WO2023127402A1

WO2023127402A1 - Photosensitive composition, cured product, and method for producing patterned cured film

Info

Publication number: WO2023127402A1
Application number: PCT/JP2022/044585
Authority: WO
Inventors: 二郎引田; 和之古谷
Original assignee: 東京応化工業株式会社
Priority date: 2021-12-28
Filing date: 2022-12-02
Publication date: 2023-07-06

Abstract

Provided are: a photosensitive composition which can form a cured product that is finely patterned and exhibits excellent adhesion to a substrate even if heat treated at a low temperature; a cured product of said photosensitive composition; and a method for producing a patterned cured film using the photosensitive composition.　This photosensitive composition contains an alkali-soluble resin (A), a photopolymerization initiator (C) and a silane coupling agent (D). The alkali-soluble resin (A) contains a product of a reaction between: a compound (A-1) having a specific structure having a carboxyl group; and an epoxy compound (A-2) which contains a cyclic structure other than an oxirane ring and has 3 or more epoxy group-containing groups bonded to the cyclic structure. The silane coupling agent (D) contains a silane coupling agent (D1) having a radical-polymerizable group-containing group.

Description

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

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

In the production of functional layers such as insulating layers in various semiconductor devices, and in the production of image display panels such as liquid crystal display panels and organic EL display panels, insulating layers and various optical functional layers in display devices are cured by exposure. The resulting negative-working photosensitive composition is widely used.

Such a photosensitive composition includes, for example, an acrylic resin, a silane coupling agent 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. 2015/194639

Such a functional layer or the like (cured product) is produced, for example, by applying and exposing a photosensitive composition, followed by heating. Also, by performing position-selective exposure, a patterned cured product having a desired shape can be formed.
However, when a conventional photosensitive composition such as that disclosed in Patent Document 1 is used to produce a finely patterned cured product by heating at a low temperature, there is a problem that it is difficult to form a cured product with excellent adhesion to the substrate. be.

The present invention has been made in view of the above problems, and a photosensitive composition capable of forming a cured product that is finely patterned and has excellent adhesion to a substrate even by heat treatment at a low temperature, and the photosensitive composition. An object of the present invention is to provide a cured product of a product and a method for producing a patterned cured film using the above photosensitive composition.

The present inventors have found that the alkali-soluble resin (A) contains an alkali-soluble resin (A), a photopolymerization initiator (C), and a silane coupling agent (D), and the alkali-soluble resin (A) has a specific structure having a carboxy group. Using a reaction product of a compound (A-1) 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, In addition, the inventors have found that the above problems can be solved by using a silane coupling agent (D1) having a radically polymerizable group-containing group as the silane coupling agent (D), and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention comprises an alkali-soluble resin (A), a photopolymerization initiator (C), and a silane coupling agent (D),
The alkali-soluble resin (A) has the following formula (a-1):

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

Z ^a represents a residue obtained by removing two carboxylic anhydride groups from tetracarboxylic dianhydride, and R ^a0 is a hydrogen atom or —CO—Y ^a —COOH. Y ^a represents a residue obtained by removing the carboxylic anhydride group from the dicarboxylic anhydride, t1 represents an integer of 0 or more and 20 or less,
In formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 each independently represents a hydrogen atom or a methyl group. , R ^a3 each independently represents a linear or branched alkylene group, t2 represents 0 or 1, and W ^a represents the following formula (a-3):

represents a group represented by
Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and which may have a substituent. )
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. including things
The silane coupling agent (D) is a photosensitive composition containing a silane coupling agent (D1) having a radically polymerizable group-containing group.

A 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;
position-selectively exposing the coating film;
and developing the exposed coating film with a developer.

According to the present invention, a photosensitive composition capable of forming a cured product that is finely patterned and has excellent adhesion to a substrate even by heat treatment at a low temperature, a cured product of the photosensitive composition, and the above-described photosensitive and a method for producing a patterned cured film using the composition.

<<Photosensitive composition>>
The photosensitive composition contains an alkali-soluble resin (A), a photoinitiator (C) and a silane coupling agent (D).
The alkali-soluble resin (A) has the following formula (a-1):

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

represents a group represented by
Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and which may have a substituent. )
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. Including things.

In addition, the silane coupling agent (D) includes a silane coupling agent (D1) having a radically polymerizable group-containing group.

The photosensitive composition contains a reaction product of the above compound (A-1) as the alkali-soluble resin (A) and the epoxy compound (A-2), and a radically polymerizable group as the silane coupling agent (D). When it contains a silane coupling agent (D1) having a group in combination, even if the heat treatment (post-baking) after exposure is performed at a low temperature (for example, 110 ° C. or less, preferably 100 ° C. or less), fine patterning is obtained. Moreover, a cured product having excellent adhesion to the substrate can be formed.
Therefore, even if the post-exposure heat treatment is performed at a low temperature, it is possible to form a cured product consisting of fine lines (for example, a fine line pattern with a width of 10 μm or less, preferably 8 μm or less) that has excellent adhesion to the substrate. Therefore, for example, even if the substrate has a heat-sensitive member such as a light-emitting layer and is difficult to heat to a high temperature, a cured product that is finely patterned and has excellent adhesion to the substrate can be formed.

In addition, when the above-mentioned photosensitive composition is used, even if heat treatment after exposure is performed at a low temperature, sufficiently high solvent resistance of the cured product can be easily obtained.
Organic solvents are often used in the manufacturing process of manufacturing functional layers such as insulating layers in various semiconductor devices and image display panels such as liquid crystal display panels and organic EL display panels. Since the photosensitive composition gives a cured product with high solvent resistance, it is suitable for applications in which an organic solvent is used in the manufacturing process.

Furthermore, the photosensitive composition comprises a reaction product of the above compound (A-1) as an alkali-soluble resin (A) and an epoxy compound (A-2), and a radically polymerizable silane coupling agent (D). When the photosensitive composition contains a silane coupling agent (D1) having a group-containing group in combination and does not contain a colorant, a cured product having high light transmittance and excellent transparency can be formed using the photosensitive composition.

The essential or optional components contained in the photosensitive composition and the method for preparing the photosensitive composition will be described below.

<Alkali-soluble resin (A)>
The photosensitive composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) contains a reaction product of the aforementioned compound (A-1) and the aforementioned epoxy compound (A-2). Hereinafter, this reactant is also referred to as “reactant (AI)”.
Here, in this specification, the alkali-soluble resin (A) refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, etc.) that imparts alkali-solubility in the molecule.

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

The reactant (AI), novolak resin (A-II), modified epoxy resin (A-III), and acrylic resin (A-IV) are described below.

[Reactant (AI)]
As described above, it is a reaction product of the aforementioned compound (A-1) and the aforementioned epoxy compound (A-2). Methods for producing compound (A-1), epoxy compound (A-2), and reactant (AI) are described below.

[Compound (A-1)]
The 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 formula (a-1), X ^a represents a group represented by formula (a-2) below. t1 represents an integer of 0 or more and 20 or less.

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

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

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

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

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

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

A diol compound represented by formula (a-2a) can be produced, for example, by the following method.
First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is, if necessary, replaced by a group represented by —R ^a3 —OH according to a conventional method, Glycidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).
Then, the epoxy compound represented by formula (a-2c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by formula (a-2a).
In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 and t2 are as described for formula (a-2). Ring A in formulas (a-2b) and (a-2c) is as described for formula (a-3).
The method for producing the diol compound represented by formula (a-2a) is not limited to the above method.

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

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

In the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. , biphenyl ether tetracarboxylic dianhydride, and the like.
In the above formula (a-1), t1 represents an integer of 0 or more and 20 or less.

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

The alkyl group that can be selected as R ^a4 in formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group within this range, the heat resistance of the 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 reactant (AI). is more preferable, and 1 or more and 3 or less is particularly preferable.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

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

t3 in formula (a-4) represents 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, more preferably 3, from the viewpoint of facilitating purification of the tetracarboxylic dianhydride.
From the viewpoint of chemical stability of the tetracarboxylic dianhydride, the lower limit of t3 is preferably 1, more preferably 2.
t3 in formula (a-4) is particularly preferably 2 or 3.

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

Examples of the tetracarboxylic dianhydride represented by formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″, 6,6''-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6'' -tetracarboxylic dianhydride”), methylnorbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-(methylnorbornane)-5,5″,6,6″-tetra Carboxylic acid dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (also known as "norbornane- 2-spiro-2′-cyclohexanone-6′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride”), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'- spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α′-spiro-2″-norbornane-5, 5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α′-spiro-2″-norbornane-5,5″,6,6′ '-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride , norbornane-2-spiro-α-cyclononanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone -α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2' '-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5' ',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''- tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α -(methylcyclopentanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone) -α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride and the like.

The weight average molecular weight of compound (A-1) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, and even more preferably 2000 or more and 10000 or less. By adjusting the above range, the use of the reactant (AI) as the alkali-soluble resin (A) makes it particularly easy to increase the solvent resistance of the cured product of the photosensitive composition.

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

The cyclic structure having 3 or more epoxy group-containing groups means that 3 or more epoxy group-containing groups are bonded to the monocyclic structure or condensed cyclic structure.
For example, a glycidyl ether type phenol novolac epoxy resin does not fall under the epoxy compound (A-2). A glycidyl ether type phenol novolak 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 monocyclic benzene ring structure. For this reason, glycidyl ether type phenol novolac epoxy resins do not satisfy the requirement that "three or more epoxy group-containing groups are bonded to a monocyclic structure or condensed cyclic structure".

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

In formula (A-2a), X ^a1 , X ^a2 and X ^a3 are epoxy group-containing groups. In 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 X ^a4 and x1 X ^a5 are epoxy group-containing groups. x1 is an integer of 3 or more.

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

In 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 each independently an oxiranyl group, an epoxycycloalkyl group, or an epoxypolycycloalkyl group.
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 oxirane ring. An epoxypolycycloalkyl group means a group in which at least one saturated carbon-carbon bond in a polycycloalkyl group such as a norbornyl group or a tricyclodecanyl group is substituted with a structure containing the following oxirane ring.

Preferred specific examples of epoxycycloalkyl groups and epoxypolycycloalkyl groups include the following groups.

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

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

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

In 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 X ^a4 and x1 X ^a5 are epoxy group-containing groups. x1 is an integer of 3 or more.

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

Suitable examples of epoxycycloalkylalkyl groups and epoxypolycycloalkylalkyl groups include the following groups.

The number of carbon atoms in the alkyl groups for X ^a4 and X ^a5 is not particularly limited. Examples of the alkyl group include 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as methyl group, ethyl group, propyl group, and isopropyl group. can be mentioned linear or branched alkyl groups.

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

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

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

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

(Method for producing reactant (AI))
The method for producing the reactant (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 reactant (A-I) 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 selected from the group consisting of

In formulas (A-1a), (A-1b), and (A-1c), X ^a , Y ^a , Z ^a , and t1 are as described above for formula (a-1). In formula (A-1a), formula (A-1b), and formula (A-1c), each R ^A is independently a hydrogen atom, a group represented by the following formula (Ai), or the following formula (Aii ) is a group represented by In formulas (A-1a), (A-1b), and (A-1c), multiple ^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). In formulas (Ai) and (Aii), R ⁰² , R ⁰³ and R ⁰⁴ are each independently a hydrogen atom or an organic group constituting an epoxy group-containing group possessed by the epoxy compound (A-2). be. Each R ⁰¹ is independently a single bond or an organic group constituting an epoxy group-containing group of the epoxy compound (A-2). When both R ⁰⁴ and R ⁰¹ are organic groups constituting epoxy group-containing groups, they may be combined to form a ring. R ^EP is a cyclic group that has two or more epoxy group-containing groups that may be reacted with a carboxy group in compound (A-1) and gives a cyclic structure in epoxy compound (A-2).

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

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

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

In formula (A-1d), X ^a , Y ^a , Z ^a and t1 are as described above for formula (a-1). Each ^RA is independently a hydrogen atom, a group represented by the above formula (Ai), or a group represented by the above 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 of the epoxy compound (A-2). Each R ⁰¹ is independently a single bond or an organic group constituting an epoxy group-containing group of the epoxy compound (A-2). When R ⁰⁴ and R ⁰¹ are organic groups constituting an epoxy group-containing group, they may be combined to form a ring. R ^EP is a cyclic group that has two or more epoxy group-containing groups that may be reacted with a carboxy group in compound (A-1) and gives a cyclic structure in epoxy compound (A-2). When R ^A shown in formula (A-1d) is a group represented by formula (Ai) above or a group represented by formula (Aii) above, R ^EP in R ^A has two or more The epoxy group-containing group of may react with the carboxy group in compound (A-1). The ratio at which two or more epoxy group-containing groups possessed by R ^EP react with the carboxy group in compound (A-1) depends on the charging ratio of compound (A-1) and epoxy compound (A-2) and the compound ( It can be adjusted as appropriate by adjusting the conditions for the reaction between A-1) and the epoxy compound (A-2).
In formula (A-1d), x2 and x3 are each an integer of 0 or more, preferably an integer of 1 or more and 4 or less.
For example, when R ^EP in formula (A-1d) is derived from the epoxy compound represented by formula (A-2a), x2 and x3 are each 1 or 0, and the sum of x2 and x3 is 1. be. If x2 is 0, then x3 is 1. In this case, the carboxyl 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 formula (A-1d) is derived from the epoxy compound represented by formula (A-2b), x2 and x3 are each integers of 0 or more and (x1×2−2) or less. x1 is as described for formula (A-2b). R ^EP in formula (A1-d) is derived from the epoxy compound represented by formula (A-2b), and the total number of epoxy group-containing groups as X ^a4 and X ^a5 in formula (A-2b) is x4. When x2 is 0 or more and less than (x4-2), the carboxy group and unreacted epoxy group of compound (A-1) are present in the reactant represented by formula (A1-d). Including groups are present.

When producing the reactant (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). More preferably, the reaction is carried out in an amount of 5 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less.
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 according to the application of the photosensitive composition. For example, when all the epoxy groups of the epoxy compound (A-2) are reacted with the carboxy groups of the compound (A-1), no unreacted epoxy groups remain. The storage stability of the photosensitive composition is good. In this case, the curing reaction of the photosensitive composition is the reaction between the ethylenically unsaturated double bonds of the reactant (AI).

When the epoxy group is not left, the charging ratio of the compound (A-1) and the epoxy compound (A-2) is as follows: 1 equivalent of the epoxy group of the epoxy compound (A-2) to the compound (A-1) A ratio of 0.90 equivalents or more to 1.20 equivalents or less of the carboxy group possessed by is preferable.
If the charging ratio is within this range, the remaining epoxy groups can be minimized, gelation during the reaction can be suppressed, and the reaction product (AI) with good storage stability can be easily obtained.

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

When the epoxy group is to remain, the ratio of the compound (A-1) and the epoxy compound (A-2) to be charged is such that the compound (A1) has one equivalent of the epoxy group of the epoxy compound (A-2). A ratio of 0.20 equivalents or more and less than 0.90 equivalents of carboxy groups is preferred.

The reaction between compound (A-1) and epoxy compound (A-2) is preferably carried out in an organic solvent.
Solvents 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, tripropylene glycol monoethyl ether and other (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene (Poly)alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2- 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-methoxy Butyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate , n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, aromatic hydrocarbons such as xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and the like.

In order to cause the compound (A-1) to react well with the epoxy compound (A-2) to obtain the reactant (AI) having a sufficiently high molecular weight, the compound (A1 ) and the concentration of the epoxy compound (A-2) is preferably 30% by mass or more and 70% by mass or less, 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 carried out at -20°C or higher and 100°C or lower, preferably -10°C or higher and 60°C or lower, more preferably 0°C or higher and 40°C or lower. can be implemented. The reaction temperature may be constant or may vary during the reaction.

The reaction time of the compound (A-1) and the epoxy compound (A-2) is not particularly limited. For example, the reaction time between the compound (A-1) and the epoxy compound (A-2) is preferably 1 hour or more and 24 hours or less, 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, for example, until the weight average molecular weight of the reactant (AI) reaches 5000 or more, and until it reaches 6000 or more. more preferably done. In addition, a weight average molecular weight is a molecular weight of polystyrene conversion measured by a gel permeation chromatography.

[Novolac 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 photosensitive compositions can be used. As the novolac resin (A-II), those obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst are preferred.

(Phenols)
Phenols used for producing the novolak resin (A-II) include, for example, phenol; cresols such as o-cresol, m-cresol and p-cresol; 2,3-xylenol and 2,4-xylenol , 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; 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-trimethylphenol, etc.; polyhydric phenols, such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; alkyl polyhydric phenols, such as alkylresorcinol, alkylcatechol and alkylhydroquinone. (All alkyl groups have from 1 to 4 carbon atoms.); α-naphthol; β-naphthol; hydroxydiphenyl; These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferred, and the combined use of m-cresol and p-cresol is more preferred. In this case, various properties such as heat resistance of the cured product formed using the photosensitive composition can be adjusted by adjusting the mixing ratio of both.
The mixing ratio of m-cresol and p-cresol is not particularly limited, but the molar ratio of m-cresol/p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in such a ratio, it is easy to obtain a photosensitive composition capable of forming a cured product having excellent heat resistance.

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

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

(acid catalyst)
Examples of acid catalysts used in producing the novolak resin (A-II) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfate, and organic acids such as p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

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

As the novolac resin (A-II), at least two novolak resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using a combination of large and small novolak resins 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 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). As the alkali-soluble resin (A), the epoxy compound (a-3a) and unsaturated group-containing carbon Polybasic acid anhydride (a-3c) adduct (A-III) of reaction product with acid (a-3b) may be included. Such an adduct is also referred to as "modified epoxy resin (A-III)".
In the specification and claims of the present application, a compound that falls under the above definition but does not fall under the aforementioned compound (A-1) is referred to as modified epoxy resin (A-III).

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

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

Specific examples of the epoxy compound (a-3a) include 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; Glycidylamine type epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanurate; (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, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

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

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

When R ^a7 is an alkyl group having 1 to 12 carbon atoms, specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl 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- Octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, and n-dodecyl groups.

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

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

The epoxy compound (a-3a) having a biphenyl skeleton represented by the above formula (a-3a-1) is not particularly limited, but examples thereof include epoxy compounds represented by the following formula (a-3a-2). be able to.

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

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, so the epoxy compound represented by the following formula (a-3a-3) are preferred.

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

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

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

In the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b), the ratio of the amounts of both used is the epoxy equivalent of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid ( The ratio to the carboxylic acid equivalent of a-3b) is generally 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 preferred.
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 terms of the equivalent ratio, the crosslinking efficiency tends to improve, which is preferable.

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

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

The polybasic acid anhydride (a-3c) is preferably a compound having two or more benzene rings, since it is easy to obtain a photosensitive composition with an excellent balance between sensitivity and developability. In addition, 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 preferred.

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

In addition, the acid value of the modified epoxy resin (A-III) is preferably 10 mgKOH/g or more and 150 mgKOH/g or less, more preferably 70 mgKOH/g or more and 110 mgKOH/g or less, in terms of resin solid content. By setting the acid value of the resin to 10 mgKOH/g or more, sufficient solubility in the developing solution can be obtained, and by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained, and surface properties can be improved. can be made better.

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

[Acrylic resin (A-IV)]
Acrylic resin (A-IV) is also preferred as a component constituting alkali-soluble resin (A).
As the acrylic resin (A-IV), a resin containing structural units derived from (meth)acrylic acid and/or structural units derived from other monomers such as (meth)acrylic acid esters can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylic acid ester is a compound represented by the following formula (a-4-1) and is not particularly limited as long as it does not interfere with the object of the present invention.

In formula (a-4-1) above, R ^a9 is a hydrogen atom or a methyl group, and R ^a10 is a monovalent organic group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. Moreover, this organic group may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic group of R ^a10 are not particularly limited as long as the effects of the present invention are not impaired, and include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, and cyanato groups. , isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkylthioether group, aryl ether group, arylthioether group, amino group (—NH ₂ , —NHR, —NRR′: R and R′ each independently represent a hydrocarbon group) and the like. A hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Moreover, the organic group as R ^a10 may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, or an oxetanyl group.
An acyl group having an unsaturated double bond such as an acryloyloxy group or a methacryloyloxy group is, for example, an acrylic resin (A-IV) containing a structural unit having an epoxy group, at least part of the epoxy group. , and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

R ^a10 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. Moreover, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

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

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

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

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

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

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

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

(Meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N -methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide and the like.

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

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

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

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

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

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

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

The weight average molecular weight of the acrylic resin (A-IV) is preferably 2000 or more and 50000 or less, more preferably 3000 or more and 30000 or less. By setting the amount within the above range, there is a tendency that the film-forming ability of the photosensitive composition and the developability after exposure are easily balanced.

The content of the alkali-soluble resin (A) is preferably 40% by mass or more and 95% by mass or less, more preferably 45% by mass or more and 80% by mass or less, relative to the total mass of the solid content of the photosensitive composition. more preferred. By setting it as said range, it is easy to obtain the photosensitive composition which is excellent in 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 preferred. Such monomers include monofunctional monomers and multifunctional monomers.
When the photosensitive composition contains the photopolymerizable monomer (B), it is particularly easy to obtain a cured product having excellent organic solvent resistance using the photosensitive composition.
In this specification, the photopolymerizable monomer (B) means a photopolymerizable monomer that does not correspond to the silane coupling agent (D1) having a radically polymerizable group-containing group, which will be described later.

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

On the other hand, polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol. Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3 - (meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin poly glycidyl ether poly(meth)acrylate, urethane (meth)acrylate (that is, tolylene diisocyanate, trimethylhexamethylene diisocyanate, or a reaction product of hexamethylene diisocyanate or the like with 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, Polyfunctional monomers such as (meth)acrylamidomethylene ether, condensates of polyhydric alcohols and N-methylol(meth)acrylamide, and triacrylformal. These polyfunctional monomers can be used singly or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, trifunctional or higher polyfunctional monomers are preferred because they tend to increase adhesion to substrates, strength and organic solvent resistance of the cured product of the photosensitive composition. , more preferably a tetra- or higher polyfunctional monomer, and more preferably a penta- or higher polyfunctional monomer.
Specifically, it is preferable to use a pentafunctional or higher polyfunctional monomer, 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 with respect to the total mass of the solid content of the photosensitive composition. is more preferred. By setting the amount within the above range, there is a tendency that sensitivity, developability, and resolution are easily balanced. In this specification, the solid content is a component other than the organic solvent (S).

<Photoinitiator (C)>
The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used, but it is preferable to use a photoradical polymerization initiator.

Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-(2- methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, O-acetyl-1-[6-(pyrrol-2-ylcarbonyl)-9-ethyl-9Hcarbazol-3-yl]eth nonoxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone 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-ethylhexylbenzoate, 4-dimethylamino-2-isoamylbenzoate, benzyl-β-methoxyethyl Acetal, benzyl dimethyl ketal, 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-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o -chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4 '-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2 -diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyl Dichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-( 9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s -triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s -triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]- 4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl- 6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis- and trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine.

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

Among the photopolymerization initiators (C), oxime ester compounds are preferred from the viewpoint of the sensitivity of the photosensitive composition.
As the oxime ester compound, a compound having a partial structure represented by the following formula (c1) is preferable.

(In formula (c1),
n1 is 0 or 1,
R ^c2 is a monovalent organic group,
R ^c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group,
* is a bond. )

The compound having the partial structure represented by formula (c1) preferably has a carbazole skeleton, fluorene skeleton, diphenyl ether skeleton, or phenyl sulfide skeleton.
The compound having the partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).

Compounds having a partial structure represented by formula (c1) include compounds represented by the following formula (c2).

(In the formula (c2), R ^c1 is a group represented by the following formula (c3), (c4), or (c5),
n1 is 0 or 1,
R ^c2 is a monovalent organic group,
R ^c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group. )

(In formula (c3), R ^c4 and R ^c5 are each independently a monovalent organic group,
n2 is an integer of 0 or more and 3 or less,
When n2 is 2 or 3, multiple R ^c5 may be the same or different, and multiple R ^c5 may combine with each other to form a ring.
* is a bond. )

(In the formula (c4), R ^c6 and R ^c7 each independently represent an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, a substituted is a cyclic organic group or a hydrogen atom,
R ^c6 and R ^c7 may combine with each other to form a ring,
R ^c7 and the benzene ring in the fluorene skeleton may be bonded to each other to form a ring,
R ^c8 is a nitro group or a monovalent organic group,
n3 is an integer of 0 to 4,
* is a bond. )

(In formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group,
A is S or O;
n4 is an integer of 0 to 4,
* is a bond. )

In formula (c3), R ^c4 is a monovalent organic group. R ^c4 can be selected from various organic groups as long as the objects of the present invention are not impaired. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of R ^c4 include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and a carbon atom A saturated aliphatic acyl group optionally having 2 to 20 substituents, an alkoxycarbonyl group having 2 to 20 carbon atoms and optionally having a substituent, a phenyl group optionally having a substituent , an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, having a substituent optionally substituted naphthyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, substituted a heterocyclyl group optionally having a group, a heterocyclylcarbonyl group optionally having a substituent, and the like.

Among R ^c4 , an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group as R ^c4 is preferably 2 or more, more preferably 5 or more, and 7 because the compound represented by formula (c3) has good solubility in the photosensitive composition. The above are particularly preferred. Further, from the viewpoint of good compatibility between the compound represented by formula (c3) and other components in the photosensitive composition, the number of carbon atoms in the alkyl group as R ^c4 is 15 or less. is preferred, and 10 or less is more preferred.

When R ^c4 has a substituent, preferred examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. aliphatic acyl groups, aliphatic acyloxy groups having 2 to 20 carbon atoms, phenoxy groups, benzoyl groups, benzoyloxy groups, groups represented by —PO(OR) ₂ (R has 1 to 6 carbon atoms alkyl group), a halogen atom, a cyano group, a heterocyclyl group, and the like.

When R ^c4 is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ^c4 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or such monocyclic rings are fused together or such monocyclic rings are fused with a benzene ring. is a heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of monocyclic rings constituting the condensed ring is 3 or less. Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
When R ^c4 is a heterocyclyl group, examples of substituents that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.

Preferable specific examples of R ^c4 described above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl groups.
Further, n-octyl group and 2-ethylhexyl group are preferred, and 2-ethylhexyl group is more preferred, from the viewpoint of good solubility of the compound represented by formula (c3) in the photosensitive composition.

In formula (c3), R ^c5 is a monovalent organic group, a halogen atom, or a nitro group. The monovalent organic group for R ^c5 can be selected from various organic groups as long as the object of the present invention is not impaired. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Examples of monovalent organic groups suitable as R ^c5 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents. optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy a phenylalkyl group optionally having substituents, a naphthyl group optionally having substituents, a naphthoxy group optionally having substituents, a naphthoyl group optionally having substituents, a substituent an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, amino group substituted with one or two organic groups, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, HX ₂ C- or H ₂ Substituents including a group represented by XC— (where each X is independently a halogen atom) and the like.

When R ^c5 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R ^c5 is an alkyl group, it may be linear or branched. Specific examples of R ^c5 being an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl groups. , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group and the like. In addition, when R ^c5 is an alkyl group, the alkyl group may contain an ether bond (--O--) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.

When R ^c5 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, when R ^c5 is an alkoxy group, it may be linear or branched. Specific examples of R ^c5 being an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n -pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Further, when R ^c5 is an alkoxy group, the alkoxy group may contain an ether bond (--O--) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.

When R ^c5 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples of R ^c5 being a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of R ^c5 being a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c5 is a saturated aliphatic acyl group or saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples of when R ^c5 is a saturated aliphatic acyl group include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Noyl group, n-hexadecanoyl group and the like. Specific examples of R ^c5 being a saturated aliphatic acyloxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c5 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples of R ^c5 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyl oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and An isodecyloxycarbonyl group and the like can be mentioned.

When R ^c5 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. When R ^c5 is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples of R ^c5 being a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group. Specific examples of when R ^c5 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. . When R ^c5 is a phenylalkyl group or a naphthylalkyl group, R ^c5 may further have a substituent on the phenyl group or naphthyl group.

When R ^c5 is a heterocyclyl group, the heterocyclyl group is the same as when R ^c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
When R ^c5 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^c5 is a heterocyclyl group.

When R ^c5 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted 7 to 20 carbon atoms The following phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthoyl groups, optionally substituted naphthylalkyl groups having 11 to 20 carbon atoms, and heterocyclyl and the like. Specific examples of these suitable organic groups are the same as for R ^c5 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group and the like.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c5 further have a substituent, the substituent includes a group represented by HX ₂ C-- or H ₂ XC-- (eg, HX ₂ C— or H ₂ XC—, a halogenated alkoxy group containing a group represented by HX ₂ C— or H 2 XC—, a halogenated alkyl group containing a group represented by HX 2 C— or H ₂ XC—), Alkyl group, alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated fat having 2 to 7 carbon atoms group acyloxy group, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group , a benzoyl group, a halogen, a nitro group, a cyano group, and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c5 further have substituents, the number of substituents is not limited as long as the object of the present invention is not impaired, and is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c5 have multiple substituents, the multiple substituents may be the same or different.

Substituents contained in R ^c5 when the benzoyl group further has a substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a 2-thenoyl group. (thiophen-2-ylcarbonyl group), furan-3-ylcarbonyl group and phenyl group.

The halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, etc., and is preferably a fluorine atom.

The substituent containing a group represented by HX ₂ C-- or H ₂ XC-- includes a halogenated alkoxy group containing a group represented by HX ₂ C-- or H ₂ XC--, HX ₂ C-- or H ₂ XC- A group having a halogenated alkoxy group including a group represented by -, a halogenated alkyl group including a group represented by HX ₂ C- or H ₂ XC-, represented by HX ₂ C- or H ₂ XC- and a group having a halogenated alkyl group containing a group, such as a halogenated alkoxy group containing a group represented by HX ₂ C-- or H ₂ XC--, or represented by HX ₂ C-- or H ₂ XC-- More preferably, it is a group having a halogenated alkoxy group containing group.

_The group having a halogenated alkyl group containing a group represented by HX ₂ C-- or H 2 XC-- is substituted with a halogenated alkyl group containing a group represented by HX ₂ C-- or H ₂ XC--. aromatic groups (e.g., phenyl group, naphthyl group, etc.), cycloalkyl groups ₍ e.g., _cyclopentyl group, cyclohexyl groups, etc.), etc., and is preferably an aromatic group substituted with a halogenated alkyl group including a group represented by HX ₂ C-- or H ₂ XC--.

_The group having a halogenated alkoxy group containing a group represented by HX ₂ C-- or H 2 XC-- is substituted with a halogenated alkoxy group containing a group represented by HX ₂ C-- or H ₂ XC--. aromatic groups (e.g., phenyl group, naphthyl group, etc.), alkyl groups substituted with halogenated alkoxy groups including groups represented by HX ₂ C- or H ₂ XC- (e.g., methyl group, ethyl group , n-propyl group, i-propyl group, etc.), a cycloalkyl group substituted with a halogenated alkoxy group including a group represented by HX ₂ C- or H ₂ XC- (e.g., cyclopentyl group, cyclohexyl group, etc. ) and the like, preferably an aromatic group substituted with a halogenated alkoxy group including a group represented by HX ₂ C-- or H ₂ XC--.

^Rc5 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ^c5 may have.

Among the monovalent organic groups, R ^c5 is an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or an aromatic ring which may have a substituent. Good phenylthioalkyl groups are preferred. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, most preferably a methyl group. preferable. Among the optionally substituted phenyl groups, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferred.

In the group represented by formula (c3), when a plurality of R ^c5 are present and the plurality of R ^c5 are bonded to each other to form a ring, the formed ring includes a hydrocarbon ring, a heterocyclic ring, and the like. be done. Heteroatoms contained in heterocycles include, for example, N, O and S. Aromatic rings are particularly preferred as the ring formed by combining a plurality of R ^c5 s. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As such an aromatic ring, an aromatic hydrocarbon ring is preferred. Specific examples of the case where a plurality of R ^c5 in formula (c3) are bonded to each other to form a benzene ring are shown below.

In the group represented by formula (c4), R ^c8 is a nitro group or a monovalent organic group. R ^c8 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by —(CO) _n1 — on the condensed ring in formula (c4). In formula (c4), the bonding position of R ^c8 is not particularly limited. When the group represented by formula (c4) has one or more R ^c8 , one of the one or more R ^c8 is fluorene, because the compound represented by formula (c4) is easily synthesized. Attachment to the 7-position of the backbone is preferred. That is, when the group represented by formula (c4) has 1 or more R ^c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are multiple R ^c8s , the multiple R ^c8s may be the same or different.

(In formula (c6), R ^c6 , R ^c7 , R ^c8 and n3 are the same as R ^c6 , R ^c7 , R ^c8 and n3 in formula (c4).)

When R ^c8 is a monovalent organic group, R ^c8 is not particularly limited as long as the object of the present invention is not impaired. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of the monovalent organic group for R ^c8 include the same preferred examples of the monovalent organic group as R ^c5 in formula (c3).

In formula (c4), R ^c6 and R ^c7 are each an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic It is an organic group or a hydrogen atom. R ^c6 and R ^c7 may combine with each other to form a ring. Among these groups, chain alkyl groups which may have a substituent are preferable as R ^c6 and R ^c7 . When R ^c6 and R ^c7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c6 and R ^c7 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable. Specific examples of R ^c6 and R ^c7 being chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and 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, and isodecyl group. In addition, when R ^c6 and R ^c7 are alkyl groups, the alkyl group may contain an ether bond (--O--) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.

When R ^c6 and R ^c7 are chain alkyl groups having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. . In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. A chain alkyl group having a substituent is preferably linear.

The substituents that the alkyl group may have are not particularly limited as long as they do not interfere with the object of the present invention. Suitable examples of substituents include alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, and alkoxycarbonyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferred. Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclyl groups. Specific examples of the cycloalkyl group are the same as the preferred examples when R ^c8 is a cycloalkyl group. Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups. Specific examples of the heterocyclyl group are the same as the preferred examples when R ^c8 is a heterocyclyl group. When R ^c8 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

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

When R ^c6 and R ^c7 are chain alkoxy groups having no substituents, the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable. Specific examples of R ^c6 and R ^c7 being chain alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert -butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. Further, when R ^c6 and R ^c7 are alkoxy groups, the alkoxy groups may contain an ether bond (--O--) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.

When R ^c6 and R ^c7 are chain alkoxy groups having substituents, the substituents that the alkoxy groups may have are the same as in the case where R ^c6 and R ^c7 are chain alkyl groups.

When R ^c6 and R ^c7 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups. When R ^c6 and R ^c7 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as in the case where R ^c6 and R ^c7 are chain alkyl groups.

When R ^c6 and R ^c7 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is either a phenyl group or a group formed by combining a plurality of benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.

When R ^c6 and R ^c7 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. Although the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, A tetracyclododecyl group, an adamantyl group, and the like can be mentioned.

When R ^c6 and R ^c7 are heterocyclyl groups, the same heterocyclyl groups as R ^c5 in formula (c3) can be mentioned.

R ^c6 and R ^c7 may combine with each other to form a ring. A group consisting of a ring formed by R ^c6 and R ^c7 is preferably a cycloalkylidene group. When R ^c6 and R ^c7 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

When R ^c7 forms a ring with the benzene ring of the fluorene skeleton, the ring may be either an aromatic ring or an aliphatic ring.

When the group formed by combining R ^c6 and R ^c7 is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and pyridine. ring, pyrazine ring, pyrimidine ring, and the like.

Examples of preferred groups among R ^c6 and R ^c7 described above include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in the linear alkylene group for A ¹ is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When ^A2 is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When ^A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. When ^A2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, preferably linear. When ^A2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that ^Rc6 and ^Rc7 have as substituents. When ^A2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that ^Rc6 and ^Rc7 have as substituents.

Preferred specific examples of R ^c6 and R ^c7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl; group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n -pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and cyanoalkyl groups such as 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl groups. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy carbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n -Alkoxycarbonylalkyl groups such as heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n- pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n- butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Preferred groups among those described above for R ^c6 and R ^c7 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.

In the formula (c5), it is particularly preferable that A is S because it is easy to obtain a photopolymerization initiator with excellent sensitivity.

In formula (c5), R ^c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
When R ^c9 in formula (c5) is a monovalent organic group, it can be selected from various organic groups within the range that does not impede the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of the organic group represented by ^Rc9 in formula (c5) include the same monovalent organic groups as ^Rc5 in formula (c3).

In R ^c9 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; benzoyl group; nitro group; optionally substituted benzofuranylcarbonyl group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group a 4-(phenyl)phenylcarbonyl group is more preferred.

In formula (c5), n4 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 n4 is 1, the position to which R ^c9 is bonded is preferably para to the bond to which the phenyl group to which R ^c9 is bonded is bonded to an oxygen atom or a sulfur atom.

In formulas (c1) and (c2), the monovalent organic group as ^Rc2 is not particularly limited as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
Preferred examples of the monovalent organic group as ^Rc2 include the same monovalent organic groups as ^Rc5 in formula (c3). Specific examples of these groups are the same as the groups described for R ^c5 in formula (c3).
^Rc2 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are those in which the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^c5 in the formula (c3) further have a substituent. It is the same as the base.

Among the organic groups, R ^c2 is a substituent containing the group represented by the above HX ₂ C-- or H ₂ XC--, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or A cycloalkylalkyl group and a phenylthioalkyl group optionally having a substituent on the aromatic ring are preferred. Alkyl group, optionally substituted phenyl group, number of carbon atoms in cycloalkyl group contained in cycloalkylalkyl group, number of carbon atoms in alkylene group contained in cycloalkylalkyl group, cycloalkylalkyl group, aromatic Regarding the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group optionally having substituents on the ring, or the phenylthioalkyl group optionally having substituents on the aromatic ring, the formula (c3 ) is the same as R ^c5 .

As R ^c2 , a group represented by —A ³ —CO—OA ⁴ is also preferable. ^A3 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. ^A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

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

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

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

Moreover, as R ^c2 , a group represented by the following formula (c7) or (c8) is also preferable.

(in formulas (c7) and (c8), R ^c10 and R ^c11 are each independently a monovalent organic group,
n5 is an integer of 0 to 4,
When R ^c10 and R ^c11 are present at adjacent positions on the benzene ring, R ^c10 and R ^c11 may combine with each other to form a ring,
R ^c12 is a monovalent organic group,
n6 is an integer of 1 or less and 8 or less,
n7 is an integer of 1 or more and 5 or less,
n8 is an integer from 0 to (n7+3). )

The organic groups as R ^c10 and R ^c11 in formula (c7) are the same as R ^c8 in formula (c4). R ^c10 includes a halogenated alkoxy group containing a group represented by HX ₂ C-- or H ₂ XC--, a halogenated alkyl group containing a group represented by HX ₂ C-- or H ₂ XC--, an alkyl group, or A phenyl group is preferred. When R ^c10 and R ^c11 combine to form a ring, the ring may be either an aromatic ring or an aliphatic ring. Preferred examples of the group represented by formula (c7) in which R ^c10 and R ^c11 form a ring include naphthalen-1-yl and 1,2,3,4- A tetrahydronaphthalen-5-yl group and the like can be mentioned.
In the above formula (c7), n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In formula (c8) above, R ^c12 is an organic group. Examples of the organic group include groups similar to the organic groups described for R ^c8 in formula (c4). Among organic groups, alkyl groups are preferred. Alkyl groups may be straight or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. R ^c12 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.

In the above formula (c8), n7 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the formula (c8), n8 is 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0.
In formula (c8), n6 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (c2), R ^c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group. When R ^c3 is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed.

In formulas (c1) and (c2), R ^c3 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, A cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified, and among these, a methyl group or a phenyl group is more preferable.

Preferable specific examples of the compound represented by formula (c2) and having a group represented by formula (c3) as R ^c1 include the following compounds.

Preferable specific examples of the compound represented by formula (c2) and having a group represented by formula (c4) as R ^c1 include the following compounds.

Preferable specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R ^c1 include the following compounds.

As the photopolymerization initiator (C), a phosphine oxide compound is also preferable from the viewpoint of good deep-part curability of the photosensitive composition. As the phosphine oxide compound, a phosphine oxide compound containing a partial structure represented by the following formula (c9) is preferable.

In formula (c9), R ^c21 and R ^c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic group having 7 to 20 carbon atoms. group acyl groups. However, both R ^c21 and R ^c22 are not aliphatic acyl groups or aromatic acyl groups.

The number of carbon atoms in the alkyl groups of R ^c21 and R ^c22 is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less. The alkyl groups as R ^c21 and R ^c22 may be linear or branched.
Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert- pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4,-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and An n-dodecyl group can be mentioned.

The number of carbon atoms in the cycloalkyl groups for R ^c21 and R ^c22 is preferably 5 or more and 12 or less. Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups.

The number of carbon atoms in the aryl groups of R ^c21 and R ^c22 is preferably 6 or more and 12 or less. The aryl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and the like. Specific examples of aryl groups include phenyl and naphthyl groups.

The number of carbon atoms in the aliphatic acyl groups for R ^c21 and R ^c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less. Aliphatic acyl groups may be straight or branched.
Specific examples of aliphatic acyl groups include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, and tetradecanoyl groups. , pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and icosanoyl groups.

The number of carbon atoms in the aromatic acyl groups for R ^c21 and R ^c22 is 7 or more and 20 or less. The aromatic acyl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and the like. Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6- Trimethylbenzoyl, α-naphthoyl, and β-naphthoyl groups are included.

Preferable specific examples of the phosphine oxide compound containing the structural moiety represented by formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine. oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
From the viewpoint of deep-part curability of the photosensitive composition, the phosphine oxide compound containing the structural moiety represented by formula (c9) is an α-hydroxyalkylphenone-based compound such as 2-hydroxy-2-methylpropiophenone. is also preferably used with an initiator of
When a phosphine oxide compound containing the structural moiety represented by formula (c9) and an α-hydroxyalkylphenone-based initiator such as 2-hydroxy-2-methylpropiophenone are used in combination, the mass of both The mass ratio of the phosphine oxide compound containing the structural moiety represented by formula (c9) to the total is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and 40% by mass. % or more and 60 mass % or less is more preferable.

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 of the photosensitive composition (total solid content) excluding the mass of the organic solvent (S) described later. is preferable, and more preferably 1% by mass or more and 20% by mass or less. By setting the content of the photopolymerization initiator (C) within the above range, it is possible to obtain a photosensitive composition that has good curability and is less likely to cause defects in pattern shape.

A photoinitiator aid may be combined with the photopolymerization initiator (C). Photoinitiation aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate 2- ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylp-toluidine, 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-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropione thiol compounds such as acids, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate; These photoinitiators can be used singly or in combination of two or more.

<Silane coupling agent (D)>
The photosensitive composition contains a silane coupling agent (D).
The silane coupling agent (D) contains a silane coupling agent (D1) having a radically polymerizable group-containing group.

The photosensitive composition contains a silane coupling agent (D1) having a radically polymerizable group-containing group together with the reaction product of the compound (A-1) and the epoxy compound (A-2), so that after exposure Even if the heat treatment (post-baking) of (1) is performed at a low temperature (for example, 110° C. or lower, preferably 100° C. or lower), a finely patterned cured product having excellent adhesion to the substrate can be formed.

On the other hand, the photosensitive composition does not contain a silane coupling agent (D1) having a radically polymerizable group-containing group, and a silane coupling agent other than the silane coupling agent (D1) having a radically polymerizable group-containing group (e.g. , a silane coupling agent having an epoxy group-containing group and not having a radically polymerizable group), when the heat treatment after exposure is performed at a low temperature, fine patterning and excellent adhesion to the substrate can be cured. It is difficult to form things. For example, when a finely patterned cured product is formed, the adhesiveness to the substrate is poor.

The radically polymerizable group-containing group possessed by the silane coupling agent (D1) typically includes a group containing an ethylenically unsaturated double bond. The ethylenically unsaturated double bond-containing group (group containing an ethylenically unsaturated double bond) is preferably an alkenyl group-containing group containing an alkenyl group such as a vinyl group and an allyl group, and a (meth)acryloyl group-containing group. groups are more preferred, and (meth)acryloyloxy groups are even more preferred.
In the present specification, (meth)acryloyl means both acryloyl and methacryloyl, (meth)acryloyloxy means both acryloyloxy and methacryloyloxy, (meth)acryl means acryl, and methacrylate, and (meth)acrylate means both acrylate and methacrylate.

Examples of the silane coupling agent (D1) having a radically polymerizable group-containing group include compounds represented by the following formula (d1).
X ^d -R ^d1 -Si(R ^d2 ) _dm (OR ^d3 ) _(3-dm) (d1)
(In formula (d1), X ^d is a radically polymerizable group-containing group, R ^d1 is an alkylene group or a single bond, and R ^d2 is a monovalent organic group bonded to a silicon atom via a C—Si bond. , R ^d3 is an alkyl group, and dm is an integer of 0 or more and 2 or less.)

In formula (d1), X ^d is a radically polymerizable group-containing group, and examples of the radically polymerizable group-containing group include ethylenically unsaturated double bond-containing groups, vinyl groups, and alkenyl groups such as allyl groups. is preferably an alkenyl group-containing group, more preferably a (meth)acryloyl group-containing group, and even more preferably a (meth)acryloyloxy group.

In formula (d1), R ^d1 is an alkylene group or a single bond, and examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 or more and 8 or less, more preferably 1 or more and 7 or less, and particularly preferably 1 or more and 6 or less.
Preferred specific examples of R ^d1 include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group and a butane-1,4-diyl group.

In formula (d1), R ^d2 is a monovalent organic group bonded to a silicon atom via a C—Si bond, and suitable examples of the organic group include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 1 or more and 20 or less.
Among hydrocarbon groups, chain or cyclic alkyl groups, aromatic hydrocarbon groups or aralkyl groups are more preferred.
Examples of the chain or cyclic alkyl group include chain or cyclic alkyl groups having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n- butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group, cyclooctyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc., preferably methyl group or ethyl group, more preferably methyl group.
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 1 to 12 carbon atoms, specifically phenyl group, 2-methylphenyl group, 3-methylphenyl group and 4-methylphenyl group. , 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, α-naphthyl group, β-naphthyl group, biphenylyl group and the like.
The aralkyl group includes an aralkyl group having 1 to 12 carbon atoms, and specific examples include a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-α-naphthylethyl group, and 2-β-naphthylethyl groups.
The monovalent organic group bonded to the silicon atom via a C—Si bond for R ^d2 is preferably a methyl group or an ethyl group, more preferably a methyl group.

In formula (d1), R ^d3 is an alkyl group, and examples of the alkyl group include chain or cyclic alkyl groups having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, n -propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group, cyclooctyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like.

In formula (d1), dm is an integer of 0 or more and 2 or less, preferably 0 or 1, more preferably 0.

Preferable specific examples of the silane coupling agent (D1) having a radically polymerizable group-containing group include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, alkenyltrialkoxysilanes such as 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, and 1-octenyltriethoxysilane; 2-acryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltriethoxysilane, 2- methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane (meth)acryloyloxyalkyltrialkoxysilanes such as silane, 4-acryloyloxybutyltrimethoxysilane, 4-acryloyloxybutyltriethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, and 4-methacryloyloxybutyltriethoxysilane; mentioned.
Among these, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyltriethoxysilane are preferred.

The silane coupling agent (D) may contain a silane coupling agent other than the silane coupling agent (D1) having a radically polymerizable group-containing group, but a silane coupling agent having a radically polymerizable group-containing group It is preferable not to contain a silane coupling agent other than (D1).
The mass ratio of the silane coupling agent (D1) having a radically polymerizable group-containing group in the silane coupling agent (D) is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably, 100% by mass is particularly preferable.

The content of the silane coupling agent (D1) having a radically polymerizable group-containing group is 0.1 mass with respect to the mass of the photosensitive composition (total solid content) excluding the mass of the organic solvent (S) described later. % or more and 30 mass % or less, more preferably 0.5 mass % or more and 20 mass % or less, and particularly preferably 1 mass % or more and 10 mass % or less.

<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 (poly ) Alkylene glycol monoalkyl ethers; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 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-methoxybutylpropionate, 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 -Amide such as dimethylformamide and N,N-dimethylacetamide.

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, the above More preferred are other ethers, other esters as described above. 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 concentration of the photosensitive composition is 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less.

<Other ingredients>
The photosensitive composition may contain various additives as required. Additives include sensitizers, curing accelerators, fillers, adhesion promoters such as dispersants, antioxidants, aggregation inhibitors, polymerization inhibitors such as thermal polymerization inhibitors, antifoaming agents, surfactants, Coloring agents such as dyes and pigments are included.

Examples of surfactants include fluorine-based surfactants, silicon-based surfactants, and nonionic surfactants, preferably silicon-based surfactants. Examples of silicone-based surfactants include polyether-modified polysiloxane, and more specific examples include polyether-modified polydimethylsiloxane.

The content of the surfactant is, for example, 0.01 to 5 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). is preferred.

Examples of the polymerization inhibitor include phenol-based polymerization inhibitors, such as compounds represented by the following formula. In addition, the polymerization inhibitor is used to suppress the change (gelation) of the photopolymerizable monomer (B) in the container over time.

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

<<Method for producing cured film>>
A cured product is obtained by exposing the photosensitive composition described above. Although the form of the cured product is not particularly limited, it is preferably a cured film.
As a typical method for producing a cured film,
Forming a coating film by applying the aforementioned photosensitive composition onto a substrate;
and exposing the coating film.

Alternatively, a cured film patterned into a desired shape (patterned cured film) can be obtained by subjecting the coating film to position-selective exposure and developing the exposed coating film with a developer. can.

When the exposed coating film is not developed, heat treatment (post-baking) is performed on the exposed coating film, and when the exposed coating film is developed, the developed coating film is subjected to heat treatment (post-baking).
The above-mentioned photosensitive composition contains a reactant (AI) that satisfies predetermined requirements as an alkali-soluble resin (A), and contains a silane coupling agent (D1) having a radically polymerizable group-containing group. Even if the post-exposure heat treatment (post-baking) is performed at a low temperature (for example, 110° C. or lower, preferably 100° C. or lower), a finely patterned cured film having excellent adhesion to the substrate can be formed. Of course, even if the post-exposure heat treatment (post-baking) is performed at a high temperature (for example, over 110° C.), a finely patterned cured film with excellent adhesion to the substrate can be formed.

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

Then, the coating film is irradiated with light (e.g., broadband light) containing g-line (436 nm), h-line (405 nm), and/or i-line (365 nm), ultraviolet rays, active energy rays such as excimer laser light, etc. Exposure is performed by irradiation. For exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. Although the exposure amount varies depending on the composition of the photosensitive composition, it is, for example, 20 mJ/cm ² or more and 500 mJ/cm ² or less, preferably about 20 mJ/cm ² or more and 100 mJ/cm ² or less.
When performing position-selective exposure, exposure is performed through a negative mask having a desired pattern.

When the coating film is subjected to position-selective exposure, the exposed coating film is developed with a developer. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic developers such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Thereafter, the cured film patterned by development or the cured film after exposure is preferably subjected to heat treatment (post-baking) at a low temperature (for example, 110° C. or lower, preferably 100° C. or lower).
Further exposure may be performed after heat treatment (post-baking). The active energy ray, the exposure apparatus, the amount of exposure, and the like used for exposure are the same as those described above.

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

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

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, and then 77.2 g of pyromellitic dianhydride and 1 g of tetraethylammonium bromide were mixed. Then, the temperature was gradually raised to 110° C. or higher and 115° C. or lower, and the reaction was carried out 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. Disappearance of acid anhydride groups was confirmed by IR spectrum.

[Preparation Example 2] Synthesis of resin A1 (reaction product (AI) of compound (A-1) represented by formula (a-1) and epoxy compound (A-2)) obtained in Preparation Example 1 86.8 g of a solution of compound A-1-1 (weight average molecular weight (Mw): 2000, Mw/Mn: 2.0) dissolved in propylene glycol monomethyl ether monoacetate (concentration of compound A-1-1: 54 .7% by mass), 2.5 g of epoxy compound A-2-1 having the following structure, and 10.7 g of propylene glycol monomethyl ether monoacetate were mixed, and the two 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 reactant (resin A1) was 9800, and Mw/Mn was 7.8.

[Example 1]
73.0 parts by mass of the reaction product (resin A1) obtained in Preparation Example 2 as the alkali-soluble resin (A) and 18.3 parts by mass of dipentaerythritol hexaacrylate (B1) as the photopolymerizable monomer (B) and 2.7 parts by mass (5.4 parts by mass in total) of C1 and C2 having the following structure as the photopolymerization initiator (C), and 2 parts of D1 having the following structure as the silane coupling agent (D). .7 parts by mass, 0.5 parts by mass of E1 (polymerization inhibitor) having the following structure, and 0.1 part by mass of BYK-310 (manufactured by BYK-Chemie, surfactant), with a solid content concentration of 45% by mass was dissolved in propylene glycol monomethyl ether acetate (PM) to obtain a photosensitive composition.

[Comparative Example 1]
A photosensitive composition was obtained in the same manner as in Example 1, except that D2 having the above structure was used as the silane coupling agent (D) instead of D1.

[Comparative Example 2]
Example 1 was repeated except that the compound A-1-1 obtained in Preparation Example 1 was used as the alkali-soluble resin (A) instead of the reactant (resin A1) obtained in Preparation Example 2. to obtain a photosensitive composition.

<Transmittance>
After coating the photosensitive compositions obtained in Examples and Comparative Examples on a glass substrate (EAGLEXG manufactured by Corning, 100 mm × 100 mm × 0.7 mm) by a spin coater, the photosensitive composition on the glass substrate was heated to 70°C. was heated for 120 seconds to form a coating film having a thickness of 8.0 μm. The entire surface of the formed coating film was exposed with an exposure amount of 100 mJ/cm ² . The coated film after exposure was heated (post-baked) at 100° C. for 20 minutes to obtain a cured film of the photosensitive composition.
The light transmittance (%) (wavelength: 400 nm) of the resulting cured film was measured using MCPD-3700 (manufactured by Otsuka Electronics Co., Ltd.). Table 1 shows the results.

<Chemical resistance>
After coating the photosensitive compositions obtained in Examples and Comparative Examples on a glass substrate (EAGLEXG manufactured by Corning, 100 mm × 100 mm × 0.7 mm) by a spin coater, the photosensitive composition on the glass substrate was heated to 70°C. was heated for 120 seconds to form a coating film having a thickness of 8.0 μm. The entire surface of the formed coating film was exposed to mixed light of g, h, and i lines at an exposure amount of 100 mJ/cm ² using an ultraviolet irradiation device (HMW-532D, manufactured by ORC). Puddle development was performed by dropping an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by mass onto the exposed coating film, and then allowing the film to stand still for 60 seconds. The developed coating film was heated (post-baked) at 100° C. for 20 minutes to obtain a cured film of the photosensitive composition.
The resulting cured film was immersed in propylene glycol monomethyl ether acetate at room temperature (23° C.) for 5 minutes. 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.
A film remaining rate of 99% or more was evaluated as ◯, a case of more than 97% and less than 99% was evaluated as Δ, and a case of 97% or less was evaluated as x. Table 1 shows the results.

<Fine Line Adhesion> Substrate Adhesion of Fine Line Pattern The photosensitive compositions obtained in Examples and Comparative Examples were applied onto a glass substrate (EAGLEXG manufactured by Corning, 100 mm×100 mm×0.7 mm) using a spin coater. The photosensitive composition on the glass substrate was heated at 70° C. for 120 seconds to form a coating film with a thickness of 8.0 μm. Through a negative mask designed to form a line-and-space pattern on the formed coating film with an exposure gap of 50 μm and 13 types of lines with widths varying from 8 μm to 1 μm in increments of 1 μm in the range of 8 μm to 20 μm. Then, a proximity exposure apparatus (product name: TME-150RTO, manufactured by Topcon Corporation) was used to irradiate (exposure) mixed light of g, h, and i lines. The exposure dose was 20 mJ/cm ² . Puddle development was performed by dropping an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by mass onto the exposed coating film, and then allowing the film to stand still for 60 seconds. The developed coating film was heated (post-baked) at 100° C. for 20 minutes to obtain a patterned cured film (resist pattern) of the photosensitive composition.
The obtained cured film was observed with an optical microscope, and the minimum width (μm) at which a line-and-space pattern was formed without peeling is described in the "minimum width" column of Table 1.
In addition, the case where peeling was not observed in the line portion of the line and space pattern with a width of 10 μm was evaluated as ◯, and the case where peeling was observed in the line portion with the line and space pattern with a width of 10 μm was evaluated as x. Note that the peeling was caused by development. In Comparative Example 2, the development solubility of compound A-1-1 was low, and a line-and-space pattern could not be formed, and was evaluated as XX.

As shown in Table 1, the reaction product of the above compound (A-1) as the alkali-soluble resin (A) and the epoxy compound (A-2), and the radically polymerizable group as the silane coupling agent (D) When the photosensitive composition of Example 1 containing the silane coupling agent (D1) having a containing group was used in combination, even a thin line with a width of 8 μm exhibited excellent adhesion to the substrate, and post-baking was performed at a low temperature. It can be seen that a cured product which is finely patterned and which has excellent adhesion to the substrate can be formed even if it is carried out. Moreover, the cured product formed using the photosensitive composition of Example 1 was excellent in solvent resistance and had a high light transmittance at a wavelength of 400 nm.
On the other hand, in Comparative Example 1 using a silane coupling agent having an epoxy group-containing group that is not a radically polymerizable group-containing group instead of the silane coupling agent (D1) having a radically polymerizable group-containing group, peeling occurred during development. This resulted in fine lines with poor adhesion to the substrate. Further, the photosensitive composition of Comparative Example 2 using the compound A-1-1 instead of the reaction product of the compound (A-1) and the epoxy compound (A-2) formed a pattern. could not.

Claims

Contains an alkali-soluble resin (A), a photopolymerization initiator (C), and a silane coupling agent (D),
The alkali-soluble resin (A) has the following formula (a-1):

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

Z a represents a residue obtained by removing two carboxylic anhydride groups from tetracarboxylic dianhydride, and R a0 is a hydrogen atom or —CO—Y a —COOH. Y a represents a residue obtained by removing the carboxylic anhydride group from the dicarboxylic anhydride, t1 represents an integer of 0 or more and 20 or less,
In formula (a-2), R a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R a2 each independently represents a hydrogen atom or a methyl group. , R a3 each independently represents a linear or branched alkylene group, t2 represents 0 or 1, and W a represents the following formula (a-3):

represents a group represented by
Ring A in formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring and which may have a substituent. )
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. including things
The photosensitive composition, wherein the silane coupling agent (D) contains a silane coupling agent (D1) having a radically polymerizable group-containing group.
The photosensitive composition according to claim 1, wherein the radically polymerizable group-containing group is a (meth)acryloyl group-containing group.
Claim 1 or 2, wherein the reactant is obtained by reacting 1 part by mass of the epoxy compound (A-2) with 5 parts by mass or more and 90 parts by mass or less of the compound (A-1). The photosensitive composition according to .
The epoxy compound (A-2) is represented by the following formula (A-2a) or the following formula (A-2b):

(In formula (A-2a), X a1 , X a2 and X a3 are epoxy group-containing groups,
In formula (A-2b), X a4 and X a5 are an epoxy group-containing group or an alkyl group, and at least three of x1 X a4 and x1 X a5 are the epoxy group-containing groups and x1 is an integer of 3 or more. )
The photosensitive composition according to any one of claims 1 to 3, which is a compound represented by
The photosensitive composition according to claim 4, wherein the epoxy compound is the compound represented by the formula (A-2b), and the epoxy group-containing group is an epoxycycloalkylalkyl group.
The photosensitive composition according to any one of claims 1 to 5, further comprising a photopolymerizable monomer (B) that does not correspond to the silane coupling agent (D1).
A cured product of the photosensitive composition according to any one of claims 1 to 6.
Forming a coating film by applying the photosensitive composition according to any one of claims 1 to 6 on a substrate;
position-selectively exposing the coating film;
and developing the exposed coating film with a developer.
The method for producing a cured film according to claim 8, wherein the developed coating film is post-baked.