination of the chromatic colorants is preferable.

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

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

Known organic pigments that have been conventionally used can be used as the above five-color organic pigments.
Examples of blue organic pigments include 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 can be mentioned.
Examples of purple organic pigments include C.I. I. Pigment Violet 19, and C.I. I. Pigment Violet 23 can be mentioned.
Examples of the yellow organic pigment include 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 can be mentioned.
Examples of orange organic pigments include 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 can be mentioned.
Examples of red organic pigments include 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, which 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 preferable.
By using these organic pigments in combination, it is easy to form a black cured film having a good black hue and an excellent optical density (OD value).
It

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. These organic pigments and red organic pigments are preferably combined. And more preferably at least one organic pigment selected from purple organic pigments.
Specific combinations of pigments belonging to organic pigments of respective colors include, for example,
C. I. Pigment Blue 15:4 and C.I. I. Pigment Yellow 139 and C.I. I. Pigment Red 254,
C. I. Pigment Blue 15:6 and C.I. I. Pigment Orange 64 and C.I. I. 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. Pigment Red 254, and
C. I. Pigment Blue 15:6 and C.I. I. Pigment Violet 23 and C.I. I. Pigment Red 256 and the like are preferable.

In order to uniformly disperse the above colorant (D) in the photosensitive resin composition, a dispersant may be further used. 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.
Note that a corrosive gas caused by the dispersant may be generated from the cured film. Therefore, it is also an example of a preferred embodiment that the pigment is subjected to dispersion treatment without using a dispersant.

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. Can be mentioned.
Further, these dyes can be used as a colorant (D) by dispersing them in an organic solvent or the like by lake formation (chlorination).
In addition to these dyes, for example, JP2013-225132A, JP2014-178477A, JP2013-137543A, JP2011-38085A, JP2014-197206A, and the like. The described dyes and the like can also be preferably used.

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

Particularly, when the black matrix is formed using the photosensitive resin composition, the amount of the light-shielding agent in the photosensitive resin composition should be adjusted so that the OD value per 1 μm of the black matrix film is 4 or more. Is preferred. When the OD value per 1 μm of the coating in the black matrix is 4 or more, a 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), it is preferable that the pigment is dispersed in the presence or absence of a dispersant at an appropriate concentration and then added to the photosensitive resin composition.
In the present specification, the amount of the above-mentioned pigment used can be defined as a value including the existing 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 is well cured even when using a light source with low irradiation energy such as LED exposure.

As the sensitizer (E), compounds 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 selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (═O) as a substituent. The compound having the substituent is preferably a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound.
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 the substituent 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, and 2 to 20 carbon atoms. And aliphatic acyl groups having 7 to 11 carbon atoms (aroyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, mercapto groups, and the like.

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

The substituted carbonyloxy group is a group represented by -O-CO- ^Ae . A ^e is not particularly limited as long as the sensitizer (E) has a desired sensitizing action, and may be various organic groups. As A, 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 are preferable. ..

The aryl group or aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as it does not impair the object of the present invention. When the aryl group or aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different.
Preferable 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, and 6 to 10 carbon atoms. An aryloxy group, an aliphatic acyl group having 2 to 7 carbon atoms, an aromatic acyl group (aroyl group) having 7 to 11 carbon atoms, a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and Examples thereof include a mercapto group.

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

In a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound substituted by 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 action can be obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 or more and 6 or less, and most preferably 3 or 4.
The monocycle forming the condensed polycycle does not necessarily have to be an aromatic ring as long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity.

Preferred examples of the condensed polycyclic aromatic hydrocarbon compound or the condensed polycycle contained in the condensed polycyclic aromatic heterocyclic compound include an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a xanthene ring, and thiol. A xanthene ring is mentioned. Among these rings, anthracene ring, naphthacene ring, and thioxanthene ring are preferable.

Specific examples of the compound containing an anthracene ring and preferably used 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,9,10-bis(isobutylcarbonyloxy)anthracene , 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(n-heptylcarbonyloxy)anthracene, 9,10-bis(2 -Ethylhexanoyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10-bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n-decylcarbonyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(2-naphthoyloxy)anthracene, 2-methyl-9,10-bis(acetyl) Oxy)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-pentyl) Carbonyloxy)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(propionyl) Oxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isopropylcarbonyloxy)anthracene 1,1-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-pentylcarbonyl) Oxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9,10-bis(benzoyloxy)anthracene, 1-methyl-9,10-bis(4-methyl) Benzoyloxy)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)-9,1 0-bis(n-propylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(tert-butyl)-9,10-bis(n-butylcarbonyl) Oxy)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- Examples thereof include 9,10-bis(4-(tert-butyl)-benzoyloxy)anthracene and 2-pentyl-9,10-bis(2-naphthoyloxy)anthracene.

Anthracene compounds substituted with a halogen atom are also preferable as the sensitizer (E). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Specific examples of the anthracene compound substituted with a halogen atom, which is preferable as the sensitizer (E), include 2-chloro-9,10-bis(acetyloxy)anthracene and 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-pentylcarbonyl) Oxy)anthracene, 1-fluoro-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(benzoyloxy)anthracene, 1-fluoro-9,10-bis(4-methyl) Benzoyloxy)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-butyl) Carbonyloxy)anthracene, 2-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n -Hexylcarbonyloxy)anthracene, 2-bromo-9,10-bis(benzoyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzoyloxy)anthracene, 2-bromo-9,10-bis( 2-naphthoyloxy)anthracene, 1-bromo-9,10-bis(acetyloxy)anthracene, 1-bromo-9,10-bis(propionyloxy)anthracene, 1-bromo-9,10-bi Sus(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- Examples include 9,10-bis(benzoyloxy)anthracene, 1-bromo-9,10-bis(4-methylbenzoyloxy)anthracene, and 1-bromo-9,10-bis(2-naphthoyloxy)anthracene. Be done.

Anthracene compounds substituted with an alkoxy group are also preferable as the sensitizer (E).
Specific examples of the anthracene compound substituted with an alkoxy group and preferable as the sensitizer (E) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 9,10-bis(n-). Propyloxy)anthracene, 9,10-bis(n-butyloxy)anthracene, 9,10-bis(n-pentyloxy)anthracene, 9,10-bis(isopentyloxyoxy)anthracene, 9,10-bis(n -Hexyloxy)anthracene, 9,10-bis(n-heptyloxy)anthracene, 9,10-bis(n-octyloxy)anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-(n-propyloxy)anthracene, 9-(n-butyloxy)anthracene, 9-(n-pentyloxy)anthracene, 9-(isopentyloxyoxy)anthracene, 9-(n-hexyl) Oxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy)anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9. , 10-diethoxyanthracene, 2-methyl-9,10-bis(n-propyloxy)anthracene, 2-methyl-9,10-bis(n-butyloxy)anthracene, 2-methyl-9,10-bis( n-pentyloxy)anthracene, 2-methyl-9,10-bis(isopentyloxyoxy)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(isopentyloxyoxy)anthracene, 2-ethyl-9,10-bis(n-hexyloxy)anthracene, 2 -Ethyl-9,10-bis(n-he Butyloxy)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-hexyl) Oxy)anthracene, 2-ethyl-9-(n-heptyloxy)anthracene, 2-ethyl-9-(n-octyloxy)anthracene, 2-ethyl-9-(2-ethylhexyloxy)anthracene, 2-chloro- 9,10-Dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis(n-propyloxy)anthracene, 2-chloro-9,10-bis(n-butyloxy) Anthracene, 2-chloro-9,10-bis(n-pentyloxy)anthracene, 2-chloro-9,10-bis(isopentyloxyoxy)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-ethylhexyl) (Oxy)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(isopentyloxyoxy)anthracene, 2-bromo-9,10-bis(n-hexyloxy)anthracene, 2-bromo-9,10- Bis(n-heptyloxy)anthracene, 2-bromo-9,10-bis(n-octyloxy)anthracene, 2-bromo-9,10-bis(2-ethylhexyloxy)anthracene, 2-chloro-9-methoxy Anthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9-(n-propyloxy)anthracene, 2-chloro-9-(n-butyloxy)anthracene, 2-chloro-9-(n-pentyloxy) Anthracene, 2-chloro-9-(isopentyloxyoxy)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-propyl). Oxy)anthracene, 2-bromo-9-(n-butyloxy)anthracene, 2-bromo-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxyoxy)anthracene, 2-bromo-9. -(N-Hexyloxy)anthracene, 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, and 2-bromo-9-(2-ethylhexyloxy) Anthracene and the like can be mentioned.

Among the above-described anthracene compounds, 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9 and 10-bis(acetyloxy)anthracene are preferred from the viewpoint of ease of production and performance as the sensitizer (E). ,10-Bis(n-propylcarbonyloxy)anthracene,9,10-bis(isopropylcarbonyloxy)anthracene,9,10-bis(n-butylcarbonyloxy)anthracene,9,10-bis(isobutylcarbonyloxy)anthracene , 9,10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis(2 -Ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene are preferred.

Specific examples of the compound containing a naphthacene ring, which is preferably 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-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. An alkylcarbonyloxy group-substituted naphthacene compound such as 12-bis(n-heptylbonyloxy)naphthacene;
2-Methyl-5,11-dioxo-6,12-bis(benzoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2-methyl-5 ,11-Dioxo-6,12-bis(m-toluoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene, 2-methyl-5,11 -Dioxo-6,12-bis(α-naphthoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene, 2-ethyl-5,11-dioxo -6,12-bis(benzoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12- Bis(m-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis( aroyloxy group-substituted naphthacene compounds such as α-naphthoyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthoyloxy)naphthacene;
2-methyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-methyl-5 11-dioxo-6,12-bis(n-propyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 2-methyl-5,11- Dioxo-6,12-bis(n-butyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-pentyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-heptyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis(methoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis( n-Propyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n- Butyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-pentyloxy) Carbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-heptyloxy) Carbonyloxy)naphthacene, and an alkoxycarbonyloxy group-substituted naphthacene compound such as 2-ethyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene;
2-Methyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-methyl -5,11-Dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-methyl -5,11-Dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene, 2-ethyl -5,11-Dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5. 11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5. Aroyloxycarbonyl such as 11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene An oxy group-substituted naphthacene compound may be mentioned.

Among the 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-butylcarbonyl) Oxy)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 the compound containing a thioxanthene ring which is preferably used as the sensitizer (E) include thioxanthen-9-one, 2-methyl-9H-thioxanthen-9-one and 2-isopropyl-9H-. Examples thereof include thioxanthen-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, and 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. Is more preferable. When the photosensitive resin composition contains a sensitizer within the above range, the curing reaction due to exposure particularly progresses uniformly, and it is easy to form a patterned cured film having a particularly favorable edge angle.

<Organic solvent (S)>
The photosensitive resin composition may typically contain an organic solvent (S) for the purpose of adjusting coating properties. 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. ) Alkylene glycol monoalkyl ethers; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol 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, 3-heptanone; methyl 2-hydroxypropionate, Lactic acid alkyl esters such as ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutyrate. Lepropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate. , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N,N-dimethylformamide, N,N-dimethylacetamide, and other amides. 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 depending on the application of the photosensitive resin composition. The amount of the organic solvent (S) used is, for example, 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>
The photosensitive resin composition may contain various other additives other than the above, if necessary. Specific examples include dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, coagulation inhibitors, thermal polymerization inhibitors, defoamers and surfactants.

Examples of the thermal polymerization inhibitor used in the photosensitive resin composition include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include silicone-based and fluorine-based compounds, and examples of the surfactant include anion-based, cation-based and nonionic compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition is prepared by uniformly mixing the desired amounts of the above components. 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 having excellent straightness and adhesion to a substrate and having a good cross-sectional shape.
Specifically, forming a coating film by coating the above-mentioned photosensitive resin composition on a substrate,
Position-selectively exposing the coating film,
Developing the exposed coating film;
A patterned cured film is produced by the method, including:

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 by using a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), or a non-contact type coating device such as a curtain flow coater. Is applied.

Next, the coating film is dried if necessary. The drying method is not particularly limited. As a drying method, for example, (1) a method of drying at a temperature of 80° C. or higher and 120° C. or lower, preferably 90° C. or higher and 100° C. or lower for 60 seconds or more and 120 seconds or less on a hot plate, (2) room temperature And leaving it in a warm air heater or infrared heater for several tens of minutes to several hours to remove the solvent.

Next, 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 an active energy ray such as ultraviolet rays or excimer laser light through a negative mask. The energy dose for irradiation varies depending on the composition of the photosensitive resin composition, but is preferably about 10 mJ/cm ² or more and 2000 mJ/cm ² or less.

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

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

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

[Examples 1-28 and Comparative Examples 1-13]
In Examples and Comparative Examples, a cardo resin synthesized according to the following method was used as the alkali-soluble resin (A) (component (A)).
First, in a 500 mL four-necked flask, 235 g of a bisphenolfluorene type epoxy resin (epoxy equivalent 235), tetramethylammonium chloride 110 mg, 2,6-di-tert-butyl-4-methylphenol 100 mg, and acrylic acid 72.0 g. Was charged, and the mixture was heated and dissolved at 90 to 100° C. while blowing air at a rate of 25 mL/min. Next, the temperature of the solution was gradually increased in a cloudy state and heated to 120° C. to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but the stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until it was less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, the mixture was cooled to room temperature to obtain a bisphenolfluorene type epoxy acrylate represented by the following formula, which was colorless and transparent and solid.

Next, 600 g of 3-methoxybutyl acetate was added to and dissolved in 307.0 g of the above-obtained bisphenolfluorene-type epoxy acrylate, and then 80.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, and the temperature was gradually raised to react at 110 to 115° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 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. The disappearance of the acid anhydride group was confirmed by IR spectrum.

In the examples and comparative examples, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer (B) (component (B)).

In the examples and comparative examples, the compounds described below were used as the photopolymerization initiator (C) (component (C)). In 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 the oxime ester compound as a photopolymerization initiator (C-II) other than the photopolymerization initiator (CI).

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

In Examples and Comparative Examples, the following D1 and D2 were used as the coloring agent (D) (component (D)). In addition, the amount of the colorant (D) described in Table 1 described later is not the amount of the dispersion liquid but the solid content amount (the amount of the pigment and the dispersant) in the dispersion liquid.
D1: Carbon black dispersion (carbon black content 20% by mass, dispersant content 5% by mass)
D2: Organic pigment mixed dispersion (CI Pigment Blue 15:6/CI Pigment Violet 23/CI Pigment Red 256=40% by mass/20% by mass/40% by mass, solid content concentration 15) mass%)

The amounts of the alkali-soluble resin (A), the photopolymerizable monomer (B), the photopolymerization initiator (C) of the type shown in Table 1, and the colorant of the type shown in Table 1 ( D), 0.2 parts by mass of a silane coupling agent ((3-phenylaminopropyl)trimethoxysilane), and 0.5 parts by mass of a surfactant, and organic so that the solid content concentration becomes 15% by mass. The photosensitive resin composition of each Example and Comparative Example was obtained by uniformly dissolving and dispersing in a solvent (S). As the organic solvent (S), a mixed solvent of 15% by mass of 3-methoxybutyl acetate and 85% by mass of propylene glycol monomethyl ether acetate was used.

The photosensitive resin compositions of Examples and Comparative Examples were applied onto a glass substrate (100 mm×100 mm) using a spin coater, prebaked at 90° C. for 120 seconds, and a coating film having a thickness of 1.0 μm was formed. Formed. Next, using a proximity exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask in which a line pattern having a width of 6 μm was formed. .. The exposure amount was set to three levels 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 post-baked at 230° C. for 30 minutes to form a line pattern.

<Straightness evaluation>
The rattling 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 “◯”, and the case where there was rattling was evaluated as “poor”.

<Adhesion evaluation>
The presence or absence of peeling of the formed line pattern was observed with an optical microscope to evaluate the pattern adhesion. The case where peeling was not observed was evaluated as “◯”, and the case where peeling was observed was evaluated as “x”.

<Taper angle>
As shown in FIG. 1, the taper angle is evaluated by measuring the angle θ formed between the substrate 90a and the side surface of the line portion 10 in the cross section in the width direction of the line portion 10 in the line pattern formed by the exposure of 40 mJ/cm ² . did.
In the case of the trapezoidal shape as shown in FIG. 1, θ is more than 0 degrees and less than 90 degrees, which is a forward taper shape. Further, in the case of the inverted trapezoidal shape as shown in FIG. 2, θ is more than 90 degrees and less than 180 degrees, which is an inverse taper shape.
In FIGS. 1 and 2, the surface where the substrate 90a and the line portion 10 of the cured pattern of the photosensitive resin composition are in contact is used as a reference surface, and the angle between the parallel line of the reference surface and the side surface of the line is expressed as θ. , The same as the above θ.
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 Δ: 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°C or less

The technical significance of the taper angle θ will be supplemented below. The taper angle θ is preferably 90 degrees to ensure fidelity to the mask pattern.
When a black matrix formed using a photosensitive resin composition is incorporated into an image display panel, liquid crystal may be arranged in contact with the black matrix. The molecular orientation of the liquid crystal is controlled by the voltage. By controlling this molecular orientation, the light transmittance changes drastically in the optical system including the 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 at the pattern boundary portion of the black matrix is different from that of the pattern flat portion (corresponding to the above line portion or space portion) due to the influence of the boundary step. Shows the behavior. As an optical phenomenon, even if the light transmittance is 0% at the pattern flat portion, the light ray is transmitted at the pattern boundary portion, and it is observed as light bleeding or light leakage at the pattern boundary portion. Not suitable as a panel or image display device.
This light bleeding phenomenon is remarkable when the taper angle θ of the black matrix pattern is more than 90 degrees, and is reduced when the line taper angle θ is 90 degrees or less. When a drive test is performed on the image display panel and the image display device, the taper angle θ is particularly suitable to be 85 degrees or less. If the angle is less than 70 degrees, the light transmission region becomes narrow (corresponding to narrowing of the space other than the line portion 10 in FIG. 1) and the amount of light decreases, which is not suitable as an image display panel or an image display device.
Therefore, for the liquid crystal display panel and the liquid crystal display device, 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, an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (CI) which is an oxime ester compound having a structure represented by the above formula (C1) , A photopolymerization initiator (C-I) and a photopolymerization initiator (C-II) other than the photopolymerization initiator (C-I) in a predetermined ratio, respectively, were used to form a patterned resin composition. It can be seen that the cured film has excellent straightness and adhesion to the substrate, and has a good cross-sectional shape.
On the other hand, either the photopolymerization initiator (C-I) or the photopolymerization initiator (C-II) is not contained, or the photopolymerization initiator (C-I) and the photopolymerization initiator (C-) are contained. The patterned cured film formed by using the photosensitive resin composition of Comparative Example not containing II) and II in a predetermined ratio can have both good straightness and good adhesion to a substrate. The cross-sectional shape was also poor.

Claims (9)

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 (C1-1):

In the structure represented by, a hydrogen atom bonded to the aromatic ring, excluding t2+t3 hydrogen atoms, X ⁰² and X ⁰³ are each independently a monovalent organic group, ⁰⁴ and X ⁰⁵ are each independently a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and 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 by a C—N bond, t4 and t5 are each independently 0 or 1, and t4 and At least one of t5 is 1. )
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. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C-II) is an oxime ester compound and/or an aminoketone compound. The photosensitive resin composition according to claim 2, wherein the photopolymerization initiator (C) contains the oxime ester compound and the aminoketone compound as the photopolymerization initiator (C-II). The oxime ester compound as the photopolymerization initiator (C-II) has the following formula (C2):

(In the formula (C2), R ^c1 represents a monovalent organic group, and R ^c2 represents the following formulas (C2-1) to (C2-3):

R ^c3 represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. And
In formula (C2-1), R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and n2 is , An integer between 0 and 4 inclusive,
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, and R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent or a substituent. Is a cyclic organic group which may have a hydrogen atom, R ^c8 and R ^c9 may be bonded to each other to form a ring, and n3 is an integer of 0 or more and 4 or less. )
The photosensitive resin composition according to claim 2, which is a compound represented by: R ^c1 is 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, and R ^c10 and R ^c11 are adjacent positions on the benzene ring. When present in, 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, and n7 is 0 or more. It is an integer of (n6+3) or less, and R ^c12 is a monovalent organic group.)
The photosensitive resin composition according to claim 4, which is a group represented by: Furthermore, the photosensitive resin composition of any one of Claims 1-5 containing a coloring agent (D). The photosensitive resin composition according to claim 6, wherein the colorant (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 7 onto a substrate;
Exposing the coating film position-selectively,
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 claim 1.

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