JP2022013302A - Photosensitive composition, cured product, method for producing cured film, and resin - Google Patents

Abstract

To provide a photosensitive composition capable of forming a cured product excellent in organic solvent resistance, a cured product of the photosensitive composition, a method for producing a cured film using the photosensitive composition, and a resin capable of being suitably blended in the photosensitive composition.SOLUTION: The photosensitive composition contains an alkali-soluble resin (A) and a photopolymerization initiator (C). As the alkali-soluble resin (A), there is used a reaction product of a compound (A-1) of a specific structure having a carboxy group and an epoxy compound (A-2) containing a cyclic structure other than an oxirane ring and having three or more epoxy group-containing groups bonded to the cyclic structure.SELECTED DRAWING: None

Description

The present invention comprises a photosensitive composition, a cured product of the photosensitive composition, a method for producing a cured film using the above-mentioned photosensitive composition, and a resin which can be suitably blended in the above-mentioned photosensitive tree composition. Regarding.

Curing by exposure in the manufacture of functional layers such as insulating layers in various semiconductor elements, the manufacture of image display panels such as liquid crystal display panels and organic EL display panels, and the manufacture of insulating layers and various optical functional layers in display devices. Negative photosensitive compositions to be obtained are widely used.

The photosensitive composition includes, for example, an acrylic resin, a silane coupling material having a specific structure, and a polymerizable compound as a photosensitive composition capable of forming a cured film having sufficient adhesion to a substrate. A photosensitive composition has been proposed (see Patent Document 1).

International Publication No. 2015/194339

In the manufacture of functional layers such as insulating layers in various semiconductor devices and the manufacture of image display panels such as liquid crystal display panels and organic EL display panels, organic solvents are often used in the manufacturing process. However, even if the known photosensitive composition described in Patent Document 1 is used, there is a problem that it is difficult to form a cured product having excellent organic solvent resistance.

The present invention has been made in view of the above problems, and uses a photosensitive composition capable of forming a cured product having excellent organic solvent resistance, a cured product of the photosensitive composition, and the above-mentioned photosensitive composition. It is an object of the present invention to provide a method for producing a cured film and a resin that can be suitably blended in the above-mentioned photosensitive composition.

In a photosensitive composition containing an alkali-soluble resin (A) and a photopolymerization initiator (C), the present inventors have a compound (A-1) having a specific structure having a carboxy group, other than an oxylan ring. The above-mentioned problems are solved by using a reaction product with an epoxy compound (A-2) having a cyclic structure and having three or more epoxy group-containing groups bonded to the cyclic structure as an alkali-soluble resin (A). We have found that it can be solved and have completed the present invention. Specifically, the present invention provides the following.

（式（ａ－１）中、Ｘ^ａは、下記式（ａ－２）：

で表される基を示し、Ｚ^ａは、テトラカルボン酸二無水物から２つのカルボン酸無水物基を除いた残基を示し、Ｒ^ａ０は、水素原子又は－ＣＯ－Ｙ^ａ－ＣＯＯＨで表される基を示し、Ｙ^ａは、ジカルボン酸無水物からカルボン酸無水物基を除いた残基を示し、ｔ１は、０以上２０以下の整数を示し、
式（ａ－２）中、Ｒ^ａ１は、それぞれ独立に水素原子、炭素原子数１以上６以下の炭化水素基、又はハロゲン原子を示し、Ｒ^ａ２は、それぞれ独立に水素原子又はメチル基を示し、Ｒ^ａ３は、それぞれ独立に直鎖又は分岐鎖のアルキレン基を示し、ｔ２は、０又は１を示し、Ｗ^ａは、下記式（ａ－３）：

で表される基を示し、
式（ａ－３）中の環Ａは、芳香族環と縮合していてもよく置換基を有していてもよい脂肪族環を示す。）
で表される化合物（Ａ－１）と、オキシラン環以外の環式構造を含み、且つ、前記環式構造に結合する３以上のエポキシ基含有基を有するエポキシ化合物（Ａ－２）との反応物を含む、感光性組成物である。 The first aspect of the present invention comprises an alkali-soluble resin (A) and a photopolymerization initiator (C).
The alkali-soluble resin (A) has the following formula (a-1):

(In the formula (a-1), Xa is the following formula ( ^a -2):

Indicates a group represented by, Z ^a indicates a residue obtained by removing two carboxylic acid anhydride groups from tetracarboxylic acid dianhydride, and R ^a0 is represented by ^a hydrogen atom or -CO-Ya-COOH. Ya indicates ^a residue obtained by removing the carboxylic acid anhydride group from the dicarboxylic acid anhydride, and t1 indicates 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 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group, respectively. , R ^a3 independently represent a linear or branched alkylene group, t2 represents 0 or 1, and Wa is the following formula ( ^a -3) :.

Indicates a group represented by
Ring A in formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring or may have a substituent. )
Reaction between the compound (A-1) represented by (A-1) and an epoxy compound (A-2) containing a cyclic structure other than the oxylan ring and having three or more epoxy group-containing groups bonded to the cyclic structure. It is a photosensitive composition containing a substance.

The second aspect of the present invention is a cured product of the photosensitive composition according to the first aspect.

A third aspect of the present invention is to apply the photosensitive composition according to the first aspect on a substrate to form a coating film.
It is a method for producing a cured film including exposing a coating film.

（式（ａ－１）中、Ｘ^ａは、下記式（ａ－２）：

で表される基を示し、Ｚ^ａは、テトラカルボン酸二無水物から２つのカルボン酸無水物基を除いた残基を示し、Ｒ^ａ０は、水素原子又は－ＣＯ－Ｙ^ａ－ＣＯＯＨで表される基を示し、Ｙ^ａは、ジカルボン酸無水物からカルボン酸無水物基を除いた残基を示し、ｔ１は、０以上２０以下の整数を示し、
式（ａ－２）中、Ｒ^ａ１は、それぞれ独立に水素原子、炭素原子数１以上６以下の炭化水素基、又はハロゲン原子を示し、Ｒ^ａ２は、それぞれ独立に水素原子又はメチル基を示し、Ｒ^ａ３は、それぞれ独立に直鎖又は分岐鎖のアルキレン基を示し、ｔ２は、０又は１を示し、Ｗ^ａは、下記式（ａ－３）：

で表される基を示し、
式（ａ－３）中の環Ａは、芳香族環と縮合していてもよく置換基を有していてもよい脂肪族環を示す。）
で表される化合物（Ａ－１）と、オキシラン環以外の環式構造を含み、且つ、前記環式構造に結合する３以上のエポキシ基含有基を有するエポキシ化合物（Ａ－２）との反応物である、樹脂である。 A fourth aspect of the present invention is the following formula (a-1):

(In the formula (a-1), Xa is the following formula ( ^a -2):

Indicates a group represented by, Z ^a indicates a residue obtained by removing two carboxylic acid anhydride groups from tetracarboxylic acid dianhydride, and R ^a0 is represented by ^a hydrogen atom or -CO-Ya-COOH. Ya indicates ^a residue obtained by removing the carboxylic acid anhydride group from the dicarboxylic acid anhydride, and t1 indicates 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 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group, respectively. , R ^a3 independently represent a linear or branched alkylene group, t2 represents 0 or 1, and Wa is the following formula ( ^a -3) :.

Indicates a group represented by
Ring A in formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring or may have a substituent. )
Reaction between the compound (A-1) represented by (A-1) and an epoxy compound (A-2) containing a cyclic structure other than the oxylan ring and having three or more epoxy group-containing groups bonded to the cyclic structure. It is a resin, which is a thing.

According to the present invention, a photosensitive composition capable of forming a cured product having excellent resistance to organic solvents, a cured product of the photosensitive composition, a method for producing a cured film using the above-mentioned photosensitive composition, and the above-mentioned photosensitive composition. It is possible to provide a resin that can be suitably blended in a sex composition.

（式（ａ－１）中、Ｘ^ａは、下記式（ａ－２）：

で表される基を示し、Ｚ^ａは、テトラカルボン酸二無水物から２つのカルボン酸無水物基を除いた残基を示し、Ｒ^ａ０は、水素原子又は－ＣＯ－Ｙ^ａ－ＣＯＯＨで表される基を示し、Ｙ^ａは、ジカルボン酸無水物からカルボン酸無水物基を除いた残基を示し、ｔ１は、０以上２０以下の整数を示し、
式（ａ－２）中、Ｒ^ａ１は、それぞれ独立に水素原子、炭素原子数１以上６以下の炭化水素基、又はハロゲン原子を示し、Ｒ^ａ２は、それぞれ独立に水素原子又はメチル基を示し、Ｒ^ａ３は、それぞれ独立に直鎖又は分岐鎖のアルキレン基を示し、ｔ２は、０又は１を示し、Ｗ^ａは、下記式（ａ－３）：

で表される基を示し、
式（ａ－３）中の環Ａは、芳香族環と縮合していてもよく置換基を有していてもよい脂肪族環を示す。）
で表される化合物（Ａ－１）と、オキシラン環以外の環式構造を含み、且つ、前記環式構造に結合する３以上のエポキシ基含有基を有するエポキシ化合物（Ａ－２）との反応物を含む。 << Photosensitive composition >>
The photosensitive composition contains an alkali-soluble resin (A) and a photopolymerization initiator (C).
The alkali-soluble resin (A) has the following formula (a-1):

(In the formula (a-1), Xa is the following formula ( ^a -2):

Indicates a group represented by, Z ^a indicates a residue obtained by removing two carboxylic acid anhydride groups from tetracarboxylic acid dianhydride, and R ^a0 is represented by ^a hydrogen atom or -CO-Ya-COOH. Ya indicates ^a residue obtained by removing the carboxylic acid anhydride group from the dicarboxylic acid anhydride, and t1 indicates 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 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group, respectively. , R ^a3 independently represent a linear or branched alkylene group, t2 represents 0 or 1, and Wa is the following formula ( ^a -3) :.

Indicates a group represented by
Ring A in formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring or may have a substituent. )
Reaction between the compound (A-1) represented by (A-1) and an epoxy compound (A-2) containing a cyclic structure other than the oxylan ring and having three or more epoxy group-containing groups bonded to the cyclic structure. Including things.

A cured product formed by using the photosensitive composition by containing the reaction product of the above compound (A-1) and the epoxy compound (A-2) as an alkali-soluble resin (A) in the photosensitive composition. Can improve the solvent resistance of.

When the photosensitive composition contains the reaction product of the above compound (A-1) and the epoxy compound (A-2) as the alkali-soluble resin (A), the cured product is 90 ° C. or higher and 250 ° C. or lower for 10 minutes. Even after post-baking under mild conditions of 60 minutes or less, it is easy to obtain sufficiently high solvent resistance of the cured product.

Further, when the photosensitive composition contains the reaction product of the above compound (A-1) and the epoxy compound (A-2) as the alkali-soluble resin (A) and does not contain a colorant, the photosensitive composition is used. It can be used to form a cured product having high light transmittance and excellent transparency.

Hereinafter, essential or arbitrary components contained in the photosensitive composition and a method for preparing the photosensitive composition will be described.

<Alkali-soluble resin (A)>
The photosensitive composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) contains a reaction product of the above-mentioned compound (A-1) and the above-mentioned epoxy compound (A-2). Hereinafter, this reactant is also referred to as “reactant (AI)”.
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.) having alkali solubility in the molecule.

The photosensitive composition may contain, as the alkali-soluble resin (A), an alkali-soluble resin other than the reactant (AI) together with the above-mentioned reactant (AI). The mass ratio of the reaction product (AI) in the alkali-soluble resin (A) is preferably 50% by mass or more, preferably 80% by mass, from the viewpoint that the desired effect can be easily obtained by using the reaction product (AI). The above is more preferable, 90% by mass or more is further preferable, and 100% by mass is particularly preferable.
Examples of the alkali-soluble resin other than the reaction product (AI) include novolak resin (A-II), modified epoxy resin (A-III), and acrylic resin (A-IV).

Hereinafter, the reactants (AI), the novolak resin (A-II), the modified epoxy resin (A-III), and the acrylic resin (A-IV) will be described.

[Reactant (AI)]
As described above, it is a reaction product of the above-mentioned compound (A-1) and the above-mentioned epoxy compound (A-2). The following methods for producing the compound (A-1), the epoxy compound (A-2), and the reactant (AI) will be described.

[Compound (A-1)]
Compound (A-1) is a cardo resin having a so-called cardo structure. As the compound (A-1), a compound represented by the following formula (a-1) is used.

In the formula (a-1), Xa represents ^a group represented by the following formula (a-2). t1 represents an integer of 0 or more and 20 or less.

In the above formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group. Shown, R ^a3 independently represents a linear or branched alkylene group, t2 represents 0 or 1, and Wa represents ^a group represented by the following formula (a-3).

In the formula (a-2), as ^Ra3 , an alkylene group having 1 or more and 20 or less carbon atoms is preferable, an alkylene group having 1 or more and 10 or less carbon atoms is more preferable, and an alkylene group having 1 or more and 6 or less carbon atoms is more preferable. Is particularly preferable, and ethane-1,2-diyl group, propane-1,2-diyl group, and propane1,3-diyl group are most preferable.

Ring A in formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring or 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, and adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring that may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

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

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

In the formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and t2 are as described in the formula (a-2). The ring A in the formula (a-2a) is as described in the formula (a-3).

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.
First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is replaced with a group represented by —R ^a3 -OH according to a conventional method, if necessary. Glysidylation 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 a diol compound represented by the formula (a-2a).
In the formula (a-2b) and the formula (a-2c), ^Ra1 , ^Ra3 , and t2 are as described for the formula (a-2). The ring A in the formula (a-2b) and the formula (a-2c) is as described in the formula (a-3).
The method for producing the diol compound represented by the formula (a-2a) is not limited to the above method.

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

In the above formula (a-1), R ^a0 is a hydrogen atom or ^a group represented by -CO-YA-COOH. Here, Ya represents ^a residue obtained by removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides are phthalic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydro. Phthalic anhydride, glutaric anhydride and the like can be mentioned.

Further, in the above formula (a-1), Za indicates ^a residue obtained by removing two acid anhydride groups from the tetracarboxylic dianhydride. Examples of tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydride represented by the following formula (a-4), pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, and biphenyltetracarboxylic acid dianhydride. Examples thereof include biphenyl ether tetracarboxylic acid dianhydride.
Further, in the above equation (a-1), t1 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、ｔ３は、０以上１２以下の整数を示す。）

(In the formula (a-4), R ^a4 , R ^a5 , and R ^a6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, and a fluorine atom. Indicated, t3 indicates an integer of 0 or more and 12 or less.)

The alkyl group that can be selected as ^Ra4 in the formula (a-4) is an alkyl group having 1 or more and 10 or less carbon atoms. By setting the number of carbon atoms contained in the alkyl group in this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and 1 or more and 4 or less, from the viewpoint of easily increasing the heat resistance of the reaction product (AI). Is more preferable, and 1 or more and 3 or less are particularly preferable.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

As R ^a4 in the formula (a-4), a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms is more preferable independently from the viewpoint of easily increasing the heat resistance of the reactant (AI). R ^a4 in the 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.
The plurality of ^Ra4s in the formula (a-4) are preferably the same group because it is easy to prepare a high-purity tetracarboxylic dianhydride.

T3 in the equation (a-4) indicates an integer of 0 or more and 12 or less. By setting the value of t3 to 12 or less, purification of the tetracarboxylic dianhydride can be facilitated.
The upper limit of t3 is preferably 5 and more preferably 3 because the purification of the tetracarboxylic dianhydride is easy.
From the viewpoint of the chemical stability of the tetracarboxylic dianhydride, the lower limit of t3 is preferably 1 and more preferably 2.
2 or 3 is particularly preferable for t3 in the formula (a-4).

The alkyl groups having 1 or more and 10 or less carbon atoms that can be selected as R ^a5 and R ^a6 in the formula (a-4) are the same as the alkyl groups having 1 or more and 10 or less carbon atoms that can be selected as R ^a4 . ..
R ^a5 and R ^a6 have hydrogen atoms or carbon atoms 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 the purification of tetracarboxylic acid dianhydride is easy. More preferably, it is 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 norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-Tetracarboxylic acid dianhydride (also known as "norbornane-2-spiri-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5'', 6,6'' -Tetracarboxylic acid dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane) -5,5'', 6,6''-tetra Norbornane-2-anhydrogenate, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (also known as "norbornane-" 2-Spiro-2'-Cyclohexanone-6'-Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride "), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''-(methylnorbornane) -5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopropanol-α'- Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-norborn-2''-norbornane-5, 5'', 6,6''-tetracarboxylic acid 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 acid dianhydride , Norbornane-2-spiro-α-cyclononanon-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclodecanone -Α'-Spyro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2' '-Norbornane-5,5'', 6,6''-Tetracarboxylic acid dianhydride, Norbornane-2-spiro-α-cyclododecanone-α'-Norbornane-5,5'-Norbornane-5,5' ', 6, 6''-Tetracarboxylic acid dianhydride, Norbornane Nan-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- Cyclotetradecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α' -Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'-spiro-2' '-Norbornane-5,5'', 6,6''-Tetracarboxylate dianhydride, Norbornane-2-spiro-α- (methylcyclohexanone) -α'-Spiro-2''-Norbornane-5,5 '', 6,6''-tetracarboxylic acid dianhydride and the like can be mentioned.

The weight average molecular weight of compound (A-1) is preferably 1000 or more and 40,000 or less, more preferably 1500 or more and 30,000 or less, and further preferably 2000 or more and 10,000 or less. By setting the above range, the solvent resistance of the cured product of the photosensitive composition can be particularly easily enhanced by using the reaction product (AI) as the alkali-soluble resin (A).

[Epoxy compound (A-2)]
The epoxy compound (A-2) is an epoxy compound containing a cyclic structure other than the oxylan ring and having three or more epoxy group-containing groups bonded to the cyclic structure. For example, phloroglucinol triglycyl ether corresponds to the epoxy compound (A-2). In phloroglucinol triglycidyl ether, the benzene ring structure corresponds to "cyclic structure other than oxylan ring". Further, the three glycidyloxy groups correspond to "three or more epoxy group-containing groups bonded to the cyclic structure".

The fact that the cyclic structure has 3 or more epoxy group-containing groups means that 3 or more epoxy group-containing groups are bonded to the monocyclic structure or the condensed cyclic structure.
For example, the glycidyl ether type phenol novolac epoxy resin does not fall under the epoxy compound (A-2). The glycidyl ether type phenol novolac epoxy resin usually contains a plurality of benzene ring structures as a cyclic structure and has 3 or more glycidyloxy groups as 3 or more epoxy group-containing groups. However, in the glycidyl ether type phenol novolac epoxy resin, only one glycidyloxy group is bonded to the benzene ring structure which is a monocyclic structure. Therefore, the glycidyl ether type phenol novolac epoxy resin does not satisfy the requirement that "three or more epoxy group-containing groups are bonded to the monocyclic structure or the condensed ring structure".

Suitable compounds as the epoxy compound (A-2) include compounds represented by the following formula (A-2a) or the following formula (A-2b).

In the formula (A-2a), ^Xa1 , ^Xa2 , and ^Xa3 are epoxy group-containing groups. In the formula (A-2b), X ^a4 and X ^a5 are epoxy group-containing groups or alkyl groups. In formula (A-2b), at least three of x1 ^Xa4 and x1 ^Xa5 are epoxy group-containing groups. x1 is an integer of 3 or more.

As the compound represented by the formula (A-2a), the compound represented by the following formula (A-2a1) is preferable.

In the formula (A-2a1), X ^a11 to X ^a13 are linear, branched or cyclic alkylene groups, arylene groups, -O-, -C (= O)-, -NH- and combinations thereof. It is a group consisting of. X ^a11 to X ^a13 may be the same or different, and are preferably the same. E1 to E3 are independently oxylanyl groups, epoxycycloalkyl groups, or epoxypolycycloalkyl groups, respectively.
The epoxycycloalkyl group means a group in which at least one of the saturated carbon-carbon bonds represented by> CH-CH <in the cycloalkyl group is substituted with the structure containing the following oxylan ring. Further, the epoxy polycycloalkyl group means a group in which at least one of the saturated carbon-carbon bonds in the polycycloalkyl group such as a norbornyl group and a tricyclodecanyl group is replaced with a structure containing the following oxylan ring.

Preferable specific examples of the epoxycycloalkyl group and the epoxypolycycloalkyl group include the following groups.

In the formula (A-2a1), as the linear, branched chain or cyclic alkylene group as X ^a11 to X ^a13 , an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms is preferable. As the arylene group as X ^a11 to X ^a13 , an arylene group having 6 or more carbon atoms and 10 or less carbon atoms is preferable.
X ^a11 to X ^a13 are linear groups consisting of an alkylene group having 1 or more and 3 or less carbon atoms, a phenylene group, -O-, -C (= O)-, -NH-, and a combination thereof. Is preferable, at least one of a linear alkylene group having 1 or more and 3 or less carbon atoms such as a methylene group and a phenylene group, or at least of -O-, -C (= O)-and NH-. A group consisting of a combination of one type is preferable.

Preferred specific examples of the compound represented by the formula (A-2a1) include the following compounds.

As described above, the cyclic siloxane compound represented by the following formula (A-2b) is preferably used as the epoxy compound (A-2).

In the formula (A-2b), X ^a4 and X ^a5 are epoxy group-containing groups or alkyl groups. In formula (A-2b), at least three of x1 ^Xa4 and x1 ^Xa5 are epoxy group-containing groups. x1 is an integer of 3 or more.

The epoxy group-containing groups of X ^a4 and X ^a5 are not particularly limited. As X ^a4 and X ^a5 , the same groups as the epoxy group-containing groups as X ^a1 , X ^a2 , and X ^a3 in the formula (A-2a) can be adopted.
As the epoxy group-containing group as X ^a4 and X ^a5 , a glycidyloxyalkyl group, an epoxycycloalkylalkyl group, and an epoxypolycycloalkylalkyl group are preferable.
Preferable examples of the glycidyloxyalkyl group include, for example, 3-glycidyloxy-n-propyl group, 2-glycidyloxyethyl group, and 4-glycidyloxy-n-butyl group.

Preferable examples of the epoxycycloalkylalkyl group and the epoxypolycycloalkylalkyl group include the following groups.

The number of carbon atoms of the alkyl group as X ^a4 and X ^a5 is not particularly limited. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group and the like having 1 or more and 18 or less carbon atoms (preferably 1 or more and 6 or less carbon atoms, particularly preferably 1 or more and 3 or less carbon atoms). Can be mentioned as a linear or branched alkyl group of.

As the combination of X ^a4 and X ^a5 , a combination of an alkyl group and an epoxy group-containing group is preferable.

In the formula (A-2b), x1 represents an integer of 3 or more, and among them, an integer of 3 or more and 6 or less is preferable in terms of excellent reactivity with the compound (A-1).

The epoxy compound represented by the formula (A-2b) has 3 or more epoxy group-containing groups in the molecule, preferably 3 or more and 6 or less from the viewpoint of reactivity with the compound (A-1). It is preferably 3 or 4.

Preferable specific examples of the epoxy compound represented by the formula (A-2b) include the following compounds.

(Method for producing reactant (AI))
The method for producing the reaction product (AI) is not particularly limited as long as the reaction between the compound (A-1) and the epoxy compound (A-2) can proceed satisfactorily. The reaction between the compound (A-1) and the epoxy compound (A-2) is specifically a reaction between the carboxy group of the compound (A-1) and the epoxy group of the epoxy compound. ..

The reaction product (AI) is usually a compound represented by the following formula (A-1a), a compound represented by the following formula (A-1b), and a compound represented by the following formula (A1-c). It consists of one or more species selected from the group consisting of.

In the formula (A-1a), the formula (A-1b), and the formula ( ^A -1c), Xa, ^Ya , Za, and t1 are as described above for the formula ( ^a -1), respectively. In the formula (A-1a), the formula (A-1b), and the formula (A-1c), ^RA is independently a hydrogen atom, a group represented by the following formula (Ai), or the following formula (Aii). ). In the formula (A-1a), the formula (A-1b), and the formula ( ^A -1c), a plurality of RAs may be the same or different.

The group represented by the formula (Ai) and the group represented by the formula (Aii) are groups derived from the epoxy compound (A-2), respectively. In the formula (Ai) and the formula (Aii), R ⁰² , R ⁰³ , and R ⁰⁴ are each independently a hydrogen atom or an organic group constituting an epoxy group-containing group contained in the epoxy compound (A-2). be. R ⁰¹ is an organic group that independently constitutes a single bond or an epoxy group-containing group contained in the epoxy compound (A-2). When both R ⁰⁴ and R ⁰¹ are organic groups constituting an epoxy group-containing group, they may be bonded to each other to form a ring. R ^EP is a cyclic group that gives a cyclic structure in the epoxy compound (A-2) and has two or more epoxy group-containing groups that may react with the carboxy group in the compound (A-1).

As described above, the group represented by the formula (Ai) and the group represented by the formula (Aii) are each derived from the epoxy compound (A-2). An epoxy compound having a ^REP and an epoxy group-containing group giving a group represented by the formula (Ai) or the formula (Aii) is represented by the following formula (Aii). In the formula (Aii), R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , and R ^EP are as described above for the formula (Ai) and the formula (Aii).

In the formula (A-1a), the formula (A-1b), and the formula ( ^A -1c), two or more of the plurality of RAs are represented by the formula (Ai), or the formula (Aii). When represented, in these groups, the plurality of R ^01s , the plurality of R ^02s , the plurality of R ^03s , the plurality of R ^04s , and the plurality of R ^EPs may be the same or different. good.

As an example, the reactant is a compound represented by the above formula (A1-c), and a part of ^RA in the formula (A1-c) is a group represented by the formula (Ai), and the formula (Ai). ), The structure of the compound when two or more epoxy group-containing groups of ^REP react with the carboxy group in the compound (A-1) is shown as the following formula (A-1d).

In the formula ( ^A -1d), Xa, ^Ya , Za, and t1 are as described above for the formula ( ^a -1), respectively. ^RA is a hydrogen atom, a group represented by the above formula (Ai), or a group represented by the above formula (Aii), respectively. R ⁰² , R ⁰³ , and R ⁰⁴ are organic groups that independently constitute a hydrogen atom or an epoxy group-containing group contained in the epoxy compound (A-2). R ⁰¹ is an organic group that independently constitutes a single bond or an epoxy group-containing group contained in the epoxy compound (A-2). When R ⁰⁴ and R ⁰¹ are organic groups constituting an epoxy group-containing group, they may be bonded to each other to form a ring. R ^EP is a cyclic group that gives a cyclic structure in the epoxy compound (A-2) and has two or more epoxy group-containing groups that may react with the carboxy group in the compound (A-1). When RA represented by the formula ( ^A -1d) is a group represented by the above formula (Ai) or a group represented by the above formula (Aii), two or more ^RAs of the ^RA are present. The epoxy group-containing group of the above may react with the carboxy group in the compound (A-1). The ratio of two or more epoxy group-containing groups possessed by ^REP to react with the carboxy group in the compound (A-1) is the charging ratio of the compound (A-1) and the epoxy compound (A-2) or the compound ( It is appropriately adjusted by adjusting the conditions of the reaction between A-1) and the epoxy compound (A-2).
In the formula (A-1d), x2 and x3 are integers of 0 or more, respectively, and integers of 1 or more and 4 or less are preferable.
For example, when R ^EP in the formula (A-1d) is derived from the epoxy compound represented by the formula (A-2a), x2 and x3 are 1 or 0, respectively, and the sum of x2 and x3 is 1. be. When x2 is 0, x3 is 1. In this case, the carboxy group of the compound (A-1) and the unreacted epoxy group-containing group are present in the reactant represented by the formula (A1-d).
When R ^EP in the formula (A-1d) is derived from the epoxy compound represented by the formula (A-2b), x2 and x3 are integers of 0 or more (x1 × 2-2) or less, respectively. As for x1, it is as described in the formula (A-2b). R ^EP in the formula (A1-d) is derived from the epoxy compound represented by the formula (A-2b), and the total number of epoxy group-containing groups as X ^a4 and X ^a5 in the formula (A-2b) is x4. When x2 is less than 0 or more (x4-2), the carboxy group of the compound (A-1) and the unreacted epoxy group in the reactant represented by the formula (A1-d) Containing groups are present.

When producing the reaction product (AI), for example, it is preferable to react 5 parts by mass or more and 90 parts by mass or less of the compound (A-1) with 1 part by mass of the epoxy compound (A-2). The reaction is more preferably 5 parts by mass or more and 50 parts by mass or less, and further preferably 5 parts by mass or more and 30 parts by mass or less.
The reaction between the compound (A-1) and the epoxy compound (A-2) usually proceeds spontaneously by mixing the two.

The charging ratio of the compound (A-1) and the epoxy compound (A-2) can be appropriately changed depending on the use of the photosensitive composition. For example, when all the epoxy groups of the epoxy compound (A-2) are reacted with the carboxy group of the compound (A-1), the unreacted epoxy group does not remain, so that the reactant (AI) or The storage stability of the photosensitive composition is good. In this case, the curing reaction of the photosensitive composition is a reaction between the ethylenically unsaturated double bonds of the reactants (AI).

When no epoxy group remains, the charging ratio of the compound (A-1) and the epoxy compound (A-2) is the compound (A-1) with respect to 1 equivalent of the epoxy group of the epoxy compound (A-2). It is preferable that the carboxy group contained in the epoxide group is 0.90 equivalent or more and 1.20 equivalent or less.
If the charging ratio is within this range, the residual epoxy group can be made very small, gelation during the reaction can be suppressed, and the reaction product (AI) having good storage stability can be easily obtained.

Further, by reducing the amount of the compound (A-1) used and leaving an unreacted epoxy group, the ethylenically unsaturated double bond derived from the compound (A-1) and the epoxy group are combined. The reaction product (AI) is obtained. When such a reactant (AI) is used, the reaction due to the ethylenically unsaturated double bond and the reaction due to the epoxy group can be used in combination for curing. In this case, the adhesion of the cured product to the metal material can be improved, and the shrinkage of the cured product during curing can be suppressed.

When the epoxy group remains, the compound (A1) has the compound (A1) as the charging ratio of the compound (A-1) and the epoxy compound (A-2) with respect to one equivalent of the epoxy group of the epoxy compound (A-2). A ratio in which the carboxy group is 0.20 equivalent or more and less than 0.90 equivalent is preferable.

The reaction between the compound (A-1) and the epoxy compound (A-2) is preferably carried out in an organic solvent.
Examples of the solvent that can be used for the reaction between the compound (A-1) and the epoxy compound (A-2) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, and ethylene glycol mono-. n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , Tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2- Ketones such as heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, butyric acid Other esters such as ethyl, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene , Xylene and other aromatic hydrocarbons; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

In order to satisfactorily react the compound (A-1) with the epoxy compound (A-2) to obtain a reaction product (AI) having a sufficiently increased molecular weight, the compound (A1) in the reaction solution should be obtained. ) And the total concentration of the epoxy compound (A-2) are preferably 30% by mass or more and 70% by mass or less, and more preferably 40% by mass or more and 60% by mass or less.

The temperature at which the compound (A-1) and the epoxy compound (A-2) are reacted is not particularly limited. For example, the reaction between the compound (A-1) and the epoxy compound (A-2) is −20 ° C. or higher and 100 ° C. or lower, preferably −10 ° C. or higher and 60 ° C. or lower, and more preferably 0 ° C. or higher and 40 ° C. or lower. Can be done. The reaction temperature may be constant or may vary during the reaction.

The time for reacting the compound (A-1) with the epoxy compound (A-2) is not particularly limited. For example, the time for reacting the compound (A-1) with the epoxy compound (A-2) is preferably 1 hour or more and 24 hours or less, and more preferably 2 hours or more and 12 hours or less.

The reaction between the compound (A-1) and the epoxy compound (A-2) is preferably carried out until, for example, the weight average molecular weight of the reactant (AI) reaches 5,000 or more, and 6,000 or more. More preferably done. The weight average molecular weight is a polystyrene-equivalent molecular weight measured by gel permeation chromatography.

[Novolak resin (A-II)]
The photosensitive composition may contain a novolak resin (A-II) as the alkali-soluble resin (A). As the novolak resin (A-II), various novolak resins conventionally blended in the photosensitive composition can be used. The novolak resin (A-II) is preferably obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

(Phenols)
Examples of the phenols used in producing the novolak resin (A-II) include phenols; cresols such as o-cresol, m-cresol, 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 , 5-Trialkylphenols such as trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone. (Each alkyl group has 1 or more and 4 or less carbon atoms.); Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. 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 in combination. In this case, various properties such as heat resistance of the cured product formed by using the photosensitive composition can be adjusted by adjusting the blending ratio of both.
The blending 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 a ratio within such a range, it is easy to obtain a photosensitive composition capable of forming a cured product having excellent heat resistance.

Further, a novolak resin produced by using m-cresol and 2,3,5-trimethylphenol in combination is also preferable. When such a novolak resin is used, it is particularly easy to obtain a photosensitive composition capable of forming a cured product that does not easily flow excessively by heating during post-baking.
The mixing ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the molar ratio of m-cresol / 2,3,5-trimethylphenol is 70/30 or more and 95/5 or less. Is preferable.

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

(Acid catalyst)
Acid catalysts used in the preparation of novolak resin (A-II) include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, and phosphoric acid; formic acid, oxalic acid, acetic acid, diethylsulfate, and Examples thereof include organic acids such as paratoluene sulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular weight)
The polystyrene-equivalent weight average molecular weight (Mw; hereinafter, also simply referred to as “weight average molecular weight”) of the novolak resin (A-II) is resistant to the flow of the cured product formed by using the photosensitive composition. From the viewpoint, 2000 is preferable as the lower limit value, 5000 is more preferable, 10000 is particularly preferable, 15000 is more preferable, 20000 is the most preferable, 50000 is preferable as the upper limit value, 45000 is more preferable, 40,000 is more preferable, and 35000 is the most preferable. preferable.

As the novolak resin (A-II), at least two kinds having different polystyrene-equivalent weight average molecular weights can be used in combination. By using a combination of large and small materials having different weight average molecular weights, it is possible to balance the developability of the photosensitive composition and the heat resistance of the cured product formed by using the photosensitive composition.

[Modified epoxy resin (A-III)]
The photosensitive composition may contain a modified epoxy resin (A-II) as the alkali-soluble resin (A). The alkali-soluble resin (A) has an epoxy compound (a-3a) and an unsaturated group-containing carboxylic acid because it realizes higher flow resistance during baking of the cured product and easily imparts high water resistance to the cured product. It may contain a polybasic acid anhydride (a-3c) adduct (A-III), which is a reaction product with the acid (a-3b). Such an adduct is also referred to as "modified epoxy resin (A-III)".
In the specification of the present application and the scope of claims, a compound that falls under the above definition and does not fall under the above-mentioned compound (A-1) is referred to as a modified epoxy resin (A-III).

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 containing no aromatic group. Often, aromatic epoxy compounds having an aromatic group are preferred.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a bifunctional or higher functional 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 metaxylylene diamine, tetraglycidyl bisaminomethylcyclohexane and the like. Glycyzylamine type epoxy resin; heterocyclic epoxy resin such as triglycidyl isocyanurate; fluoroglycinol 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] Trifunctional epoxy resins such as -2-propanol; tetrafunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresolsinol tetraglycidyl ether, and tetraglycidoxybiphenyl can be mentioned.

Further, 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 photosensitive composition capable of forming a cured product having an excellent balance between sensitivity and developability and 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 the formula (a-3a-1), R ^a7 is a phenyl group which may independently have a hydrogen atom, an alkyl group having 1 or more and 12 or less carbon atoms, a halogen atom, or a substituent. j is an integer of 1 or more and 4 or less.)

When R ^a7 is an alkyl group having 1 or more carbon atoms and 12 or less carbon atoms, specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and 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 thereof 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 substituents are 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. The group is mentioned.

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

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

（式（ａ－３ａ－３）中、ｋは、式（ａ－３ａ－２）と同様である。） Among the epoxy compounds represented by the formula (a-3a-2), it is particularly easy to obtain a photosensitive composition having an excellent balance between sensitivity and developability, and therefore, it is represented by the following formula (a-3a-3). 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 containing a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule is preferable. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-flufurylacrylic acid, α-cyanocinnamic acid, and cinnamic acid. Further, the unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more.

The epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) can be reacted by a known method. As a preferable reaction method, for example, the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) are mixed with a tertiary amine such as triethylamine or benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, or the like. Using a quaternary ammonium salt such as tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, or triphenylphosphine as a catalyst, 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 or longer and several tens of hours or shorter. The method can be mentioned.

The ratio of the amounts used in the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) is the epoxy equivalent of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b). The ratio of a-3b) to the carboxylic acid equivalent is usually preferably 1: 0.5 to 1: 2, more preferably 1: 0.8 to 1: 1.25, and 1: 0.9 to 1: 1. .1 is particularly preferable.
When the ratio of the amount of the epoxy compound (a-3a) used and 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 preferable because it tends to improve.

(Polybasic acid anhydride (a-3c))
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 for example, phthalic anhydride, succinic anhydride, thalic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are used. Phthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic 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 , The compound represented by the following formula (a-3c-1), and the compound represented by the following formula (a-3c-2) can be mentioned. Further, the polybasic acid anhydride (a-3c) may be used alone or in combination of two or more.

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

(In the formula (a-3c-2), ^Ra8 represents an alkylene group which may have a substituent having 1 or more and 10 or less carbon atoms.)

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings because it is easy to obtain a photosensitive composition having an excellent balance between sensitivity and developability. Further, 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.
The amount ratio used is the number of moles of OH groups in the component after the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), and the polybasic acid anhydride (a-3c). ), The equivalent ratio of the acid anhydride group 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 composition having good developability.

The acid value of the modified epoxy resin (A-III) is preferably 10 mgKOH / g or more and 150 mgKOH / g or less, and more preferably 70 mgKOH / g or more and 110 mgKOH / g or less in terms of resin solid content. Sufficient solubility in a developing solution can be obtained by setting the acid value of the resin to 10 mgKOH / g or more, and sufficient curability can be obtained by setting the acid value to 150 mgKOH / g or less, and the surface property can be improved. Can be good.

The weight average molecular weight of the modified epoxy resin (A-III) is preferably 1000 or more and 40,000 or less, and more preferably 2000 or more and 30,000 or less. When the weight average molecular weight is 1000 or more, it is easy to form a cured product having excellent heat resistance and strength. Further, when it is 40,000 or less, it is easy to obtain a photosensitive composition showing sufficient solubility in a developing solution.

[Acrylic resin (A-IV)]
Acrylic resin (A-IV) is also preferable as a component constituting the alkali-soluble resin (A).
As the acrylic resin (A-IV), 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. The (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 the object of the present invention is not impaired.

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 the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be linear, branched or cyclic.

The substituent other than the hydrocarbon group in the organic group of ^Ra 10 is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group and a cyanato group. , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfo group, sulfonate 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'independently indicate 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 substituent may be linear, branched or cyclic.

Further, the organic group as Ra 10 may have a reactive functional group such as an acryloyloxy group, a ^{metaacryloyloxy} group, an epoxy group or an oxetanyl group.
Acyl groups having an unsaturated double bond or the like, such as an acryloyloxy group and a metaacryloyloxy group, may be present in at least a part of the epoxy group in an acrylic resin (A-IV) containing a structural unit having an epoxy group, for example. , It can be produced by reacting with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

The 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. Further, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is linear or branched, the number of carbon atoms thereof 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 are 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, Examples thereof include an isodecyl group.

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. , Adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, and tetracyclododecyl group.

As a specific example of the compound represented by the formula (a-4-1) when the compound represented by the formula (a-4-1) has a chain-like group having an epoxy group as ^Ra10 , Examples thereof include (meth) acrylic acid epoxyalkyl esters such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate. ..

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. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.

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 are, for example, the following formulas (a-4-1a) to (a-4). Examples thereof include the compound represented by -1o). Among these, in order to obtain appropriate developability, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferable, and the following formulas (a-4-1a) to (a-4-1a) are preferable. The compound represented by (a-4-1c) is more preferable.

In the above formula, ^Ra 20 represents a hydrogen atom or a methyl group, Ra ²¹ represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less carbon atoms, and Ra ²² represents 2 having 1 or more and 10 or less carbon atoms. It indicates a valent hydrocarbon group, and t indicates an integer of 0 or more and 10 or less. As ^Ra21 , a linear or branched alkylene group, for example, 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 ^Ra22 include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, _{-CH2 -} Ph-CH2- (Ph is (Indicating a phenylene group) is preferable.

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

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, and 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.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like. Can be mentioned.

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

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl ballerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl. Examples thereof include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkylstyrene such as methylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Examples thereof include halostyrene such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene and 4-fluoro-3-trifluoromethylstyrene; and the like.

The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from other monomers in the acrylic resin (A-IV) 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-IV) is preferably 5% by mass or more and 50% by mass or less with respect to the mass of the acrylic resin (A-IV). More preferably, it is by mass or more and 30% by mass or less.

When the acrylic resin (A-IV) 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-IV) is 1% by mass or more. It is preferably 50% by mass or less, more preferably 1% by mass or more and 30% by mass or more, and particularly preferably 1% by mass or more and 20% by mass or less.
Since the acrylic resin (photosensitive) contains a structural unit having an unsaturated double bond in an amount within the above range, the acrylic resin can be incorporated into the cross-linking reaction in the resist film and homogenized, so that the column spacer can be made uniform. Effective for improving heat resistance and mechanical properties.

The weight average molecular weight of the acrylic resin (A-IV) is preferably 2000 or more and 50,000 or less, and more preferably 3000 or more and 30,000 or less. Within the above range, it tends to be easy to balance the film forming ability of the photosensitive composition and the developability after exposure.

The content of the alkali-soluble resin (A) is preferably 10% by mass or more and 65% by mass or less, and preferably 15% by mass or more and 50% by mass or less, based on the total mass of the solid content of the photosensitive composition. More preferred. Within the above range, it is easy to obtain a photosensitive composition having excellent developability.

<Photopolymerizable monomer (B)>
The photosensitive composition may contain a photopolymerizable monomer (B). As the photopolymerizable monomer (B) of the cured product, a monomer having an ethylenically unsaturated group is preferable. Such monomers include monofunctional monomers and polyfunctional monomers.
When the photosensitive composition contains the photopolymerizable monomer (B), it is particularly easy to obtain a cured product having excellent organic solvent resistance by using the photosensitive composition.
In particular, when the photosensitive composition contains a polyfunctional monomer, the cured product has sufficiently high solvent resistance even if the cured product is post-baked under mild conditions of 90 ° C. or higher and 250 ° C. or lower and 10 minutes or longer and 60 minutes or lower. Easy to get.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) 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 (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, 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, half (meth) acrylate of phthalic acid derivative and the like can be mentioned. These monofunctional monomers can 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-hexaneglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetra acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Elythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane, 2-hydroxy-3 -(Meta) 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 (ie, reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc. and 2-vidroxyethyl (meth) acrylate), methylenebis (meth) acrylamide, Examples thereof include polyfunctional monomers such as (meth) acrylamide methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacrylic formal. These polyfunctional monomers can be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a trifunctional or higher functional monomer is preferable because the cured product of the photosensitive composition tends to improve the adhesion to the substrate, the strength and the resistance to the organic solvent. A polyfunctional monomer having four or more functionalities is more preferable, and a polyfunctional monomer having five or more functionalities is further preferable.
Specifically, it is preferable to use a polyfunctional monomer having five or more functionalities, and it is more preferable to use dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate.

The content of the photopolymerizable monomer (B) in the photosensitive composition is preferably 1% by mass or more and 50% by mass or less, and 5% by mass or more and 40% by mass or less, based on the total mass of the solid content of the photosensitive composition. Is more preferable. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specifically, as the photopolymerization initiator (C), 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, O-acetyl-1- [6- (2- (2-) Methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime, O-acetyl-1- [6- (pyrol-2-ylcarbonyl) -9-ethyl-9H carbazole-3-yl] eta Non-oxime, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] Metanon O-acetyloxime, 2- (benzoyloxy) Imino) -1- [4- (Phenylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isoamylbenzoate, benzyl-β-methoxyethyl Acetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4- Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1 , 2-Benz anthraquinone, 2,3-diphenyla Intraquinone, azobisisobutyronitrile, benzoylperoxide, cumenehydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m) -Methylphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl- 4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p. -Dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetonone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4- Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridin, 1,7-bis- (9-acrydinyl) heptane, 1,5-bis -(9-Acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ether] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-) 2-yl) ether] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ether] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (3,4-dimethoxyphenyl) ether] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) )-S-Triazine, 2- (4-ethoxystyryl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl- 6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloro Examples thereof include methyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and the like. ..

These photopolymerization initiators can be used alone or in combination of two or more. The photopolymerization initiator (C) preferably contains two or more kinds of photopolymerization initiators in combination.
In this case, it is easy to effectively use light rays having a wide range of wavelengths included in the exposure light, and it is easy to adjust the sensitivity of the photosensitive composition to an appropriate range.

Among these, it is particularly preferable to use an oxime ester compound as the photopolymerization initiator (C) in terms of sensitivity. Examples of preferable compounds as oxime ester compounds include O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime and O-acetyl-1-. [6- (Pyrol-2-ylcarbonyl) -9-ethyl-9H carbazole-3-yl] etanone oxime and 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1- Octanone can be mentioned.

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

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group.
n1 is an integer of 0 or more and 4 or less,
n2 is 0 or 1,
R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent.
R ^c3 is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms. )

In the formula (c1), R ^c1 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group 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 benzoyloxy which may have a substituent. A 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, and a substituent. A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, an amino group, 1 , Or an amino group substituted with 2 organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When n1 is an integer of 2 or more and 4 or less, R ^c1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further possessed by the substituent.

When R ^c1 is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 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 and 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 an n-decyl group and an isodecyl group. Further, when R ^c1 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c1 is an alkoxy group 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 , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms 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 ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms 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 ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanol group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and 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 Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoloxy group, an n-pentanoyloxy group, and 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms 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 ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and 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-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, ^Rc1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or fused between such monocycles, or between such monocycles and a benzene ring. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Examples thereof include isoindole, indridin, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin and the like. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. , Saturated aliphatic acyl group having 2 or more and 20 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and 7 or more carbon atoms which may have a substituent. A phenylalkyl group of 20 or less, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, and Examples include a heterocyclyl group. Specific examples of these suitable organic groups are the same as for R ^c1 . Specific examples of the amino group substituted with the organic group 1 or 2 include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group and 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, Naftylamino 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 decanoyylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further have a substituent, the substituent includes an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, and the like. Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, alkyl group with 1 to 6 carbon atoms Examples thereof include a monoalkylamino group having, a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c1 further have a substituent, the number of the substituent 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, the naphthyl group, and the heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c1 , an alkyl group having 1 or more and 6 or less carbon atoms and 1 carbon atom have carbon atoms 1 or less because they are chemically stable, have few steric obstacles, and facilitate the synthesis of an oxime ester compound. A group selected from the group consisting of an alkoxy group having 6 or less carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable. ..

The position where R ^c1 binds to the phenyl group is the case where the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is the 1st position and the position of the methyl group is the 2nd position for the phenyl group to which R ^c1 is bonded. In addition, the 4th or 5th position is preferable, and the 5th position is more preferable. Further, n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

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

In R ^c2 , the substituent contained in the phenyl group or the carbazolyl group is not particularly limited as long as it does not impair the object of the present invention. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon atom. Cycloalkyl group with 3 or more and 10 or less, cycloalkoxy group with 3 or more and 10 or less carbon atoms, saturated aliphatic acyl group with 2 or more and 20 or less carbon atoms, alkoxycarbonyl group with 2 or more and 20 or less carbon atoms, carbon atom It has a saturated aliphatic acyloxy group having a number of 2 or more and 20 or less, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, and a substituent. A 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 which may have a substituent and has 7 or more and 20 or less carbon atoms. It has 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 naphthoxycarbonyl group which may have a substituent, and a substituent. It may have a naphthoyloxy group, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl which may have a substituent. Examples thereof include an amino group substituted with a group, an amino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cyclo having 3 to 10 carbon atoms. An alkyl group, a saturated aliphatic acyl group having 2 or more and 20 or less carbon atoms, an alkoxycarbonyl group having 2 or more and 20 or less carbon atoms, a phenyl group which may have a substituent, and a benzoyl group which may have a substituent. , A phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 or more and 20 or less carbon atoms, a naphthyl group which may have a substituent, and a substituent. May have a naphthoyl group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent and may have 11 or more and 20 or less carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclyl group. Examples thereof include a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or the carbazolyl group may have are 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. For a phenylalkyl group which may have a group, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted with one or two organic groups. , R ^c1 .

In R ^c2 , as an example of the substituent when the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, an alkyl having 1 or more and 6 or less carbon atoms is used. Group; alkoxy group with 1 or more and 6 or less carbon atoms; saturated aliphatic acyl group with 2 or more and 7 or less carbon atoms; alkoxycarbonyl group with 2 or more and 7 or less carbon atoms; saturated aliphatic group with 2 or more and 7 or less carbon atoms It is selected from the group consisting of an acyloxy group; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Benzoyl group substituted with a group; monoalkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms; dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms; morpholin-1-yl group; piperazin- 1-Il group; halogen; nitro group; cyano group can be mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. It is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

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

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

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

(R ^c5 and R ^c6 are monovalent organic groups, respectively.)

When R ^c4 in the formula (c2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. A preferred example of the case where R ^c4 is an organic group in the formula (c2) is an alkyl group having 1 or more and 6 or less carbon atoms; an alkoxy group having 1 or more and 6 or less carbon atoms; and 2 or more and 7 or less carbon atoms. Saturated aliphatic acyl group; alkoxycarbonyl group having 2 or more and 7 or less carbon atoms; saturated aliphatic acyloxy group having 2 or more and 7 or less carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; 1 to 6 carbon atoms Benzoyl group substituted with a group selected from the group consisting of the following alkyl group, morpholin-1-yl group, piperazine-1-yl group, and phenyl group; mono having an alkyl group having 1 to 6 carbon atoms. Alkoxyamino group; dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms; morpholin-1-yl group; piperazine-1-yl group; halogen; nitro group; cyano group.

In R ^c4 , it is 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 piperazine-1-yl group, and a phenyl group. The benzoyl group; nitro group is preferable, and the benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazine-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.

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

R ^c5 in the formula (c3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ^c5 are 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. It may have an alkoxycarbonyl group of 20 or more, 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. A phenylalkyl group having 7 or more and 20 or less 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 or more and 20 or less carbon atoms which may have a substituent, 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 or more and 20 or less carbon atoms is preferable, an alkyl group having 1 or more and 6 or less carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c6 in the formula (c3) is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of the group suitable for 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. Examples thereof include heterocyclyl groups which may be used. Among these groups, a phenyl group which may have a substituent is more preferable as R ^c6 , and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the substituent includes an alkyl group having 1 or more and 6 or less carbon atoms and 1 carbon atom. An alkoxy group having 6 or more carbon atoms, a saturated aliphatic acyl group having 2 or more carbon atoms and 7 or less carbon atoms, an alkoxycarbonyl group having 2 or more carbon atoms and 7 or less carbon atoms, a saturated aliphatic acyloxy group having 2 or more carbon atoms and 7 or less carbon atoms, and a carbon atom number. Monoalkylamino group having 1 or more and 6 or less alkyl groups, dialkylamino group having 1 or more and 6 or less carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and Examples include a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. It is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c3 in the formula (c1) is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

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

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

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

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

In formula (c4), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is attached to a 6-membered aromatic ring on the fluorene ring in the formula (c4), which is different from the 6-membered aromatic ring attached to the group represented by-(CO) _n5- . In the formula (c4), the binding position of R ^c7 with respect to the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has 1 or more R ^c7 , one of the 1 or more R ^c7 is a fluorene ring because the compound represented by the formula (c4) can be easily synthesized. It is preferable to bind to the 2-position of the inside. When there are a plurality of R ^c7s , the plurality of R ^c7s may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group 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 benzoyloxy which may have a substituent. A 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, and a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.

When R ^c7 is an alkyl group, the number of carbon atoms of 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 a straight chain or a branched chain. Specific examples of the case where R ^c7 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 and 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 an n-decyl group and an isodecyl group. Further, when R ^c7 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^c7 is an alkoxy group 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 , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^c7 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 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, a cyclooctyl group and the like. 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, a cyclooctyloxy group and the like.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanol group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and 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 Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^c7 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, and 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of 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 a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and 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 an isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c7 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, ^Rc7 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, O, or fused between such monocycles, or between such monocycles and a benzene ring. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazol, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indolidine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when ^Rc7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and the like. Saturated aliphatic acyl group having 2 or more and 21 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and 7 or more and 20 carbon atoms which may have a substituent. The following phenylalkyl group, naphthyl group which may have a substituent, naphthoyl group which may have a substituent, naphthylalkyl group which may have a substituent and has 11 or more and 20 or less carbon atoms, and heterocyclyl. The group etc. can be mentioned. Specific examples of these suitable organic groups are the same as for R ^c7 . Specific examples of the amino group substituted with the organic group 1 or 2 include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group and 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, Naftylamino 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 decanoyylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, alkyl group with 1 to 6 carbon atoms Examples thereof include a monoalkylamino group having, a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituent 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, the naphthyl group, and the 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, as R ^c7 , a nitro group or a group represented by R ^c12 -CO- tends to improve the sensitivity and is preferable. R ^c12 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of a suitable group 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. Examples thereof include heterocyclyl groups which may be used. Among these groups, 2-methylphenyl group, thiophen-2-yl group, and α-naphthyl group are particularly preferable as R ^c12 .
Further, when R ^c7 is a hydrogen atom, the transparency tends to be good, which is preferable. If R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.

In the formula (c4), R ^c8 and R ^c9 are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ^c8 and R ^c9 may be coupled to each other to form a ring. Among these groups, as R ^c8 and R ^c9 , a chain alkyl group which may have a substituent is preferable. When R ^c8 and R ^c9 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear 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. Specific examples of cases where R ^c8 and R ^c9 are chain alkyl groups 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, and a 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 Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ^c8 and R ^c9 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

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 it does not impair the object of the present invention. 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 in the preferred example 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, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms 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 number of preferred substituents depends on the number of carbon atoms of 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 substituents that the cyclic organic group may have are 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 via a carbon-carbon bond? , It is preferable that the group is formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

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, and 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 and tricyclodecyl group. Examples thereof include a tetracyclododecyl group and an adamantyl group.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or such monocycles, or such monocycles and benzene rings. It is a heterocyclyl group condensed with. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazol, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indolidine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done.

R ^c8 and R ^c9 may be coupled 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 form a cycloalkrylidine group, the ring constituting 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 the bond between R ^c8 and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a 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. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

As an example of a suitable group among R ^c8 and R ^c9 described above, a group represented by the formula −A ¹ − A ² can be mentioned. In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkylene group of A ¹ is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² 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 ² is an alkyl halide group, the halogen atom contained in the alkyl halide group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The alkyl halide group may be linear or branched, preferably linear. When A ² is a cyclic organic group, the example of the cyclic organic group is the same as that of the cyclic organic group that R ^c8 and R ^c9 have as a substituent. When A ² is an alkoxycarbonyl group, an example of an alkoxycarbonyl group is similar to the alkoxycarbonyl group that R ^c8 and R ^c9 have as substituents.

Suitable specific examples of R ^c8 and R ^c9 are 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 Ethyl such as group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group. 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-etoki An alkoxycarbonylalkyl group such as a sicarbonyl-n-heptyl group and an 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 Examples thereof include a fluoropropyl group and an alkyl halide group such as a 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among the above-mentioned suitable groups as R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group and 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-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^c10 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups and substituents, as in R ^c7 . 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. A good 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 naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group which may have a group, an amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, a piperazine-1-yl group and the like. Specific examples of these groups are similar to those described for R ^c7 . Further, as R ^c10 , 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 substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ^c7 may have.

Among the organic groups, R ^c10 includes an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthio which may have a substituent on the aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is the most preferable. preferable. Among the phenyl groups that 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. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. 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 that may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

Further, as R ^c10 , a group represented by ^{−A3 -} CO—O—A4 is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. ^A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ³ is an alkylene group, the number of carbon atoms of 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 ^A4 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. Suitable specific examples of ^A4 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl. Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group and the like.

Preferable specific examples of the group represented by -A ³ -CO-O-A ⁴ are 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, 3-phenoxycarbonyl-n-propyl group and the like.

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０以上４以下の整数であり、Ｒ^ｃ１３及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１以上８以下の整数であり、ｎ８は１以上５以下の整数であり、ｎ９は０以上（ｎ８＋３）以下の整数であり、Ｒ^ｃ１５は有機基である。） Although R ^c10 has been described above, the group represented by the following formula (c4a) or (c4b) is preferable as R ^c10 .

(In formulas (c4a) and (c4b), R ^c13 and R ^c14 are organic groups, respectively, n6 is an integer of 0 or more and 4 or less, and R ^c13 and R ⁸ are present at adjacent positions on the benzene ring. In this case, R ^c13 and R ^c14 may be coupled to each other to form a ring, n7 is an integer of 1 or more and 8 or less, n8 is an integer of 1 or more and 5 or less, and n9 is 0 or more (n8 + 3). It is the following integer, and R ^c15 is an organic group.)

Examples of organic groups for R ^c13 and R ^c14 in formula (c4a) are similar to R ^c7 . As R ^c13 , an alkyl group or a phenyl group is preferable. When R ^c13 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, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 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 (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalene-1-yl group and 1,2,3,4-. Examples thereof include a tetrahydronaphthalene-5-yl group. In the above formula (c4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (c4b), R ^c15 is an organic group. Examples of the organic group include groups similar to the organic group described for R ^c7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of 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. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

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

In the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 or more and 11 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the substituent which may be possessed when R ^c11 is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. Further, as the substituent which may be possessed when R ^c7 is an aryl group, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

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

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

Preferable oxime ester compounds other than the above include, for example, the oxime ester compound represented by the formula (I) described in JP-A-2015-509704 (International Publication No. 2013/083505), and the oxime ester compound represented by Formulation 2016-531926 (International Publication No. 2013/083505). Examples thereof include an oxime ester compound represented by the formula (I) described in International Publication No. 2015/036910).
Preferable specific examples of the oxime ester compound represented by the formula (I) described in JP-A-2015-509704 (International Publication No. 2013/083505) include methanone, [8-[[(acetyloxy) imino]. [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- (2-ethylhexyl) -11H-benzo [a] carbazole-5-yl]-, (2,4,6-) Trimethylphenyl).
Suitable specific examples of the oxime ester compound represented by the formula (I) described in JP-T-2016-531926 (International Publication No. 2015/036910) include 1-pentanone and 1- [4- [4- ( 2-benzofuranylcarbonyl) phenyl] thio] phenyl] -4-methyl-, 1- (o-acetyloxime) can be mentioned.

The content of the photopolymerization initiator (C) is 0.5% by mass or more and 30% by mass or less with respect to the mass (total solid content) of the photosensitive composition excluding the mass of the organic solvent (S) described later. It is preferably 1% by mass or more and 20% by mass or less. By setting the content of the photopolymerization initiator (C) in the above range, it is possible to obtain a photosensitive composition having good curability and less likely to cause defective pattern shape.

The photoinitiator (C) may be combined with a photoinitiator aid. Photoinitiator aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate 2-. Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropion Examples thereof include thiol compounds such as acid, methyl 3-mercaptopropionate, pentaeristoltetramercaptoacetate and 3-mercaptopropionate. These photoinitiator aids can be used alone or in combination of two or more.

<Organic solvent (S)>
The photosensitive composition preferably contains an organic solvent (S) for dilution. 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, and 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. (poly) ) Alkylene glycol monoalkyl ethers; (poly) alkylene such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. 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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybuty Lupropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide and other amides and the like.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, lactic acid alkyl esters, and other esters described above are preferable, and alkylene glycol monoalkyl ether acetates, described above. Other ethers and other esters described above are more preferred. These solvents can be used alone or in combination of two or more.
The content of the organic solvent (S) is preferably such that the solid content concentration of the photosensitive composition is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less.

<Other ingredients>
The photosensitive composition may contain various additives, if necessary. Additives include sensitizers, curing accelerators, fillers, dispersants, adhesion promoters such as silane coupling agents, antioxidants, anti-aggregation agents, thermal polymerization inhibitors, defoamers, surfactants, etc. Examples thereof include colorants such as dyes and pigments.

<Method for preparing photosensitive composition>
The photosensitive composition is prepared by mixing each of the above components with a stirrer. In addition, you may filter using a membrane filter or the like so that the prepared photosensitive composition becomes uniform.

≪Manufacturing method of cured film≫
A cured product can be obtained by exposing the above-mentioned photosensitive composition. The form of the cured product is not particularly limited, but a cured film is preferable.
As a typical method for producing a cured film,
By applying the above-mentioned photosensitive composition on a substrate to form a coating film,
Examples include exposing the coating film and including.

Further, by performing regioselective exposure on the coating film and developing the exposed coating film with a developing solution, a cured film patterned in a desired shape can be obtained.

When the exposed coating film is not developed, it is preferable to post-bake the exposed coating film, and when the exposed coating film is developed, the developed coating film is subjected to. On the other hand, it is preferable to perform post-baking.
Since the above-mentioned photosensitive composition contains the reaction product (AI) that satisfies the predetermined requirements as the alkali-soluble resin (A), the post-baking conditions are 90 ° C. or higher and 250 ° C. or lower, 10 minutes or longer and 60 minutes or lower. Even under mild conditions such as, a cured film having excellent resistance to organic solvents can be formed.

As a method of applying the photosensitive composition on the substrate, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used. The method can be mentioned. After coating the photosensitive composition, if necessary, the organic solvent and the like are removed from the coating film by drying.

Next, the coating film is exposed by irradiating it with active energy rays such as ultraviolet rays and excimer laser light. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive composition, but is preferably about 20 mJ / cm ² or more and 100 mJ / cm ² or less, for example.
When performing regioselective exposure, the exposure is performed through a negative mask having a desired pattern.

When regioselective exposure is performed on the coating film, the exposed coating film is developed with a developing solution. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

After that, the cured film patterned by development is post-baked as necessary. As the post-baking conditions, mild conditions such as 90 ° C. or higher and 250 ° C. or lower and 10 minutes or longer and 60 minutes or lower are preferable.

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

[Preparation Example 1]
Compound A-1-1 is the resin obtained in Preparation Example 1 below.
First, in a 500 ml four-necked flask, 235 g of bisphenol fluorene-type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid. Was charged, and the mixture was heated and dissolved at a temperature of 90 ° C. or higher and 100 ° C. or lower while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was cloudy, and the solution was heated to 120 ° C. to completely dissolve it. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene-type epoxy acrylate thus obtained to dissolve it, and then 77.2 g of pyromellitic dianhydride and 1 g of tetraethylammonium bromide were mixed. Then, the temperature was gradually raised and the reaction was carried out at a temperature of 110 ° C. or higher and 115 ° C. or lower 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 compound A-1-1. The disappearance of the acid anhydride group was confirmed by IR spectrum.

[Preparation Example 2]
Compound A-1-2 in the same manner as in Preparation Example 1, except that 77.2 g of pyromellitic dianhydride is changed to 106 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride. Got

[Example 1]
Compound A-1-1 (weight average molecular weight (Mw): 2000, Mw / Mn: 2.0) obtained in Preparation Example 1 of 47.5 g and epoxy compound A-2-1 having the following structure of 2.5 g. Was mixed with propylene glycol monomethyl ether to a concentration of 50% by mass, and both were reacted at room temperature for 6 hours. As a result, a solution containing a reaction product of compound A-1-1 and epoxy compound A-2-1 at a concentration of 50% by mass was obtained. The weight average molecular weight (Mw) of the reactants was 9800 and Mw / Mn was 7.8.

[Example 2]
1 part by mass of the reaction product obtained in Example 1, 0.8 part by mass of dipentaerythritol hexaacrylate, 6% by mass of a photopolymerization initiator having the following structure, and 1% by mass of 3-glycidoxypropyltrimethoxy. Silane and 0.2% by mass BYK-310 (surfactant manufactured by Big Chemie) were dissolved in propylene glycol monomethyl ether so as to have a solid content concentration of 22% by mass to obtain a photosensitive composition. .. The amounts (% by mass) of the photopolymerization initiator, 3-glycidoxypropyltrimethoxysilane, and BYK-310 used were the mass of the reactant obtained in Example 1 and the mass of dipentaerythritol hexaacrylate. It is a mass ratio to the total of.

The obtained photosensitive composition was applied onto a silicon substrate by a spin coater, and then the photosensitive composition on the silicon substrate was heated at 85 ° C. for 120 seconds to form a coating film having a thickness of 3 μm. The formed coating film was exposed to an exposure amount of 20 mJ / cm ² through a mask for forming a line-and-space pattern having a line width of 40 μm / space width of 40 μm. The exposed coating film was spray-developed by contacting the exposed coating film with an aqueous solution of potassium hydroxide having a concentration of 0.04% by mass for 60 seconds. The developed coating film was heated at 90 ° C. for 60 minutes to obtain a cured film of a photosensitive composition patterned in a line shape.

The obtained cured film was immersed in N-methyl-2-pyrrolidone at room temperature for 5 minutes. When the film thickness of the cured film before and after immersion was measured and the residual film ratio, which is the ratio of the film thickness after immersion to the film thickness before immersion, was calculated, the residual film ratio was 95.9%. That is, the cured film made of the cured product of the photosensitive composition obtained in Example 2 had excellent solvent resistance that was hardly dissolved in NMP.

[Comparative Example 1]
A photosensitive composition was obtained in the same manner as in Example 2 except that the reaction product was changed to the compound A-1-1 obtained in Preparation Example 1. Using the obtained photosensitive composition, the residual film ratio when the cured film made of the cured product of the photosensitive composition was immersed in NMP was calculated in the same manner as in Example 1. The calculated residual film ratio was 76.7%. That is, the cured film made of the cured product of the photosensitive composition obtained in Comparative Example 1 was easily dissolved in NMP and was inferior in solvent resistance.

[Comparative Example 2]
A photosensitive composition was obtained in the same manner as in Example 2 except that the reaction product was changed to the compound A-1-2 obtained in Preparation Example 2. Using the obtained photosensitive composition, the residual film ratio when the cured film made of the cured product of the photosensitive composition was immersed in NMP was calculated in the same manner as in Example 1. The calculated residual film ratio was 68.4%. That is, the cured film made of the cured product of the photosensitive composition obtained in Comparative Example 2 was easily dissolved in NMP and was inferior in solvent resistance.

[Example 3]
2 parts by mass of the reactant obtained in Example 1, 0.85 parts by mass of dipentaerythritol hexaacrylate, 6.5% by mass of the photopolymerization initiator used in Example 2, and 3% by mass of 3-glyce. Sidoxypropyltrimethoxysilane and 0.2% by mass BYK-310 (surfactant manufactured by Big Chemie) are dissolved in propylene glycol monomethyl ether so as to have a solid content concentration of 22% by mass, and are photosensitive. The composition was obtained. The amounts (% by mass) of the photopolymerization initiator, 3-glycidoxypropyltrimethoxysilane, and BYK-310 used were the mass of the reactant obtained in Example 1 and the mass of dipentaerythritol hexaacrylate. It is a mass ratio to the total of.

The obtained photosensitive composition was applied onto a glass substrate by a spin coater, and then the photosensitive composition on the glass substrate was heated at 80 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The formed coating film was exposed to an exposure amount of 100 mJ / cm ² . The coated film after exposure was heated at 90 ° C. for 60 minutes to obtain a cured film of the photosensitive composition.
The light transmittance (wavelength 380 to 780 nm) of the obtained cured film was measured by MCPD-3700 (manufactured by Otsuka Electronics Co., Ltd.). As a result, the average light transmittance in the wavelength range of 380 nm to 780 nm was 99%. The light transmittance at a wavelength of 400 nm was 97.1%.

[Comparative Example 3]
A photosensitive composition was obtained in the same manner as in Example 3 except that the reaction product was changed to the compound A-1-1 obtained in Preparation Example 1. Using the obtained photosensitive composition, the light transmittance of the cured film was measured in the same manner as in Example 3. As a result, the average light transmittance in the wavelength range of 380 nm to 780 nm was 99%. The light transmittance at a wavelength of 400 nm was 97%.

[Comparative Example 4]
The reaction product was changed to the compound A-1-2 obtained in Preparation Example 2, and the solvent was changed to a mixed solvent consisting of 20% by mass of 3-methoxybutyl acetate and 80% by mass of propylene glycol monomethyl ether. Other than that, a photosensitive composition was obtained in the same manner as in Example 3. Using the obtained photosensitive composition, the light transmittance of the cured film was measured in the same manner as in Example 3. As a result, the average light transmittance in the wavelength range of 380 nm to 780 nm was 99%. The light transmittance at a wavelength of 400 nm was 96.9%.

When the NMP resistance of the cured film made of the cured product of the photosensitive composition of Example 3, Comparative Example 3 and Comparative Example 4 was confirmed according to the above-mentioned method, the cured product of the photosensitive composition of Example 3 was confirmed. The NMP resistance of the cured film was superior to that of the cured film made of the cured product of the photosensitive composition of Comparative Example 3 or Comparative Example 4.
From the above, it can be seen that a cured film made of a cured product of a photosensitive composition containing a reactant satisfying a predetermined requirement and not containing a colorant has excellent solvent resistance and high transparency.

Claims (9)

It contains an alkali-soluble resin (A) and a photopolymerization initiator (C).
The alkali-soluble resin (A) has the following formula (a-1):

(In the formula (a-1), Xa is the following formula ( ^a -2):

Indicates a group represented by, Z ^a indicates a residue obtained by removing two carboxylic acid anhydride groups from tetracarboxylic acid dianhydride, and R ^a0 is represented by ^a hydrogen atom or -CO-Ya-COOH. Ya indicates ^a residue obtained by removing the carboxylic acid anhydride group from the dicarboxylic acid anhydride, and t1 indicates 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 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group, respectively. , R ^a3 independently represent a linear or branched alkylene group, t2 represents 0 or 1, and Wa is the following formula ( ^a -3) :.

Indicates a group represented by
Ring A in formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring or may have a substituent. )
Reaction between the compound (A-1) represented by (A-1) and an epoxy compound (A-2) containing a cyclic structure other than the oxylan ring and having three or more epoxy group-containing groups bonded to the cyclic structure. A photosensitive composition comprising a substance. The reaction product according to claim 1, wherein the reactant is obtained by reacting 1 part by mass of the epoxy compound (A-2) with the compound (A-1) in a range of 5 parts by mass or more and 90 parts by mass or less. Photosensitive composition. The epoxy compound (A-2) has the following formula (A-2a) or the following formula (A-2b):

(In the formula (A-2a), ^Xa1 , ^Xa2 , and ^Xa3 are epoxy group-containing groups, and in the formula (A-2b), ^Xa2 , and ^Xa3 are epoxy group-containing groups or alkyl. It is a group, and at least three of x1 ^Xa4 and x1 ^Xa5 are the epoxy group-containing groups, and x1 is an integer of 3 or more.)
The photosensitive composition according to claim 1 or 2, which is a compound represented by. The photosensitive composition according to claim 3, wherein the epoxy compound is a compound represented by the formula (A-2b), and the epoxy group-containing group is an epoxycycloalkylalkyl group. The cured product of the photosensitive composition according to any one of claims 1 to 4. The photosensitive composition according to any one of claims 1 to 4 is applied onto the substrate to form a coating film.
A method for producing a cured film, which comprises exposing the coating film. The coating film is regioselectively exposed.
The method for producing a cured film according to claim 6, which comprises developing the exposed coating film with a developing solution. When the exposed coating film is not developed, the exposed coating film is post-baked.
When developing the exposed coating film, post-baking is performed on the developed coating film.
The method for producing a cured film according to claim 6 or 7, wherein the post-baking condition is 90 ° C. or higher and 250 ° C. or lower, 10 minutes or longer and 60 minutes or shorter. The following formula (a-1):

(In the formula (a-1), Xa is the following formula ( ^a -2):

Indicates a group represented by, Z ^a indicates a residue obtained by removing two carboxylic acid anhydride groups from tetracarboxylic acid dianhydride, and R ^a0 is represented by ^a hydrogen atom or -CO-Ya-COOH. Ya indicates ^a residue obtained by removing the carboxylic acid anhydride group from the dicarboxylic acid anhydride, and t1 indicates 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 or more and 6 or less carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group, respectively. , R ^a3 independently represent a linear or branched alkylene group, t2 represents 0 or 1, and Wa is the following formula ( ^a -3) :.

Indicates a group represented by
Ring A in formula (a-3) represents an aliphatic ring that may be condensed with an aromatic ring or may have a substituent. )
Reaction between the compound (A-1) represented by (A-1) and an epoxy compound (A-2) containing a cyclic structure other than the oxylan ring and having three or more epoxy group-containing groups bonded to the cyclic structure. Epoxy, which is a thing.