JP7376347B2 - Resin composition, cured product, and siloxane-modified (meth)acrylic resin - Google Patents

Description

The present invention provides a curable resin composition containing a siloxane-modified (meth)acrylic resin (A1) with a specific structure, a cured product of the resin composition, and a method for producing a cured product using the above-mentioned resin composition. , relates to a method for producing a patterned cured film using a specific photosensitive composition as the above-mentioned resin composition, and a siloxane-modified (meth)acrylic resin suitably used as a component of the above-mentioned resin composition.

(Meta)arylates having an alicyclic epoxy group (unsaturated carboxylic acid ester compounds having an alicyclic epoxy group) are generally useful compounds in the fields of coatings, inks, adhesives, sealants, etc., and are particularly useful in the fields of coatings, inks, adhesives, sealants, etc. Polymers and cured products obtained from (meth)arylates containing a cyclic structure and an epoxy group have excellent weather resistance and properties suitable for outdoor use. Generally, this is due to the ring-opening reactivity of the epoxy group present in the alicyclic structure, the reactivity of the radically polymerizable double bond in the (meth)arylate structure, etc. This is to demonstrate the performance of

Currently, unsaturated carboxylic acid esters having an epoxy group in the molecule include (meth)arylates containing a terminal epoxy group such as glycidyl metatarylate and 1-methyl-1,2-epoxyethyl metatarylate; , 4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate are known. Further, Patent Document 1 discloses a β-hydroxyacrylate compound having an epoxy group in the molecule.

Further, Patent Document 2 states that when used as a radiation-sensitive resin, it can form a high-performance film that has excellent solvent solubility, transparency, heat resistance, etching resistance, flatness, and developability. 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane skeleton-containing unsaturated carboxylic acid esters are disclosed for the purpose of providing resin compositions with high storage stability.

Japanese Unexamined Patent Publication No. 61-263968 International Publication No. 2006-059564

It is desired that films such as insulators in display panels for various image display devices have a low dielectric constant. However, cured products of curable compositions such as those described in Patent Document 1 and Patent Document 2 have a high dielectric constant. For this reason, it has been difficult to apply the curable compositions described in Patent Document 1 and Patent Document 2 as materials for forming films constituting display panels.

In view of the problems of the prior art described above, the present invention provides a curable resin composition that provides a cured product with a low dielectric constant, a cured product of the resin composition, and a specific resin composition as the aforementioned resin composition. The present invention aims to provide a method for producing a patterned cured film using the method, and a siloxane-modified (meth)acrylic resin suitably used as a component of the above-mentioned resin composition.

The present inventors created a resin composition using a siloxane-modified (meth)acrylic resin as a curable component, which is a reaction product of a (meth)acrylic resin having an alicyclic epoxy group and an epoxy group-containing cyclic siloxane compound with a specific structure. We have discovered that the above problems can be solved by blending the compound into products, and have completed the present invention. More specifically, the present invention provides the following.

（式（ａ－Ｉ）中、Ｒ^ａ０１、及びＲ^ａ０２は、エポキシ基を含有する１価の基又はアルキル基を示し、ｘ１は３以上の整数を示し、ｘ１個のＲ^ａ０１及びｘ１個のＲ^ａ０２のうち、少なくとも２個はエポキシ基を含有する１価の基である。） The first aspect of the present invention includes a siloxane-modified (meth)acrylic resin (A1),
The siloxane-modified (meth)acrylic resin (A1) is composed of a (meth)acrylic resin (A-I) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group and the following formula (a-I). This is a resin composition that is a reaction product with the epoxy group-containing cyclic siloxane compound (A-II) shown below.

(In formula (a-I), R ^a01 and R ^a02 represent a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x1 R ^a01 and x1 At least two of R ^a02 are monovalent groups containing an epoxy group.)

A second aspect of the present invention is a cured product obtained by curing the resin composition according to the first aspect by heating and/or exposure.

A third aspect of the present invention is a method for producing a cured product, which involves heating and/or exposing the resin composition according to the first aspect.

The fourth aspect of the present invention is
The resin composition according to the first aspect comprises a (meth)acrylic resin (A1) containing a structural unit having an alkali-soluble group, a photopolymerizable monomer (B), and a photopolymerization initiator (C). Coating a resin composition containing the resin composition on a substrate to form a coating film;
positionally selectively exposing the coating film;
Developing the exposed coating film with an alkaline developer to pattern the coating film;
heating the patterned coating film;
This is a method for manufacturing a patterned cured film.

（式（ａ－Ｉ）中、Ｒ^ａ０１、及びＲ^ａ０２は、エポキシ基を含有する１価の基又はアルキル基を示し、ｘ１は３以上の整数を示し、ｘ１個のＲ^ａ０１及びｘ１個のＲ^ａ０２のうち、少なくとも２個はエポキシ基を含有する１価の基である。） A fifth aspect of the present invention is a (meth)acrylic resin (AI) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group, and a (meth)acrylic resin (AI) represented by the following formula (a-I). This is a siloxane-modified (meth)acrylic resin that is a reaction product with an epoxy group-containing cyclic siloxane compound (A-II).

(In formula (a-I), R ^a01 and R ^a02 represent a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x1 R ^a01 and x1 At least two of R ^a02 are monovalent groups containing an epoxy group.)

According to the present invention, there is provided a curable resin composition that provides a cured product with a low dielectric constant, a cured product of the resin composition, and a patterned cured film using a specific resin composition as the aforementioned resin composition. and a siloxane-modified (meth)acrylic resin suitably used as a component of the resin composition described above.

（式（ａ－Ｉ）中、Ｒ^ａ０１、及びＲ^ａ０２は、エポキシ基を含有する１価の基又はアルキル基を示し、ｘ１は３以上の整数を示し、ｘ１個のＲ^ａ０１及びｘ１個のＲ^ａ０２のうち、少なくとも２個はエポキシ基を含有する１価の基である。） ≪Resin composition≫
The resin composition includes a siloxane-modified (meth)acrylic resin (A1). The siloxane-modified (meth)acrylic resin (A1) is composed of a (meth)acrylic resin (A-I) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group and the following formula (a-I). This is a reaction product with the epoxy group-containing cyclic siloxane compound (A-II).

(In formula (a-I), R ^a01 and R ^a02 represent a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x1 R ^a01 and x1 At least two of R ^a02 are monovalent groups containing an epoxy group.)

In the specification and claims of this application, "(meth)acrylic" means both acrylic and methacrylic. In the specification and claims of this application, "(meth)acrylate" means both acrylate and methacrylate. In the specification and claims of this application, "(meth)acryloyl" means both acryloyl and methacryloyl.

Since the above resin composition contains the compound represented by the above siloxane-modified (meth)acrylic resin (A1) formula (1), which is an epoxy compound, it can be cured by a reaction involving an epoxy group.
The method of curing the resin composition is not particularly limited. The resin composition to which a heat-sensitive curing agent is added as necessary can be cured by heating. Further, a resin composition to which a photosensitive curing agent is added can be cured by exposure to light.

The resin composition may contain a photopolymerizable compound and a photopolymerization initiator. A resin composition containing the above-mentioned siloxane-modified (meth)acrylic resin (A1) which is an epoxy compound, a photopolymerizable compound and a photopolymerization initiator can be cured by exposure alone or a combination of exposure and heating.

The siloxane-modified (meth)acrylic resin (A1) and preferred embodiments of the resin composition will be described below. Note that the resin composition is not limited to the composition described below as long as it contains the siloxane-modified (meth)acrylic resin (A1).

<Siloxane-modified (meth)acrylic resin (A1)>
As mentioned above, the siloxane-modified (meth)acrylic resin (A1) contains a (meth)acrylic resin (A-I) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group, and the above-mentioned epoxy group. It is a reaction product with the containing cyclic siloxane compound (A-II).
When the resin composition contains the siloxane-modified (meth)acrylic resin (A1), the resin composition provides a cured product with a low dielectric constant.
The method for producing the (meth)acrylic resin (A-I), the epoxy group-containing cyclic siloxane compound (A-II), and the siloxane-modified (meth)acrylic resin (A1) will be described below.

[(meth)acrylic resin (AI)]
The (meth)acrylic resin (AI) is a (meth)acrylic resin containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group. The (meth)acrylic resin (A-I) may be a homopolymer of (meth)acrylate having an alicyclic epoxy group, and may be a homopolymer of (meth)acrylate having an alicyclic epoxy group and other monomers. It may also be a copolymer with a body.

((meth)acrylate with alicyclic epoxy group)
The alicyclic group constituting the (meth)acrylate having an alicyclic epoxy group may be monocyclic or polycyclic. From the viewpoint of easily obtaining a cured product with a low dielectric constant, it is preferable that the alicyclic group is a polycyclic alicyclic group, and the (meth)acrylate having an alicyclic epoxy group has a polycycloalkane skeleton.
Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Specific examples of (meth)acrylates having an alicyclic epoxy group include compounds represented by the following formulas (a-4-1a) to (a-4-1o). Among these, in order to keep the developability within an appropriate range, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferred; ) to (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 aliphatic saturated 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, or 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 (representing a phenylene group) is preferred.

（式（１）中、環Ａは、環Ｂと縮合する５又は６員脂環を含む環を表し、環Ｂは、環Ａ及びＣと縮合し、環Ｂ内を橋架けする架橋基を含む脂環を表し、環Ｃは、環Ｂと縮合する５又は６員脂環を含む環を表し、Ｒ^１は（メタ）アクリロイル基を表し、Ｒ^２は、アルキル基、アルカノイル基、アロイル基、又はトリヒドロカルビルシリル基を表し、環Ａ、環Ｂ及び環Ｃは置換基を有していてもいなくてもよい。） ・Compound represented by formula (1) As the (meth)acrylate having an alicyclic epoxy group, a compound represented by the following formula (1) is also preferable because it easily forms a cured product with a low dielectric constant. . The compound represented by formula (1) will be explained below.

(In formula (1), ring A represents a ring containing a 5- or 6-membered alicyclic ring that is fused with ring B, and ring B is fused with rings A and C and represents a bridging group that bridges the inside of ring B. Ring C represents a ring containing a 5- or 6-membered alicyclic ring condensed with Ring B, R ¹ represents a (meth)acryloyl group, and R ² represents an alkyl group, an alkanoyl group, an aroyl group. , or a trihydrocarbylsilyl group, and ring A, ring B, and ring C may or may not have a substituent.)

In formula (1), ring A is a ring containing a 5- or 6-membered alicyclic ring condensed with ring B. Ring B is an alicyclic ring that is condensed with rings A and C and contains a bridging group that bridges the inside of ring B. Ring C is a ring containing a 5- or 6-membered alicyclic ring condensed with Ring B. Rings A, B and C may or may not have substituents.

Ring A may or may not contain a bridging group that bridges within ring A, similar to ring B. Ring A is preferably a 6-membered alicyclic ring because the compound represented by formula (1) can be easily synthesized.
Ring C may or may not contain a bridging group similar to ring B that bridges the inside of ring C. From the viewpoint of easy synthesis of the compound represented by formula (1), ring C is preferably a 5-membered alicyclic ring. From the viewpoint of selectivity of the epoxy group ring-opening reaction during production, a 5-membered alicyclic ring is preferred.

Ring B can contribute to heat resistance by having a crosslinking group that bridges the inside of ring B.
Ring B includes a 5- to 8-membered alicyclic ring containing the above-mentioned crosslinking group. Ring B is preferably a 6- or 7-membered alicyclic ring containing the above-mentioned crosslinking group, and more preferably a 6-membered alicyclic ring containing the above-mentioned crosslinking group.

Examples of the bridging group that bridges the inside of ring B include divalent groups having 1 or more and 5 or less carbon atoms. The number of carbon atoms in the crosslinking group is more preferably 1 or more and 3 or less, and even more preferably 1 or 2. The above-mentioned crosslinking group is preferably an alkylene group, an ether bond (-O-), a thioether bond (-S-), a carbonyl group (-CO-), or a divalent group combining at least two thereof, and an alkylene group , an ether bond, a thioether bond, or a divalent group combining at least two thereof, an alkylene group, an ether bond, or a thioether bond are particularly preferable, and an alkylene group is most preferable.

Examples of the alkylene group include alkylene groups having 1 to 5 carbon atoms and which may have a substituent. The number of carbon atoms in the alkylene group is more preferably 1 or more and 3 or less, and even more preferably 1 or 2. Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, etc., with methylene group, ethylene group, or propylene group being preferred, and methylene group or ethylene group being more preferred.

Examples of the substituent that the alkylene group may have and the substituents that rings A, B, and C may have include a halogen atom or a hydrocarbon group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group include hydrocarbon groups having 1 or more and 10 or less carbon atoms. Suitable examples of hydrocarbon groups include alkyl groups and the like.
Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, Examples include n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group. Among these alkyl groups, alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert -butyl group is preferred.
The alkyl group may have a substituent. When the alkyl group has a substituent, examples of the substituent include a halogen atom.

（式（２）中、Ｌは前記架橋基を表し、前記架橋基が、アルキレン基、エーテル結合、チオエーテル結合、ケト基又はそれらの少なくとも２つを組み合わせた２価の基であり、Ｒ^３びＲ^４、それぞれ独立に、水素原子、ハロゲン原子又は炭化水素基を表し、＊は環Ａとの結合手を表し、＊＊は環Ｃとの結合手を表す。） As the ring B, a ring represented by the following formula (2) is preferable.

(In formula (2), L represents the crosslinking group, the crosslinking group is an alkylene group, an ether bond, a thioether bond, a keto group, or a divalent group combining at least two thereof, and R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group, * represents a bond with Ring A, and ** represents a bond with Ring C.)

Specific examples and preferred examples of the crosslinking group for L are as described above.
Specific examples and preferred examples of the halogen atom and hydrocarbon group as R ³ and R ⁴ include "substituents that the alkylene group may have, substituents that rings A, B, and C may have," Specific examples and preferred examples of the halogen atom or hydrocarbon group mentioned above can be mentioned as "group". R ³ and R ⁴ are preferably a hydrogen atom, a halogen atom, or an alkyl group, and more preferably a hydrogen atom.

In formula (1), R ² is an alkyl group, an alkanoyl group, an aroyl group, or a trihydrocarbylsilyl group.

The alkyl group as R ² may be linear or branched, preferably linear. The number of carbon atoms in the alkyl group as R ² is preferably 1 or more and 10 or less, more preferably 1 or more and 4 or less, and even more preferably 1 or 2. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, Examples include n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group. Among these alkyl groups, alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert -butyl group is preferred, methyl group and ethyl group are more preferred, and methyl group is even more preferred.

The alkanoyl group as R ² may be linear or branched, preferably linear. The number of carbon atoms in the alkanoyl group as R ² is preferably 2 or more and 10 or less, more preferably 2 or more and 4 or less, and even more preferably 2. Specific examples of the alkanoyl group include acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyl group. Among these alkanoyl groups, acetyl group and propanoyl group are preferred, and acetyl group is more preferred.

Examples of the aroyl group as R ² include a benzoyl group and a naphthoyl group.

The trihydrocarbylsilyl group as R ² is a group in which three hydrocarbon groups are bonded to a silicon atom.
The three hydrocarbon groups in the trihydrocarbylsilyl group may be the same or different. When producing the compound represented by formula (1), the three hydrocarbon groups in the trihydrocarbylsilyl group are Preferably, they are the same.

In the trihydrocarbylsilyl group, the hydrocarbon group bonded to the silicon atom may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. It may also be a group such as
In the trihydrocarbylsilyl group, when the hydrocarbon group bonded to the silicon atom is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may contain one or more unsaturated bonds.
In the trihydrocarbylsilyl group, when the hydrocarbon group bonded to the silicon atom is an aliphatic hydrocarbon group, the structure of the aliphatic hydrocarbon group may be linear or branched, It may be cyclic or a combination of these structures.

In the trihydrocarbylsilyl group, the number of carbon atoms of the hydrocarbon group bonded to the silicon atom is preferably 1 or more and 10 or less, since the molecular weight and epoxy equivalent of the compound represented by formula (1) do not become excessively large. The number is more preferably 6 or less, and even more preferably 1 or more and 4 or less.

As the hydrocarbon group in the trihydrocarbylsilyl group, for example, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group are preferable.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, Examples include n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group. Among these alkyl groups, alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert -butyl group is preferred.

Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group.

Specific examples of the aryl group include phenyl group, naphthalen-1-yl group, and naphthalen-2-yl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

Preferred specific examples of the trihydrocarbylsilyl group explained above include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-isobutylsilyl group, tri-sec -butylsilyl group, tri-tert-butylsilyl group, ethyldimethylsilyl group, n-propyldimethylsilyl group, isopropyldimethylsilyl group, n-butyldimethylsilyl group, isobutyldimethylsilyl group, sec-butyldimethylsilyl group, and tert- Butyldimethylsilyl group is mentioned.

（式（３）及び式（４）中、環Ｂは、環Ｂ内を橋架けする上記架橋基を含む脂環を表し、Ｒ^１は（メタ）アクリロイル基を表し、Ｒ^２は、アルキル基、アルカノイル基、アロイル基、又はトリヒドロカルビルシリル基を表し、Ｒ^１１は、単結合又は－ＣＨＲ^１５－で表される２価の基を表し、Ｒ^１１が単結合である場合、Ｒ^１２及びＲ^１３、又はＲ^１３及びＲ^１４が、互いに結合してオキシラン環（エポキシ基）を形成し、Ｒ^１１が－ＣＨＲ^１５－で表される２価の基である場合、Ｒ^１２及びＲ^１３、Ｒ^１３及びＲ^１４、又はＲ^１４及びＲ^１５が、互いに結合してオキシラン環を形成し、Ｒ^１２～Ｒ^１５のうちオキシラン環を形成していない基は、水素原子を表す。） It is preferable that the compound represented by the above formula (1) is a compound represented by the following formula (3) or (4).

(In formulas (3) and (4), ring B represents an alicyclic ring containing the above-mentioned bridging group that bridges within ring B, R ¹ represents a (meth)acryloyl group, and R ² represents an alkyl group. , represents an alkanoyl group, an aroyl group, or a trihydrocarbylsilyl group, R ¹¹ represents a single bond or a divalent group represented by -CHR ¹⁵ -, and when R ¹¹ is a single bond, R ¹² and R ¹³ , or R ¹³ and R ¹⁴ combine with each other to form an oxirane ring (epoxy group), and R ¹¹ is a divalent group represented by -CHR ¹⁵ -, R ¹² and R ¹³ , R ¹³ and R ¹⁴ or R ¹⁴ and R ¹⁵ combine with each other to form an oxirane ring, and the group that does not form an oxirane ring among R ¹² to R ¹⁵ represents a hydrogen atom.)

In formulas (3) and (4), specific examples and preferred examples of ring B include the same alicyclic rings as the specific examples and preferred examples of ring B in formula (1). It is preferable that ring B is a ring represented by formula (2).

R ¹¹ is preferably a divalent group represented by -CHR ¹⁵ -, R ¹¹ is a divalent group represented by -CHR ¹⁵ -, R ¹² and R ¹³ , R ¹³ and R ¹⁴ , Or, it is more preferable that R ¹⁴ and R ¹⁵ combine with each other to form an oxirane ring, and a group that does not form an oxirane ring among R ¹² to R ¹⁵ represents a hydrogen atom.

（式（Ｍ１）中、環Ａは、環Ｂと縮合する５又は６員脂環を含む環を表し、環Ｂは、環Ａ及びＣと縮合し、環Ｂ内を橋架けする架橋基を含む脂環を表し、環Ｃは、環Ｂと縮合する５又は６員脂環を含む環を表し、環Ａ、環Ｂ及び環Ｃは置換基を有していてもいなくてもよい。）

（式（Ｍ２）中、環Ａ、環Ｂ、及び環Ｃは、式（Ｍ１）中のこれらと同様であり、Ｒ^１は（メタ）アクリロイル基を表す。） The method for producing the compound represented by formula (1) is not particularly limited. A preferred manufacturing method is
Reacting a compound represented by the following formula (M1) with (meth)acrylic acid to produce a compound represented by the following formula (M2);
Alkylating, alkanoylating, aroylating, or trihydrocarbylsilylating the hydroxyl group of the compound represented by the following formula (M2);
Examples include methods including:

(In formula (M1), ring A represents a ring containing a 5- or 6-membered alicyclic ring that is fused with ring B, and ring B is fused with rings A and C and represents a bridging group that bridges within ring B. Ring C represents a ring containing a 5- or 6-membered alicyclic ring condensed with Ring B, and Ring A, Ring B, and Ring C may or may not have a substituent.)

(In formula (M2), ring A, ring B, and ring C are the same as those in formula (M1), and R ¹ represents a (meth)acryloyl group.)

The reaction between the compound represented by formula (M1) and (meth)acrylic acid may be carried out under either acidic conditions or basic conditions, and it is preferable to carry out the reaction under basic conditions. preferable. The basic conditions may be carried out in an inert solvent or in a basic solvent (eg, pyridine). Specifically, the reaction can be carried out under basic conditions using, for example, an alkylamine such as triethylamine.
Further, the above reaction between the compound represented by formula (M1) and (meth)acrylic acid may be performed in the presence of a phase transfer catalyst such as a quaternary ammonium halide such as benzyltriethylammonium chloride.

The reaction temperature is preferably -50°C or higher and lower than the boiling point of the solvent, more preferably room temperature or higher and 100°C or lower.

Further, the ratio (molar ratio) of the compound represented by formula (M1) and (meth)acrylic acid is not particularly limited, but is preferably 80/20 to 20/80, and 70/30 to 30/30. More preferably, it is 70.
The total concentration of the compound represented by formula (M1) and (meth)acrylic acid in the reaction solution is usually 0.001 mol/L or more and 6 mol/L or less, preferably 0.005 mol/L. The amount may be L or more and 4 mol/L or less, more preferably 0.01 mol/L or more and 3 mol/L or less.

The amount of the quaternary ammonium salt to be used is preferably in the range of 0.001 to 5 moles, more preferably 0.005 to 1 mole, relative to the compound represented by formula (M1). The following range, more preferably 0.01 mole or more and 0.1 mole or less.

A solvent may be used in the above reaction. Various solvents can be used, including nitrile solvents such as acetonitrile, hydrocarbon solvents such as benzene, toluene, and xylene, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, and diethyl. Ether solvents such as ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, ethanol, isopropyl alcohol, butanol One or more types selected from alcoholic solvents such as the following can be used.

The method of alkylating, alkanoylating, aroylating, or trihydrocarbylsilylating the hydroxyl group of the compound represented by formula (M2) is not particularly limited.

Examples of the alkylation method include a method in which an alkylating agent such as an alkane halide, dialkyl sulfate, dialkyl carbonate, etc. is reacted with a compound represented by formula (M2) in the presence of a base. Examples of the alkylating agent include methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, dimethyl sulfate, dimethyl carbonate, diethyl sulfate, and diethyl carbonate. Examples of the base include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, and lithium methoxide.
The solvent used in the alkylation method is not particularly limited as long as it does not react with the compound represented by formula (M2) and the alkylating agent, and is commonly used in the alkylation reaction of hydroxyl groups using the above alkylating agent. The solvent is selected as appropriate from the solvents listed above. The reaction temperature and reaction time can be appropriately selected from the ranges normally employed in alkylation reactions using the above-mentioned alkylating agents.

Examples of the alkanoylation method include a method in which a fatty acid halide or fatty acid anhydride corresponding to an alkanoyl group is reacted with a compound represented by formula (M2). Examples of fatty acid halides include acetyl chloride, acetyl bromide, propionyl chloride, and propionyl bromide. Examples of fatty acid anhydrides include acetic anhydride, propionic anhydride, butanoic anhydride, and the like.
When using a fatty acid halide, alkanoylation is carried out in the presence of a base such as pyridine, triethylamine, sodium hydroxide, or potassium hydroxide for the purpose of capturing hydrogen halide produced by the reaction between the hydroxyl group and the fatty acid halide. is preferred.
When using a fatty acid anhydride, it is preferable to carry out the alkanoylation in the presence of a catalyst such as N,N-dimethyl-4-aminopyridine.
The solvent used in the alkanoylation method is not particularly limited as long as it does not react with the compound represented by formula (M2) and the fatty acid halide or fatty acid anhydride. The solvent is appropriately selected from solvents commonly used in chemical reactions. The reaction temperature and reaction time can be appropriately selected from the ranges normally employed in alkanoylation reactions using fatty acid halides or fatty acid anhydrides.

Examples of the aroylation method include a method in which an aromatic carboxylic acid halide corresponding to an aroyl group is reacted with a compound represented by formula (M2). Examples of the aromatic carboxylic acid halide include benzoic acid chloride, benzoic acid bromide, α-naphthoic acid chloride, α-naphthoic acid bromide, β-naphthoic acid chloride, and β-naphthoic acid bromide. The reaction between the aromatic carboxylic acid halide and the compound represented by formula (M2) can be carried out in the same manner as the reaction between fatty acid halide and the compound represented by formula (M2).
The solvent used in the aroylation method is not particularly limited as long as it does not react with the compound represented by formula (M2) and the aromatic carboxylic acid halide, and the aroylation reaction of a hydroxyl group using an aromatic carboxylic acid halide The solvent is appropriately selected from commonly used solvents. The reaction temperature and reaction time can be appropriately selected from the ranges normally employed in alloying reactions using aromatic carboxylic acids.

Examples of the trihydrocarbisilylation method include a method in which a compound represented by formula (M2) is reacted with a silylating agent depending on the type of trihydrocarbylsilyl group. Examples of the silylating agent include trihydrocarbyl monohalosilanes such as trihydrocarbyl monochlorosilane and trihydrocarbyl monobromosilane, and trihydrocarbyl monoalkoxysilanes such as trihydrocarbyl monomethoxysilane and trihydrocarbyl monoethoxysilane.

Preferred examples of trihydrocarbyl monohalosilane include trimethylmonochlorosilane, triethylmonochlorosilane, tri-n-propylmonochlorosilane, triisopropylmonochlorosilane, tri-n-butylmonochlorosilane, tri-isobutylmonochlorosilane, and tri-sec- Butyl monochlorosilane, tri-tert-butyl monochlorosilane, ethyldimethylmonochlorosilane, n-propyldimethylmonochlorosilane, isopropyldimethylmonochlorosilane, n-butyldimethylmonochlorosilane, isobutyldimethylmonochlorosilane, sec-butyldimethylmonochlorosilane, and tert - trialkyl monochlorosilane such as butyldimethylmonochlorosilane;
Trimethyl monobromosilane, triethyl monobromosilane, tri-n-propyl monobromosilane, triisopropyl monobromosilane, tri-n-butyl monobromosilane, tri-isobutyl monobromosilane, tri-sec-butyl monobromosilane, Tri-tert-butyl monobromosilane, ethyldimethylmonobromosilane, n-propyldimethylmonobromosilane, isopropyldimethylmonobromosilane, n-butyldimethylmonobromosilane, isobutyldimethylmonobromosilane, sec-butyldimethylmonobromosilane , and trialkyl monobromosilanes such as tert-butyldimethylmonobromosilane;
Trimethylmonomethoxysilane, triethylmonomethoxysilane, tri-n-propylmonomethoxysilane, triisopropylmonomethoxysilane, tri-n-butylmonomethoxysilane, tri-isobutylmonomethoxysilane, tri-sec-butylmonomethoxysilane, Tri-tert-butylmonomethoxysilane, ethyldimethylmonomethoxysilane, n-propyldimethylmonomethoxysilane, isopropyldimethylmonomethoxysilane, n-butyldimethylmonomethoxysilane, isobutyldimethylmonomethoxysilane, sec-butyldimethylmonomethoxysilane , and trialkylmonomethoxysilanes such as tert-butyldimethylmonomethoxysilane;
Trimethylmonoethoxysilane, triethylmonoethoxysilane, tri-n-propylmonoethoxysilane, triisopropylmonoethoxysilane, tri-n-butylmonoethoxysilane, tri-isobutylmonoethoxysilane, tri-sec-butylmonoethoxysilane, Tri-tert-butylmonoethoxysilane, ethyldimethylmonoethoxysilane, n-propyldimethylmonoethoxysilane, isopropyldimethylmonoethoxysilane, n-butyldimethylmonoethoxysilane, isobutyldimethylmonoethoxysilane, sec-butyldimethylmonoethoxysilane , and trialkylmonoethoxysilanes such as tert-butyldimethylmonoethoxysilane.

The amount of the silylating agent used in the reaction between the compound represented by formula (M2) and the silylating agent is preferably equal to or more than the number of moles of the compound represented by formula (M2), and 1. More preferably 2 times the mole or more, even more preferably 1.5 times the mole or more, particularly preferably 2.0 times the mole or more. There is no particular upper limit to the amount of the silylating agent to be used, but from the viewpoint of cost, it is preferably 5.0 times or less, and 3.0 times or less, relative to the number of moles of the compound represented by formula (M2). More preferred.

The reaction between the compound represented by formula (M2) and the silylating agent is usually carried out in an organic solvent. As the organic solvent, an organic solvent that does not have a functional group that can react with the silylating agent, such as a hydroxyl group, a carboxy group, or an amino group, is used.
Specific examples of organic solvents include alkyl halides such as carbon tetrachloride, chloroform, dichloromethane, bromopropane, bromobutane, bromopentane, bromohexane, methyl iodide, ethyl iodide, and propyl iodide; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone and cyclohexanone; hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, petroleum ether, benzine, kerosene, toluene, xylene, mesitylene, and benzene Can be mentioned.

The temperature during the reaction between the compound represented by formula (M2) and the silylation agent is not particularly limited as long as the silylation reaction proceeds favorably. The reaction temperature is, for example, preferably -20°C or more and 100°C or less, more preferably -10°C or more and 80°C or less, and even more preferably 0°C or more and 50°C or less.

The reaction time is not particularly limited as long as the silylation reaction proceeds well. The reaction time is, for example, 5 minutes or more and 12 hours or less, preferably 10 minutes or more and 6 hours or less.

When the silylation agent is trihydrocarbyl monohalosilane, hydrogen halide is produced as a by-product during the silylation reaction. In order to capture by-produced hydrogen halide, a base such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine may be added to the reaction solution.

The compound represented by formula (1) produced as described above is preferably recovered from the reaction solution according to a conventional method, purified if necessary, and then converted into a component of the resin composition or as described below. It is used as a raw material for (meth)acrylic resin (A1).

(other monomers)
As mentioned above, the (meth)acrylic resin (A1) is a copolymer of a (meth)acrylate having an alicyclic epoxy group and a monomer other than the (meth)acrylate having an alicyclic epoxy group. It may be.
From the viewpoint of curability of the resin composition, the content of structural units derived from (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A1) is preferably 50% by mass or more, and 60% by mass. The content is more preferably 70% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content of the structural unit derived from the (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A1) is not particularly limited, but may be 95% by mass or less, and 90% by mass or less It may be 80% by mass or less.

Examples of other monomers include unsaturated carboxylic acids, (meth)acrylic esters without epoxy groups, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and maleimides. It will be done. These compounds can be used alone or in combination of two or more. In terms of the storage stability of the resin composition and the chemical resistance of the cured product formed using the resin composition against alkalis, etc., the (meth)acrylic resin (A1) has units derived from unsaturated carboxylic acids. Preferably, it does not contain.
On the other hand, when the resin composition is a negative photosensitive composition that can be developed with an alkaline developer, it is preferable that the (meth)acrylic resin (A1) has a structural unit having an alkali-soluble group. The alkali-soluble group is not particularly limited, and examples include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
From the viewpoint of stability of the resin composition over time, the alkali-soluble group is preferably a carboxy group. That is, it is preferable that the (meth)acrylic resin (A1) contains a unit derived from an unsaturated carboxylic acid.

Examples of unsaturated carboxylic acids include (meth)acrylic acid; (meth)acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. Among these, (meth)acrylic acid is preferred.

When the (meth)acrylic resin (A1) contains a structural unit derived from an unsaturated carboxylic acid, the content of the structural unit derived from an unsaturated carboxylic acid in the (meth)acrylic resin (A1) is 3% by mass or more. It is preferably 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less.

Examples of (meth)acrylic acid esters that do not have an epoxy group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and tert-octyl (meth)acrylate. Chain or branched alkyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; (meth)acrylic acid ester having a group having an alicyclic skeleton. Among (meth)acrylic esters that do not have an epoxy group, (meth)acrylic esters that have a group having an alicyclic skeleton are preferred.

In the (meth)acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of the (meth)acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (a1-1) to (a1-8). Among these, compounds represented by the following formulas (a1-3) to (a1-8) are preferred, and compounds represented by the following formula (a1-3) or (a1-4) are more preferred.

In the above formula, R ^A1 represents a hydrogen atom or a methyl group, R ^A2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^A3 represents a hydrogen atom or a carbon atom number. Indicates an alkyl group of 1 or more and 5 or less. R ^A2 is preferably a single bond, a linear or branched alkylene group, such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, or hexamethylene group. As R ^A3 , a methyl group and an ethyl group are preferable.

When the (meth)acrylic resin (A1) contains a structural unit derived from a (meth)acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton in the (meth)acrylic resin (A1) The content of the structural unit derived from the (meth)acrylic ester having is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and 7% by mass or more and 20% by mass or less. More preferred.

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

Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxy Aliphatic vinyl ethers such as ethyl 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 -Vinyl aryl ethers such as dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether; and the like.

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

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene. , ethoxymethylstyrene, acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo; Examples include halostyrenes such as styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.
From the viewpoint of low dielectric constant of the cured product of the resin composition, it is preferable that the amount of structural units derived from styrenes in the (meth)acrylic resin (A1) is as small as possible. More preferably, it does not contain structural units derived from styrenes.

Examples of maleimides include carbon atoms such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, and Nn-hexylmaleimide. Maleimide N-substituted with an alkyl group having 1 to 10 atoms; Maleimide N-substituted with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, etc. : N-arylmaleimide substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N-α-naphthylmaleimide, N-β-naphthylmaleimide; N-benzylmaleimide, N-phenethylmaleimide Examples include N-aralkylmaleimides substituted with N-substituted aralkyl groups having 7 or more and 20 or less carbon atoms.

The weight average molecular weight of the (meth)acrylic resin (A1) is not particularly limited as long as it does not impede the object of the present invention, but the weight average molecular weight in terms of polystyrene is preferably 3,000 or more and 30,000 or less, and 5,000 or less. It is more preferably 15,000 or less.

[Epoxy group-containing cyclic siloxane compound (A-II)]
A compound represented by the following formula (a-I) is used as the epoxy group-containing cyclic siloxane compound (A-II).

In formula (a-I), R ^a01 and R ^a02 represent a monovalent group containing an epoxy group or an alkyl group. However, at least two of x1 R ^a01 and x1 R ^a02 in the compound represented by formula (a-I) are monovalent groups containing an epoxy group. Furthermore, x1 in formula (aI) represents an integer of 3 or more. Note that R ^a01 and R ^a02 in the compound represented by formula (b1-III) may be the same or different. Moreover, a plurality of R ^a01s may be the same or different. A plurality of R ^a02s may also be the same or different.
Examples of the alkyl group include linear or branched alkyl groups having 1 or more and 18 or less carbon atoms, such as a methyl group, ethyl group, propyl group, and isopropyl group. The number of carbon atoms in the alkyl group is preferably 1 or more and 6 or less, particularly preferably 1 or more and 3 or less.

x1 in formula (a-I) represents an integer of 3 or more, and among them, siloxane-modified (meth)acrylic resin (A1) which has excellent reactivity with (meth)acrylic resin (A-I) and excellent curability. ) is preferably an integer of 3 or more and 6 or less.

The compound represented by formula (a-I) has two or more epoxy groups in its molecule, and is a siloxane-modified compound that has excellent reactivity with (meth)acrylic resin (A-I) and excellent curability. From the viewpoint of obtaining the (meth)acrylic resin (A1), the number is preferably 2 or more and 6 or less, particularly preferably 2 or more and 5 or less.

（上記式（ａ－Ｉａ）及び式（ａ－Ｉｂ）中、Ｄ^１及びＤ^２は、それぞれ独立にアルキレン基を表し、ｍｓは０以上２以下の整数を表す。） As the monovalent group containing an epoxy group, an alicyclic epoxy group and a glycidyl ether group represented by -D ^A -O-R ^a03 are preferable, an alicyclic epoxy group is more preferable, and an alicyclic epoxy group represented by the following formula ( More preferred is an alicyclic epoxy group represented by a-Ia) or the following formula (a-Ib). ^DA represents an alkylene group, and R ^a03 represents a glycidyl group.
Examples of the alkylene group as D ^A include linear or branched alkylene groups having 1 to 18 carbon atoms, such as methylene group, methylmethylene group, dimethylmethylene group, dimethylene group, and trimethylene group. etc. can be mentioned.

(In the above formulas (a-Ia) and (a-Ib), D ¹ and D ² each independently represent an alkylene group, and ms represents an integer of 0 to 2.)

More specifically, examples of the compound represented by formula (a-I) include cyclic siloxanes having two or more glycidyl groups in the molecule, which are represented by the following formula. Further, as the compound represented by formula (a-I), for example, the trade name "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738" ”, “X-40-2740” (manufactured by Shin-Etsu Chemical Co., Ltd.), and other commercially available products can be used.

<Production method of siloxane-modified (meth)acrylic resin (A1)>
The siloxane-modified (meth)acrylic resin (A1) is a (meth)acrylic resin (A-I) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group, and the above-mentioned epoxy group-containing cyclic siloxane compound. It is a reaction product with (A-II).

The amount of the epoxy group-containing cyclic siloxane compound (A-II) to be reacted with the (meth)acrylic resin (AI) when producing the siloxane-modified (meth)acrylic resin (A1) is not particularly limited.
The amount of the epoxy group-containing cyclic siloxane compound (A-II) to be reacted with the (meth)acrylic resin (A-I) is, for example, 1 mass per 100 parts by mass of the (meth)acrylic resin (A-I). Parts by weight or more and 50 parts by weight or less, more preferably 1 parts by weight or more and 30 parts by weight or less, and even more preferably 1 parts by weight or more and 15 parts by weight or less.

The reaction is typically carried out in the presence of an organic solvent. The organic solvent can be appropriately selected, for example, from the organic solvents described later as components of the resin composition. The amount of the organic solvent used is, for example, 50 parts by mass or more based on the total of 100 parts by mass of the (meth)acrylic resin (A-I) and the epoxy group-containing cyclic siloxane compound (A-II). It is preferably 5000 parts by mass or less, more preferably 100 parts by mass or more and 3000 parts by mass or less, and more preferably 150 parts by mass or more and 2000 parts by mass or less.

The reaction temperature and reaction time are not particularly limited as long as the reaction is desired. From the viewpoint of allowing the desired reaction to proceed favorably, the reaction temperature is preferably 0°C or more and 150°C or less, more preferably 10°C or more and 120°C or less, and even more preferably 20°C or more and 100°C or less. The reaction time is preferably 5 minutes or more and 12 hours or less, more preferably 10 minutes or more and 6 hours or less.

The reaction between the (meth)acrylic resin (AI) and the epoxy group-containing cyclic siloxane compound (A-II) may be carried out in the presence of a catalyst to promote the reaction. Suitable examples of the catalyst include imidazole compounds, secondary amine compounds, tertiary amine compounds, organic phosphine compounds, and tetraphenyl boron salts, with imidazole compounds and tertiary amine compounds being more preferred. .
Specific examples of imidazole compounds include 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole, and the like.
Specific examples of tertiary amine compounds include 1,8-diaza-bicyclo[5.4.0]-7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylethanolamine, tris(dimethylaminomethyl ) Phenol etc.
Specific examples of secondary amine compounds include diethylamine, dipropylamine, dibutylamine, and the like.
Specific examples of organic phosphine compounds include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, and the like.
Specific examples of the tetraphenyl boron salt include tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, and the like.

The amount of the catalyst used is not particularly limited, and is 0.1 parts by mass based on the total of 100 parts by mass of the (meth)acrylic resin (AI) and the epoxy group-containing cyclic siloxane compound (A-II). Parts by weight or more and 20 parts by weight or less, 0.2 parts by weight or more and 10 parts by weight or less, more preferably 0.5 parts by weight or more and 5 parts by weight or less.

As an example, when the (meth)acrylic resin (AI) has a carboxyl group and an epoxycyclohexyl group, and the epoxy group-containing cyclic siloxane compound (A-II) has an epoxycyclohexyl group, (meth)acrylic resin (A-I) has an epoxycyclohexyl group. The following reaction may occur as a reaction between the resin (AI) and the epoxy group-containing cyclic siloxane compound (A-II). Among the reactions below, reactions involving water can be caused by a trace amount of moisture in the reaction apparatus or by a trace amount of moisture brought into the reaction system along with an organic solvent or the like.

The siloxane-modified (meth)acrylic resin (A1) prepared according to the above method is used in the preparation of a resin composition either as a reaction solution as it is or in a state isolated from the reaction solution according to a conventional method.

[Preferred embodiment of resin composition]
Hereinafter, preferred embodiments of the resin compositions will be described, including a first resin composition and a second resin composition. Note that the resin composition containing the siloxane-modified (meth)acrylic resin (A1) is not limited to the first resin composition and the second resin composition described below.

(First resin composition)
The first resin composition is a resin composition containing a siloxane-modified (meth)acrylic resin (A1) and a curing agent.

The first resin composition contains a siloxane-modified (meth)acrylic resin (A1) as an epoxy compound. The first resin composition contains a curing agent that cures the siloxane-modified (meth)acrylic resin (A1), which is an epoxy compound. The curing agent may be a photosensitive curing agent, a heat-sensitive curing agent, or a combination of both.

The first resin composition may contain an epoxy compound and/or an oxetane compound that does not correspond to the siloxane-modified (meth)acrylic resin (A1).
The type of epoxy compound and/or oxetane compound that can be used together with the siloxane-modified (meth)acrylic resin (A1) is not particularly limited as long as it does not impede the object of the present invention.

In view of the low dielectric constant of the cured product, the ratio of the total mass of the siloxane-modified (meth)acrylic resin (A1) to the total mass of the epoxy compound and the oxetane compound in the first resin composition. is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

The curing agent is not particularly limited as long as it is a compound conventionally used as a curing agent for epoxy compounds or oxetane compounds. Preferred curing agents will be explained below.

・Onium salt (D1)
The onium salt (D1) can be used together with an epoxy compound, an oxetane compound, etc., and accelerates curing of the epoxy compound, oxetane compound, etc. by the action of light or heat.
Examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts, and the like. Among these, sulfonium salts and iodonium salts are preferred from the viewpoint of easy availability and good curing.

Preferred examples of the onium salt (D1) will be described below.
A preferred example of the onium salt (D1) is a sulfonium salt represented by the following formula (DI) (hereinafter also referred to as "sulfonium salt (Q)").

（式（Ｄ－Ｉ）中、Ｒ^Ｄ１及びＲ^Ｄ２は独立に、ハロゲン原子で置換されていてもよいアルキル基又は下記式（Ｄ－ＩＩ）で表される基を示し、Ｒ^Ｄ１及びＲ^Ｄ２は相互に結合して式中の硫黄原子とともに環を形成してもよく、Ｒ^Ｄ３は下記式（Ｄ－ＩＩＩ）で表される基又は下記式（Ｄ－ＩＶ）で表される基を示し、Ａ^Ｄ１はＳ、Ｏ、又はＳｅを示し、Ｘ^－は１価のアニオンを示し、但し、Ｒ^Ｄ１及びＲ^Ｄ２は、同時に、ハロゲン原子で置換されていてもよいアルキル基ではない。）

(In formula (DI), R ^D1 and R ^D2 independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following formula (D-II), and R ^D1 and R ^D2 may combine with each other to form a ring with the sulfur atom in the formula, and R ^D3 represents a group represented by the following formula (D-III) or a group represented by the following formula (D-IV). , A ^D1 represents S, O, or Se, and X ⁻ represents a monovalent anion, provided that R ^D1 and R ^D2 are not at the same time an alkyl group that may be substituted with a halogen atom.)

（式（Ｄ－ＩＩ）中、環Ｚ^Ｄ１は芳香族炭化水素環を示し、Ｒ^Ｄ４はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アルコキシカルボニル基、アシロキシ基、アルキルチオ基、チエニル基、チエニルカルボニル基、フラニル基、フラニルカルボニル基、セレノフェニル基、セレノフェニルカルボニル基、複素環式脂肪族炭化水素基、アルキルスルフィニル基、アルキルスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ１は０以上の整数を示す。）

(In formula (D-II), ring Z ^D1 represents an aromatic hydrocarbon ring, R ^D4 is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, Acyloxy group, alkylthio group, thienyl group, thienylcarbonyl group, furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy ) represents an alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more.)

（式（Ｄ－ＩＩＩ）中、Ｒ^Ｄ５はヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキレン基又は下記式（Ｄ－Ｖ）で表される基を示し、Ｒ^Ｄ６はヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキル基又は下記式（Ｄ－ＶＩ）で表される基を示し、Ａ^Ｄ２は単結合、Ｓ、Ｏ、スルフィニル基、又はカルボニル基を示し、ｎ１は０又は１を示す。）

(In formula (D-III), R ^D5 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group , or an alkylene group optionally substituted with a halogen atom, or a group represented by the following formula (DV), R ^D6 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy Indicates a (poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, an alkyl group optionally substituted with a halogen atom, or a group represented by the following formula (D-VI), ^D2 represents a single bond, S, O, sulfinyl group, or carbonyl group, and n1 represents 0 or 1.)

（式（Ｄ－ＩＶ）中、Ｒ^Ｄ７及びＲ^Ｄ８は独立に、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキレン基又は下記式（Ｄ－Ｖ）で表される基を示し、Ｒ^Ｄ９及びＲ^Ｄ１０は独立に、ハロゲン原子で置換されていてもよいアルキル基又は上記式（Ｄ－ＩＩ）で表される基を示し、Ｒ^Ｄ９及びＲ^Ｄ１０は相互に結合して式中の硫黄原子とともに環を形成してもよく、Ａ^Ｄ３は単結合、Ｓ、Ｏ、スルフィニル基、又はカルボニル基を示し、Ｘ^－は前記の通りであり、ｎ２は０又は１を示し、但し、Ｒ^Ｄ９及びＲ^Ｄ１０は、同時に、ハロゲン原子で置換されていてもよいアルキル基ではない。）

(In formula (D-IV), R ^D7 and R ^D8 are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthiocarbonyl group, group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group , a cyano group, a nitro group, an alkylene group optionally substituted with a halogen atom, or a group represented by the following formula (DV), and R ^D9 and R ^D10 are independently substituted with a halogen atom. represents an optional alkyl group or a group represented by the above formula (D-II), R ^D9 and R ^D10 may be bonded to each other to form a ring with the sulfur atom in the formula, and A ^D3 is a single a bond, S, O, a sulfinyl group, or a carbonyl group, X ^- is as described above, n2 represents 0 or 1, provided that R ^D9 and R ^D10 are simultaneously substituted with a halogen atom. is not a good alkyl group.)

（式（Ｄ－Ｖ）中、環Ｚ^Ｄ２は芳香族炭化水素環を示し、Ｒ^Ｄ１１はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ２は０以上の整数を示す。）

（式（Ｄ－ＶＩ）中、環Ｚ^Ｄ３は芳香族炭化水素環を示し、Ｒ^Ｄ１２はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、チエニルカルボニル基、フラニルカルボニル基、セレノフェニルカルボニル基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ３は０以上の整数を示す。）

(In formula (DV), ring Z ^D2 represents an aromatic hydrocarbon ring, R ^D11 is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, Alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl It represents a sulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more.)

(In formula (D-VI), ring Z ^D3 represents an aromatic hydrocarbon ring, R ^D12 is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, Alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group , an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m3 is 0 or more. (Indicates an integer.)

(Sulfonium salt (Q))
The sulfonium salt (Q) will be explained below. The sulfonium salt (Q) is characterized in that, in the benzene ring in the above formula (DI), a methyl group is bonded to the carbon atom ortho to the carbon atom to which A ^D1 is bonded. Since the sulfonium salt (Q) has a methyl group at the above position, it has higher sensitivity to active energy rays such as ultraviolet rays than conventional sulfonium salts.

In the above formula (DI), both R ^D1 and R ^D2 are preferably groups represented by the above formula (D-II). R ^D1 and R ^D2 may be the same or different.
In the above formula (DI), when R ^D1 and R ^D2 combine with each other to form a ring with the sulfur atom in the formula, the number of atoms constituting the formed ring is 3 or more including the sulfur atom. It is preferably 10 or less, more preferably 5 or more and 7 or less. The formed ring may be polycyclic, and preferably is a polycyclic ring in which monocyclic rings having 5 or more and 7 or less ring atoms are condensed.
In the above formula (DI), both R ^D1 and R ^D2 are preferably phenyl groups.
In the above formula (DI), R ^D3 is preferably a group represented by the above formula (D-III).
In the above formula (DI), A ^D1 is preferably S or O, and more preferably S.

In the above formula (D-II), R ^D4 is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, a substituted It is preferably an amino group or a nitro group, and more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom.
In the above formula (D-II), m1 can be selected depending on the type of ring Z ^D1 , and is, for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2. It may be.

In the above formula (D-III), R ^D5 is an alkylene group; an alkylene group substituted with a hydroxy group, an optionally substituted amino group, or a nitro group; or a group represented by the above formula (DV) is preferable, and a group represented by the above formula (DV) is more preferable.
In the above formula (D-III), R ^D6 is an alkyl group; an alkyl group substituted with a hydroxy group, an optionally substituted amino group, or a nitro group; or a group represented by the above formula (D-VI) is preferable, and a group represented by the above formula (D-VI) is more preferable.
In the above formula (D-III), A ^D2 is preferably S or O, and more preferably S.
In the above formula (D-III), n1 is preferably 0.

In the above formula (D-IV), R ^D7 and R ^D8 are independently an alkylene group; an alkylene group substituted with a hydroxy group, an optionally substituted amino group, or a nitro group; or the above formula (D-V) A group represented by the above formula (DV) is preferable, and a group represented by the above formula (DV) is more preferable. R ^D7 and R ^D8 may be the same or different.
In the above formula (D-IV), both R ^D9 and R ^D10 are preferably groups represented by the above formula (D-II). R ^D9 and R ^D10 may be the same or different.
In the above formula (D-IV), when R ^D9 and R ^D10 combine with each other to form a ring with the sulfur atom in the formula, the number of atoms constituting the formed ring is 3 or more including the sulfur atom. It is preferably 10 or less, more preferably 5 or more and 7 or less. The formed ring may be polycyclic, and preferably is a polycyclic ring in which monocyclic rings having 5 or more and 7 or less ring atoms are condensed.
In the above formula (D-IV), A ^D3 is preferably S or O, and more preferably S.
In the above formula (D-IV), n2 is preferably 0.

In the above formula (DV), R ^D11 is preferably an alkyl group that may be substituted with a halogen atom, a hydroxy group, an amino group that may be substituted, or a nitro group; More preferably, it is an optionally alkyl group.
In the above formula (DV), m2 can be selected depending on the type of ring Z ^D2 , for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2. It may be.

In the above formula (D-VI), R ^D12 is an alkyl group optionally substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group, a substituted It is preferably an amino group or a nitro group, and more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom.
In the above formula (D-VI), m3 can be selected depending on the type of ring Z ^D3 , and is, for example, an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2. It may be.

In the above formula (DI), X ⁻ is a monovalent anion. Preferable examples of X ⁻ include monovalent polyatomic anions, such as MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4-c ⁻ , R ^x1 _c GaY _4-c ⁻ , R More preferred are anions represented by ^x2 SO ₃ ^- , (R ^x2 SO ₂ ) ₃ C ^- , or (R ^x2 SO ₂ ) ₂ N ^- . Furthermore, X ⁻ may be a halogen anion, such as fluoride ion, chloride ion, bromide ion, iodide ion, etc.

M represents a phosphorus atom, a boron atom, or an antimony atom.
Y represents a halogen atom (preferably a fluorine atom).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be Rf by fluorine substitution include straight chain alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched chain alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.), and cyclo Examples include alkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.). In Rf, the ratio of hydrogen atoms of these alkyl groups being substituted with fluorine atoms is preferably 80 mol% or more, more preferably 90 mol% or more, based on the number of moles of hydrogen atoms that the original alkyl group had. % or more, particularly preferably 100%. When the substitution ratio by fluorine atoms is within these preferable ranges, the photosensitivity of the sulfonium salt (Q) becomes even better. Particularly preferable Rfs include CF ₃ -, CF ₃ CF ₂ ^- , (CF ₃ ) ₂ CF ^- , CF ₃ CF 2 CF ₂ ^- , CF ₃ CF ₂ CF _{2 CF 2} ^- , (CF ₃ ) ₂ CFCF ₂ ^- , CF ₃ CF ₂ (CF ₃ )CF ^- and (CF ₃ ) ₃ C ^- . The b Rf's are mutually independent and therefore may be the same or different from each other.

P represents a phosphorus atom, and F represents a fluorine atom.

R ^x1 represents a phenyl group in which some of the hydrogen atoms are substituted with at least one element or electron-withdrawing group. Examples of such an element include a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, and the like. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Among these, a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferred. The c R ^x1s are mutually independent and therefore may be the same or different from each other.

B represents a boron atom, and Ga represents a gallium atom.

R ^x2 represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and fluoroalkyl group are linear , may be branched or cyclic, and the alkyl group, fluoroalkyl group, or aryl group may be unsubstituted or may have a substituent. Examples of the above-mentioned substituent include a hydroxy group, an optionally substituted amino group (for example, those exemplified in the explanation below regarding formulas (D-II) to (D-VI)), nitro Examples include groups.
Further, the carbon chain in the alkyl group, fluoroalkyl group, or aryl group represented by R ^x2 may have a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. In particular, the carbon chain in the alkyl group or fluoroalkyl group represented by ^R bond, sulfonylimide bond, urethane bond, etc.).
When the alkyl group, fluoroalkyl group, or aryl group represented by R ^x2 has the above substituent, hetero atom, or functional group, the number of the above substituent, hetero atom, or functional group may be one. There may be two or more.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.
a represents an integer of 4 or more and 6 or less.
b is preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, particularly preferably 2 or 3.
c is preferably an integer of 1 or more and 4 or less, more preferably 4.

Examples of the anion represented by MY _a ⁻ include anions represented by SbF ₆ ⁻ , PF ₆ ⁻ , or BF ₄ ⁻ .

Anions represented by (Rf) _b PF _6-b ^- include (CF ₃ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CF) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CF) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ^- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^- or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^- Examples include anions such as Among these, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ Anions represented by PF ₄ ^- , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^- or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^- are preferred.

The anion represented by R ^x1 _c BY _4-c ^- is preferably:
R ^x1 _c BY _4-c ^-
(In the formula, R ^x1 represents a phenyl group in which at least a portion of the hydrogen atoms are substituted with a halogen atom or an electron-withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4.)
For example, (C ₆ F ₅ ) ₄ B ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , C ₆ F ₅ BF ₃ ⁻ or (C ₆ H ₃ F ₂ ) ₄ B ⁻ , and the like. Among these, an anion represented by (C ₆ F ₅ ) ₄ B ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ^- is preferred.

Anions represented by R ^x1 _c GaY _4-c ^- include (C ₆ F ₅ ) ₄ Ga ^- , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- , (CF ₃ C ₆ H ₄ ) ₄ Examples include anions represented by Ga ^- , (C ₆ F ₅ ) ₂ GaF ₂ ^- , C ₆ F ₅ GaF ₃ ^- , or (C ₆ H ₃ F ₂ ) ₄ Ga ^- . Among these, an anion represented by (C ₆ F ₅ ) ₄ Ga ^- or ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ^- is preferred.

Examples of the anion represented by R ^x2 SO ₃ ^- include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorophenylsulfonate anion, and p-toluene. Examples include sulfonic acid anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion, and butanesulfonic acid anion. Among these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion, or p-toluenesulfonate anion are preferred.

Anions represented by (R ^x2 SO ₂ ) ₃ C ^- include (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₃ F ₇ SO ₂ ) ₃ C ^- or (C ₄ F ₉ SO ₂ ) ₃ C ^- , and the like.

Anions represented by (R ^x2 SO ₂ ) ₂ N ^- include (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- or (C ₄ F ₉ SO ₂ ) ₂ N ^- , and the like.

Monovalent polyatomic anions include MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4-c ⁻ , R ^x1 _c GaY _4-c ⁻ , R ^x2 SO ₃ ⁻ , (R ^x2 In addition to anions represented by SO ₂ ) ₃ C ^- or (R ^x2 SO ₂ ) ₂ N ^- , perhalogenate ions (ClO ₄ ^- , BrO ₄ ^-, etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^-, etc.), sulfate ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^-, etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^-, etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^-, etc.), hexafluorobismuthate ion (BiF ₆ ^- ), carboxylate ion (CH ₃ COO ^- , CF ₃ COO ^- , C ₆ H ₅ COO ^- , CH ₃ C ₆ H ₄ COO ^- , C ₆ F ₅ COO ^- , CF ₃ C ₆ H ₄ COO ^- , etc.), arylborate ions (B(C ₆ H ₅ ) ₄ ^- , CH ₃ CH ₂ CH ₂ CH ₂ B(C ₆ H ₅ ) ₃ ^-, etc.), thiocyanic acid Ions (SCN ⁻ ), nitrate ions (NO ₃ ⁻ ), etc. can be used.

Among these X ^- , in terms of cationic polymerization performance, MY _a ^- , (Rf) _b PF _6-b ^- , R ^x1 _c BY _4-c ^- , R ^x1 _c GaY _4-c ^- and (R ^x2 SO ₂ ⁾ _Anion represented ^by _{3C- is} preferable, _{and SbF6-} ^, _PF6- , ( _CF3CF2 ) _{3PF3- ,} ( _C6F5 ) ^{4B- ,} ₍ ( _CF3 ) _2C6 H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ and (CF ₃ SO ₂ ) ₃ C ⁻ are more preferred, and R ^x1 _c BY _{4 -c-} ^is more preferred.

In the above formulas (D-II), (DV), and (D-VI), the aromatic hydrocarbon ring is a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring] Hydrogen rings (e.g., C _8-20 fused bicyclic hydrocarbon rings such as naphthalene rings, preferably C _10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (e.g., anthracene rings), , phenanthrene ring, etc.)]. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

In the above formulas (DI) to (D-VI), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the above formulas (DI) to (D-VI), the alkyl group is a straight-chain alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- -octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched chain alkyl groups having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl) , isopentyl, neopentyl, tert-pentyl, isohexyl, isooctadecyl, etc.), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, etc.). . In particular, in the above formulas (DI), (D-II), and (D-IV) to (D-VI), the alkyl group that may be substituted with a halogen atom refers to an alkyl group and a halogen atom. means a substituted alkyl group. Examples of the alkyl group substituted with a halogen atom include groups in which at least one hydrogen atom in the above linear alkyl group, branched alkyl group, or cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, trifluoromethyl, fluoromethyl, etc.). Among the alkyl groups that may be substituted with a halogen atom, for R ^D1 , R ^D2 , R ^D9 , or R ^D10 , a trifluoromethyl group is particularly preferable, and for R ^D4 , R ^D6 , R ^D11 , or R ^D12 , a trifluoromethyl group is particularly preferable. is particularly preferably a methyl group.

In the above formulas (D-II) to (D-VI), the alkoxy group is a linear or branched alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec -butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, octadecyloxy, etc.).

In the above formulas (D-II) to (D-VI), the alkyl group in the alkylcarbonyl group includes the above-mentioned straight chain alkyl group having 1 to 18 carbon atoms, and branched chain alkyl group having 3 to 18 carbon atoms. or a cycloalkyl group having 3 to 18 carbon atoms; examples of the alkylcarbonyl group include linear, branched, or cyclic alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, , 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl group, cyclohexanoyl group, etc.).

In the above formulas (D-III) to (D-VI), examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (benzoyl, naphthoyl, etc.).

In the above formulas (D-II) to (D-VI), the alkoxycarbonyl group is a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl , butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

In the above formulas (D-III) to (D-VI), examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

In the above formulas (D-III) to (D-VI), examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

In the above formulas (D-II) to (D-VI), the acyloxy group includes a straight or branched acyloxy group having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy, etc.).

In the above formulas (D-III) to (D-VI), the arylthio group has 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio). , 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio Thio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4 -(Phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio , 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio , 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio).

In the above formulas (D-II) to (D-VI), the alkylthio group is a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio, etc.).

In the above formulas (D-III) to (D-VI), examples of the aryl group include aryl groups having 6 to 10 carbon atoms (phenyl, tolyl, dimethylphenyl, naphthyl, etc.).

In the above formula (D-II), the heterocyclic aliphatic hydrocarbon group has 2 to 20 carbon atoms (preferably 4 to 20 carbon atoms) (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl). , piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.).

In the above formulas (D-III) to (D-VI), the heterocyclic hydrocarbon group has 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, Oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxatiinyl, chromanyl, isochromanyl, dibenzo thienyl, xanthonyl, thioxanthonyl, dibenzofuranyl, etc.).

In the above formulas (D-III) to (D-VI), examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

In the above formulas (D-II) to (D-VI), the alkylsulfinyl group is a linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butyl sulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, iso-octadecylsulfinyl, etc.).

In the above formulas (D-III) to (D-VI), examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl, etc.).

In the above formulas (D-II) to (D-VI), the alkylsulfonyl group includes a straight or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.).

In the above formulas (D-III) to (D-VI), the arylsulfonyl group includes an arylsulfonyl group having 6 to 10 carbon atoms (phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc.). Can be mentioned.

In the above formulas (D-II) to (D-VI), the hydroxy(poly)alkyleneoxy group is HO(AO) _q - (wherein AO independently represents an ethyleneoxy group and/or a propyleneoxy group). , q represents an integer of 1 or more and 5 or less).

In the above formulas (D-II) to (D-VI), the optionally substituted amino group includes an amino group (-NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino , ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino , diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.).

In the above formulas (D-III) and (D-IV), the alkylene group is a linear or branched alkylene group having 1 to 18 carbon atoms (methylene group, 1,2-ethylene group, 1,1- Ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane- 1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, 2-ethylhexane-1,6-diyl group, Nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14 -diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, etc.).

Specific examples of the cation moiety of the sulfonium salt (Q) represented by the above formula (DI) include the following. Specific examples of the anion moiety of the sulfonium salt (Q) represented by the above formula (DI) include conventionally known ones such as those listed in the explanation of X ^- above. The sulfonium salt (Q) represented by the above formula (DI) can be synthesized according to the above scheme, and if necessary, the cation moiety can be combined with a desired anion moiety by further salt exchange. , R ^x1 _c BY _4-c ^- (wherein, R ^x1 represents a phenyl group in which at least a portion of the hydrogen atoms are substituted with a halogen atom or an electron-withdrawing group, Y represents a halogen atom, and c represents 1 or more (indicates an integer of 4 or less) is preferred.

Among the above group of preferable cation moieties, the cation moiety represented by the following formula is more preferable.

The content of the onium salt (D1) in the resin composition is not particularly limited as long as curing of the resin composition proceeds satisfactorily. From the standpoint of easily curing the resin composition, the content of the onium salt (D1) in the resin composition is typically determined by adjusting the content of the onium salt (D1) in a material that is cured by the onium salt (D1) such as an epoxy compound and/or an oxetane compound. 0.01 parts by mass or more and 50 parts by mass or more, preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.01 parts by mass or more and 20 parts by mass or less, and 0.05 parts by mass relative to 100 parts by mass. It is more preferably 1 part by mass or more and 15 parts by mass or less, particularly preferably 1 part by mass or more and 10 parts by mass or less.

・Curing agent for epoxy compounds or oxetane compounds (D2)
The curing agent (D2) for epoxy compounds or oxetane compounds (hereinafter also referred to as curing agent (D2)) is a curing agent other than the above-mentioned onium salt (D1), and may be appropriately selected from conventionally known curing agents. Can be done. The curing agent (D2) contributes to curing by heating when used together with an epoxy compound or an oxetane compound.

Examples of the curing agent (D2) include phenolic curing agents, acid anhydride curing agents, polyvalent amine curing agents, and catalytic curing agents.
The amount of the phenolic curing agent and the acid anhydride curing agent used is preferably 1 part by mass or more and 200 parts by mass or less, and 50 parts by mass or less, based on 100 parts by mass of the total amount of the epoxy compound and oxetane compound in the resin composition. Parts by weight or more and 150 parts by weight or less are more preferable, and 80 parts by weight or more and 120 parts by weight or less are particularly preferable. The phenolic curing agent and the acid anhydride curing agent may be used alone or in combination of two or more.
The amount of the polyvalent amine curing agent used is preferably 0.1 parts by mass or more and 50 parts by mass or less, and 0.5 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total amount of the epoxy compound and oxetane compound in the resin composition. It is more preferably less than 1 part by mass, and particularly preferably 1 part by mass and 15 parts by mass. These polyvalent amine curing agents may be used alone or in combination of two or more.
The amount of the catalytic curing agent used is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 80 parts by mass or less, based on 100 parts by mass of the total amount of the epoxy compound and oxetane compound in the resin composition. , 1 part by mass or more and 50 parts by mass or less is particularly preferable. These catalytic curing agents may be used alone or in combination of two or more.

・Curing agent that generates a base component when heated (D3)
As the curing agent (D3) that generates a base component by heat, compounds conventionally used as thermal base generators can be used without particular limitation.
For example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one can be used as an effect agent that generates a base component by heat. Note that 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one also generates a base by the action of light.

（式（ｄ１）中、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、ホスフィノ基、スルホナト基、ホスフィニル基、ホスホナト基、又は有機基を示す。） Further, a compound that generates an imidazole compound represented by the following formula (d1) when heated (hereinafter also referred to as a thermal imidazole generator) is also preferably used as a curing agent.

(In formula (d1), R ^d1 , R ^d2 , and R ^d3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, Indicates a sulfonate group, phosphinyl group, phosphonato group, or organic group.)

Examples of the organic group for R ^d1 , R ^d2 , and R ^d3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom. Further, this organic group may be linear, branched, or cyclic. This organic group is usually monovalent, but when forming a cyclic structure, it can be a divalent or higher organic group.

R ^d1 and R ^d2 may be bonded together to form a cyclic structure, and may further include a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a fused ring.

The bonds contained in the organic groups of R ^d1 , R ^d2 , and R ^d3 are not particularly limited as long as the effects of the present invention are not impaired, and the organic groups include hetero atoms such as oxygen atoms, nitrogen atoms, and silicon atoms. May contain bonds. Specific examples of bonds containing heteroatoms include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N=C(-R ^d0 )-, -C( =NR ^d0 )-: R ^d0 represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

From the viewpoint of heat resistance of the imidazole compound, examples of the bond containing a heteroatom that the organic groups of R ^d1 , R ^d2 , and R ^d3 may include include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, and an ester bond. , amide bond, urethane bond, imino bond (-N=C(-R ^d0 )-, -C(=NR ^d0 )-: R ^d0 represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond is preferred.

When the organic groups of R ^d1 , R ^d2 , and R ^d3 are substituents other than hydrocarbon groups, R ^d1 , R ^d2 , and R ^d3 are not particularly limited as long as the effects of the present invention are not impaired. Specific examples of R ^d1 , R ^d2 , and R ^d3 include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a silyl group, a silanol group, Alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, alkyl ether group, alkenyl Examples include ether group, alkylthioether group, alkenylthioether group, aryl ether group, and arylthioether group. The hydrogen atom included in the above substituent may be substituted with a hydrocarbon group. Moreover, the hydrocarbon group contained in the above-mentioned substituent may be linear, branched, or cyclic.

R ^d1 , R ^d2 , and R ^d3 include a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen. An atom is preferable, and a hydrogen atom is more preferable.

The thermal imidazole generator is not particularly limited as long as it is a compound that can generate the imidazole compound represented by the above formula (d1) by heating. Regarding compounds that generate amines by the action of heat (thermal base generators), which have been conventionally blended into various compositions, the skeleton derived from the amine generated during heating is imidazole represented by the above formula (d1). By substituting the skeleton derived from the compound, a compound used as a thermal imidazole generator can be obtained.

（式（ｄ２）中、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を示す。Ｒ^ｄ４及びＲ^ｄ５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^ｄ６、Ｒ^ｄ７、Ｒ^ｄ８、Ｒ^ｄ９、及びＲ^ｄ１０は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。Ｒ^ｄ６、Ｒ^ｄ７、Ｒ^ｄ８、Ｒ^ｄ９、及びＲ^ｄ１０は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。）
で表される化合物が挙げられる。 A suitable thermal imidazole generator has the following formula (d2):

(In formula (d2), R ^d1 , R ^d2 , and R ^d3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, A phosphino group, a phosphinyl group, a phosphonato group, or an organic group.R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group. , a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group.R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 are each independently a hydrogen atom. , halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group , or represents an organic group. Two or more of R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 may be bonded to form a cyclic structure, and may include a bond of a heteroatom. )
Examples include compounds represented by:

In formula (d2), R ^d1 , R ^d2 , and R ^d3 are the same as those described for formula (d1).

In formula (d2), R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group. , a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group.

Examples of the organic group for R ^d4 and R ^d5 include those exemplified for R ^d1 , R ^d2 , and R ^d3 . This organic group may contain a heteroatom therein, as in the case of R ^d1 , R ^d2 , and R ^d3 . Further, this organic group may be linear, branched, or cyclic.

Among the above, R ^d4 and R ^d5 each independently include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and a cycloalkyl group having 4 to 13 carbon atoms. Alkenyl group, aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having cyano group and having 2 to 11 carbon atoms, 1 or more carbon atoms having hydroxyl group an alkyl group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, Ester group having 2 to 11 carbon atoms (-COOR ^d , -OCOR ^d : R ^d represents a hydrocarbon group), aryl group having 6 to 20 carbon atoms, electron-donating group and/or electron-withdrawing group An aryl group having 6 to 20 carbon atoms substituted with a group, a benzyl group, a cyano group, and a methylthio group substituted with an electron-donating group and/or an electron-withdrawing group are preferable. More preferably, both R ^d4 and R ^d5 are hydrogen atoms, or R ^d4 is a methyl group and R ^d5 is a hydrogen atom.

In formula (d2), R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group.

Examples of the organic groups for R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 include those exemplified for R ^d1 , R ^d2 , and R ^d3 . As in the case of R ^d1 and R ^d2 , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom. Further, this organic group may be linear, branched, or cyclic.

Two or more of R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 may be bonded to form a cyclic structure, and may include a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a fused ring. For example, R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 are bonded together, and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 are bonded to benzene. A condensed ring such as naphthalene, anthracene, phenanthrene, indene, etc. may be formed by sharing ring atoms.

Among the above, R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 each independently include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 4 to 13 carbon atoms. , a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms and having a cyano group. group, an alkyl group having 1 to 10 carbon atoms and having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, carbon An acyl group having 1 to 10 atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms substituted with an electron-donating group and/or an electron-withdrawing group. A benzyl group, a cyano group, a methylthio group, or a nitro group substituted with an aryl group, an electron-donating group, and/or an electron-withdrawing group of 20 or less is preferable.

Moreover, as R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 , two or more thereof are bonded, and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 are bonded. It is also preferable that the atoms of the benzene ring are shared to form a condensed ring such as naphthalene, anthracene, phenanthrene, indene, etc.

（式（ｄ３）中、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３は、式（ｄ１）及び（ｄ２）と同義である。Ｒ^ｄ４～Ｒ^ｄ９は式（ｄ２）と同義である。Ｒ^ｄ１１は、水素原子又は有機基を示す。Ｒ^ｄ６及びＲ^ｄ７が水酸基となることはない。Ｒ^ｄ６、Ｒ^ｄ７、Ｒ^ｄ８、及びＲ^ｄ９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。）
で表される化合物が好ましい。 Among the compounds represented by the above formula (d2), the following formula (d3):

(In formula (d3), R ^d1 , R ^d2 , and R ^d3 have the same meanings as formulas (d1) and (d2). ^{R d4} to R ^d9 have the same meanings as formula (d2). R ^d11 has the same meaning as formula (d2). Represents a hydrogen atom or an organic group. R ^d6 and R ^d7 cannot be a hydroxyl group. R ^d6 , R ^d7 , R ^d8 , and R ^d9 are two or more of them that are combined to form a cyclic structure. may contain a heteroatom bond.)
Compounds represented by are preferred.

Since the compound represented by formula (d3) has the substituent -O-R ^d11 , it has excellent solubility in organic solvents.

In formula (d3), R ^d11 is a hydrogen atom or an organic group. When R ^d11 is an organic group, examples of the organic group include those exemplified for R ^d1 , R ^d2 , and R ^d3 . This organic group may contain a heteroatom within the organic group. Further, this organic group may be linear, branched, or cyclic. R ^d11 is preferably a hydrogen atom, an alkyl group or an alkoxyalkyl group having 1 to 12 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group. More preferred are a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxymethyl group, and a butoxymethyl group.

Specific examples of compounds particularly suitable as thermal imidazole generators are shown below.

・Organic solvent (S)
The resin composition may typically contain an organic solvent (S) for the purpose of adjusting coating properties. Examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether. -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n- Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. ) Alkylene glycol monoalkyl ethers; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 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 , other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N Amides such as -dimethylformamide and N,N-dimethylacetamide are included. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent (S) to be used can be appropriately determined depending on the use of the resin composition. An example of the amount of the organic solvent (S) to be used is such that the solid content concentration of the resin composition is in the range of 1% by mass or more and 50% by mass or less.

-Other components The resin composition may contain various other additives other than the above-mentioned components, if necessary. Specifically, dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, thermal polymerization inhibitors, antifoaming agents, surfactants and the like are exemplified.

The resin composition may contain an epoxy group-containing cyclic siloxane compound (A-II) that has not reacted with the (meth)acrylic resin (A-I). The resin composition preferably does not contain an epoxy group-containing cyclic siloxane compound, since it is easy to form a cured product with a low dielectric constant. When the resin composition contains the epoxy group-containing cyclic siloxane compound (A-II), its content is preferably 40% by mass or less based on the mass of the resin composition excluding the mass of the organic solvent (S), It is more preferably 10% by mass or less, even more preferably 1% by mass or less.

(Second resin composition)
The second resin composition contains the aforementioned siloxane-modified (meth)acrylic resin (A1), a photopolymerizable monomer (B), and a photopolymerization initiator (C). However, the siloxane-modified (meth)acrylic resin (A1) contains, as an alkali-soluble resin, a (meth)acrylic resin containing a structural unit having an alkali-soluble group. The alkali-soluble group is not particularly limited, and examples include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
The second resin composition contains a photopolymerizable monomer (B) and a photopolymerization initiator (C) and is cured by exposure to light. On the other hand, the second resin composition in an unexposed state contains a siloxane-modified (meth)acrylic resin (A1) containing a structural unit having an alkali-soluble group, and therefore is not soluble in an alkaline developer. be. Therefore, when using the second resin composition, it is possible to pattern the cured film by photolithography using a negative photomask.
Since the second resin composition contains the siloxane-modified (meth)acrylic resin (A1) having an epoxy group, it can also be cured by heating. The second resin composition does not need to contain a curing agent for the epoxy compound. This is because the curing reaction of the epoxy group progresses due to the action of alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups that the siloxane-modified (meth)acrylic resin has.

Hereinafter, essential or optional components that the second resin composition may contain will be explained.

・Siloxane-modified (meth)acrylic resin (A1)
The siloxane-modified (meth)acrylic resin (A1) containing a structural unit having an alkali-soluble group is as described above.

-Other resins The second resin composition may contain various alkali-soluble resins as other resins other than the siloxane-modified (meth)acrylic resin (A1).
Due to the low dielectric constant of the cured product, in the second resin composition, the siloxane-modified (meth)acrylic resin is larger than the total mass of the siloxane-modified (meth)acrylic resin (A1) and the mass of other resins. The mass ratio of (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

Hereinafter, alkali-soluble resins suitable as other resins will be explained.

Suitable alkali-soluble resins include resins (a-1) having a cardo structure (hereinafter also referred to as "cardo resins (a-1)").

As the resin having a cardo structure (a-1), a resin having a cardo structure in its structure and having a predetermined alkali solubility can be used. The cardo structure refers to a structure in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. Note that the second cyclic structure and the third cyclic structure may be the same structure or different structures.
A typical example of the cardo structure is a structure in which two aromatic rings (for example, benzene rings) are bonded to the 9-position carbon atom of a fluorene ring.

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

In formula (a-1), X ^a represents a group represented by formula (a-2) below. t1 represents an integer from 0 to 20.

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. are particularly preferred, and ethane-1,2-diyl, propane-1,2-diyl, and propane-1,3-diyl groups are most preferred.

Ring A ¹ in formula (a-3) represents an aliphatic ring which may be fused with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle.
Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.
Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The aromatic ring which may be fused to the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, with an aromatic hydrocarbon ring being preferred. Specifically, a benzene ring and a naphthalene ring are preferred.

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

The divalent group ^{X a} in formula (a-1) can be converted to a cardo by reacting a tetracarboxylic dianhydride giving the residue Z ^a with a diol compound represented by the following formula (a-2a). Introduced into resin (a-1).

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and t2 are as described for formula (a-2). Ring A ¹ in formula (a-2a) is as described for formula (a-3).

The diol compound represented by formula (a-2a) can be produced, for example, by the following method.
First, after substituting the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with a group represented by -R ^a3 -OH according to a conventional method, if necessary, Glycidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2c).
Next, the diol compound represented by formula (a-2a) is obtained by reacting the epoxy compound represented by formula (a-2c) with acrylic acid or methacrylic acid.
In formula (a-2b) and formula (a-2c), R ^a1 , R ^a3 , and t2 are as described for formula (a-2). Ring A ¹ in formula (a-2b) and formula (a-2c) is as explained for formula (a-3).
Note that 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 the above formula (a-1), R ^a0 is a hydrogen atom or a group represented by -CO-Y ^a -COOH. Here, Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and 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 dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. and biphenyl ether tetracarboxylic dianhydride. Among these, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride is preferable, and pyromellitic dianhydride is preferable since it has a wide development process margin.
In the above formula (a-1), t1 represents an integer of 0 or more and 20.

（式（ａ－４）中、Ｒ^ａ４、Ｒ^ａ５、及びＲ^ａ６は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｔ３は、０以上１２以下の整数を示す。）

(In formula (a-4), R ^a4 , R ^a5 , and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. and t3 represents 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 or more and 10 or less carbon atoms. By setting the number of carbon atoms included in the alkyl group within this range, the heat resistance of the obtained carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 4 or less, from the standpoint of easily obtaining cardo resin having excellent heat resistance. Particularly preferably 1 or more and 3 or less.
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 1 or more and 10 or less carbon atoms, each independently from the viewpoint that it is easy to obtain a cardo resin having excellent heat resistance. R ^a4 in formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
The plurality of R ^a4 's in formula (a-4) are preferably the same group because it is easy to prepare a highly pure tetracarboxylic dianhydride.

t3 in formula (a-4) represents an integer from 0 to 12. By setting the value of t3 to 12 or less, purification of the tetracarboxylic dianhydride can be facilitated.
From the viewpoint of easy purification of the tetracarboxylic dianhydride, the upper limit of t3 is preferably 5, and more preferably 3.
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.

In formula (a-4), the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a5 and R ^a6 is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a4 . .
R ^a5 and R ^a6 are a hydrogen atom or a carbon atom number of 1 to 10 (preferably 1 to 6, more preferably 1 to 5, More preferably, it is an alkyl group of 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 dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (also known as ``norbornane- 2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α- Cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'- spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2''-norbornane-5, 5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2''-norbornane-5,5'',6,6' '-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride , norbornane-2-spiro-α-cyclononanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone -α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2' '-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5' ',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''- Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α -(Methylcyclopentanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone) -α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride and the like.

The weight average molecular weight of the cardo resin (a-1) is preferably 1,000 or more and 40,000 or less, more preferably 1,500 or more and 30,000 or less, and even more preferably 2,000 or more and 10,000 or less. By setting it within the above range, it is possible to obtain sufficient heat resistance and mechanical strength for the cured product while obtaining good developability.

Novolac resin (a-2) is also preferred as an alkali-soluble resin used together with (meth)acrylic resin (A1).

As the novolak resin (a-2), various novolak resins conventionally blended into photosensitive compositions can be used. The novolak resin (a-2) is preferably a resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and an aldehyde under an acid catalyst.

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

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

Also preferred is a novolac resin produced using a combination of m-cresol and 2,3,5-trimethylphenol. When such a novolak resin is used, it is particularly easy to obtain a resin composition that can form a cured product that does not flow excessively when heated during post-baking.
The blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the m-cresol/2,3,5-trimethylphenol molar ratio is preferably 70/30 or more and 95/5 or less.

Examples of aldehydes used in producing the novolac resin (a-2) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

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

The weight average molecular weight (Mw; hereinafter also simply referred to as "weight average molecular weight") of the novolac resin (a-2) in terms of polystyrene is a measure of the resistance to flow caused by heating of the cured product formed using the photosensitive composition. From this point of view, the lower limit is preferably 2,000, more preferably 5,000, particularly preferably 10,000, even more preferably 15,000, most preferably 20,000, and the upper limit is preferably 50,000, more preferably 45,000, even more preferably 40,000, most preferably 35,000. preferable.

As the novolac resin (a-2), at least two resins having different weight average molecular weights in terms of polystyrene may be used in combination. By using a combination of resins having different weight average molecular weights, it is possible to balance the developability of the photosensitive composition and the heat resistance of a cured product formed using the photosensitive composition.

Modified epoxy resin (a-3) is also preferred as the alkali-soluble resin used together with siloxane-modified (meth)acrylic resin (A1).

A polybasic acid anhydride is added to the reaction product of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) because it is difficult to deform by heating and easily forms a cured product with high water resistance. It may also contain an adduct of (a-3c). Such an adduct is also referred to as "modified epoxy resin (a-3)".
In addition, in the specification and claims of this application, a compound that falls under the above definition and does not fall under the above-mentioned resin having a cardo structure (a-1) is referred to as a modified epoxy resin (a-3). ).

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

The epoxy compound (a-3a) is not particularly limited as long as it has an epoxy group, and may be an aromatic epoxy compound having an aromatic group or an aliphatic epoxy compound not containing an aromatic group. Often, aromatic epoxy compounds having aromatic groups are preferred.
The epoxy compound (a-3a) may be a monofunctional epoxy compound or a polyfunctional epoxy compound having two or more functionalities, and a polyfunctional epoxy compound is preferred.

Specific examples of the epoxy compound (a-3a) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, and biphenyl epoxy resin. Functional epoxy resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl amino diphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene diamine, tetraglycidyl bisaminomethyl cyclohexane, etc. Glycidylamine type epoxy resin; heterocyclic epoxy resin such as triglycidyl isocyanurate; phloroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2-[4- (2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, and 1,3-bis[4- [1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy] Trifunctional epoxy resins such as -2-propanol; tetrafunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

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

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

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

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

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

When R ^a7 is a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1.
Examples of 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. Examples include groups.

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

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

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

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

In preparing the modified epoxy compound (a-3), the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) are reacted.
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. Further, the unsaturated group-containing carboxylic acid (a-3b) may be used alone or in combination of two or more types.

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

The ratio of the amounts used in the reaction between the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) is determined by the epoxy equivalent of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b). The ratio to the carboxylic acid equivalent of a-3b) is usually preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, and 1:0.9 to 1:1. .1 is particularly 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 from 1:0.5 to 1:2 in terms of the above-mentioned equivalent ratio, the crosslinking efficiency is increased. This is preferable because it tends to improve.

The polybasic acid anhydride (a-3c) is an anhydride of a carboxylic acid having two or more carboxy groups.
Examples of the polybasic acid anhydride (a-3c) include, but are not limited to, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydro anhydride. 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). Further, the polybasic acid anhydrides (a-3c) may be used alone or in combination of two or more types.

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

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

As the polybasic acid anhydride (a-3c), a compound having two or more benzene rings is preferable because it is easy to obtain a resin composition with an excellent balance between sensitivity and developability. Furthermore, the polybasic acid anhydride (a-3c) contains at least one of the compound represented by the above formula (a-3c-1) and the compound represented by the above formula (a-3c-2). is more preferable.

The method of reacting the epoxy compound (a-3a) with the unsaturated group-containing carboxylic acid (a-3b) and then reacting with the polybasic acid anhydride (a-3c) can be appropriately selected from known methods.
In addition, the usage ratio is determined by the number of moles of OH groups in the components after the reaction of the epoxy compound (a-3a) and the unsaturated group-containing carboxylic acid (a-3b) and the polybasic acid anhydride (a-3c). ) is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. By setting it as the above-mentioned range, it is easy to obtain a resin composition with good developability.

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

The weight average molecular weight of the modified epoxy resin (a-3) is preferably 1,000 or more and 40,000 or less, more preferably 2,000 or more and 30,000 or less. When the weight average molecular weight is 1000 or more, it is easy to form a cured product with excellent heat resistance and strength. Moreover, since the weight average molecular weight is 40,000 or less, it is easy to obtain a resin composition that exhibits sufficient solubility in a developer.

(Meth)acrylic resin (a-4), which is a resin other than (meth)acrylic resin (A1), can also be used as a component constituting the alkali-soluble resin.
When the (meth)acrylic resin (A-I) that has not been modified with the epoxy group-containing cyclic siloxane compound (A-II) has an alkali-soluble group, the (meth)acrylic resin (A-I) is ) It can also be used as an acrylic resin (a-4).
As the (meth)acrylic resin (a-4), it is possible to use a resin containing structural units derived from (meth)acrylic acid and/or structural units derived from other monomers such as (meth)acrylic acid ester. can. (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 impede the purpose of the present invention.

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

Further, 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, at least a part of the epoxy group in the (meth)acrylic resin (a-4) containing a structural unit having an epoxy group. It can be produced by reacting unsaturated carboxylic acid such as acrylic acid or methacrylic acid.
After reacting at least a portion of the epoxy group with an unsaturated carboxylic acid, the group generated by the reaction may be reacted with a polybasic acid anhydride.

Specific examples of polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexa Examples include hydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride.

As a specific example, when a structural unit derived from glycidyl methacrylate is reacted with acrylic acid, a structural unit having a hydroxyl group as shown in the following reaction formula is generated. By reacting such a structural unit having a hydroxyl group with a polybasic acid anhydride such as tetrahydrophthalic acid, a structural unit having a carboxy group and an unsaturated double bond that imparts alkali solubility to the resin is generated.

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

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

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

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

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

Specific examples when the compound represented by formula (a-4-1) is an alicyclic epoxy group-containing (meth)acrylic ester include the following formulas (a-4-1a) to (a-4). -1o). Among these, in order to keep the developability within an appropriate range, compounds represented by the following formulas (a-4-1a) to (a-4-1e) are preferred; ) to (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 aliphatic saturated 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, or 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 (representing a phenylene group) is preferred.

Furthermore, the (meth)acrylic resin (a-4) may be a copolymer obtained by further polymerizing a monomer other than the (meth)acrylic acid ester. Examples of monomers other than (meth)acrylic esters include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used alone or in combination of two or more. Suitable examples of these monomers are as described for the (meth)acrylic resin (A1).

The amount of structural units derived from (meth)acrylic acid and the amount of structural units derived from other monomers in the (meth)acrylic resin (a-4) are particularly limited to the extent that they do not impede the purpose of the present invention. Not done. The amount of structural units derived from (meth)acrylic acid in the (meth)acrylic resin (a-4) is 5% by mass or more and 50% by mass or less based on the mass of the (meth)acrylic resin (a-4). is preferable, and more preferably 10% by mass or more and 30% by mass or less.

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

The weight average molecular weight of the (meth)acrylic resin (a-4) is preferably 2,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less. By setting it within the above range, there is a tendency that the film forming ability of the resin composition and the developability after exposure are easily balanced.

In the second resin composition, the total mass of the (meth)acrylic resin (A1) and the mass of other resins is the mass of the resin composition (total solid content) excluding the mass of the organic solvent (S) described below. ) is preferably 20% by mass or more and 85% by mass or less, more preferably 25% by mass or more and 75% by mass or less. By setting it as the said range, it will be easy to obtain a resin composition with excellent developability.

・Photopolymerizable monomer (B)
The second resin composition contains a photopolymerizable monomer (B). As the photopolymerizable monomer (B), compounds conventionally blended into photosensitive compositions can be used without particular limitation.

Examples of monofunctional photopolymerizable monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxymethoxymethyl (meth)acrylamide. , N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid , 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2 -Hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, dimethylamino(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate, 2,2 , 3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivatives. These monofunctional photopolymerizable monomers can be used alone or in combination of two or more.

Polyfunctional photopolymerizable 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, and 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, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy- 3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin Polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e. tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, Examples include polyfunctional monomers such as (meth)acrylamide methylene ether, a condensate of polyhydric alcohol and N-methylol (meth)acrylamide, and triacryl formal. These polyfunctional photopolymerizable monomers can be used alone or in combination of two or more.

Among these photopolymerizable monomers (B), trifunctional or higher functional photopolymerizable monomers are preferred from the viewpoint of increasing the adhesion of the resin composition to the substrate and the strength of the resin composition after curing. , polyfunctional monomers having four or more functionalities are more preferred, and polyfunctional photopolymerizable monomers having five or more functionalities are even more preferred.

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

・Photopolymerization initiator (C)
As the photopolymerization initiator, compounds used in conventionally known photosensitive compositions for the purpose of curing photopolymerizable monomers having unsaturated bonds can be used without particular limitation.

Specifically, the photopolymerization initiator (C) includes 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 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, 4-benzoyl-4'-methyldimethylsulfide, 4 -dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoate acid, 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- Ethyl anthraquinone, octamethyl anthraquinone, 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-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 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-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2- (4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2 , 4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s- Examples include triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like.

These photopolymerization initiators (C) can be used alone or in combination of two or more.

In addition, in terms of the sensitivity of the resin composition, an oxime ester compound is preferable as the photopolymerization initiator (C).
As the oxime ester compound, for example, an oxime ester compound represented by the following formula (c1) is preferable.

In the above formula (c1), R ^c11 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a phenyl group which may have a substituent. Indicates a carbazolyl group. a is 0 or 1. R ^c12 represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. R ^c13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.

When R ^c11 is an alkyl group having 1 or more and 10 or less carbon atoms which may have a substituent, the type of substituent that the alkyl group has is not particularly limited as long as it does not impede the object of the present invention.

Examples of suitable substituents that an alkyl group having 1 to 10 carbon atoms may have include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. A cycloalkoxy group having a number of 3 to 10, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, Phenyl group that may have a substituent, phenoxy group that may have a substituent, phenylthio group that may have a substituent, benzoyl group that may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a substituted Naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, A naphthylalkyl group having from 11 to 20 carbon atoms which may have one or more carbon atoms, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, or one or two organic groups. Examples include substituted amino groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups.

The alkyl group having 1 to 10 carbon atoms may be linear or branched. In this case, the number of carbon atoms in the alkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less.

When R ^c11 is a phenyl group which may have a substituent, the type of the substituent is not particularly limited as long as it does not impede the object of the present invention. Suitable examples of substituents that the phenyl group may have include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenoxy group which may have a substituent benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, Naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, amino Examples include amino groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups substituted with one or two organic groups. When R ^c11 is a phenyl group which may have a substituent, and the phenyl group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the phenyl group is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, even more preferably 1 or more and 6 or less, particularly preferably 1 or more and 3 or less, 1 is most preferred. Further, the alkyl group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group , an isononyl group, an n-decyl group, an isodecyl group, and the like. Further, the alkyl group may contain an ether bond (-O-) in the carbon chain. In this case, examples of the substituent that the phenyl group has include an alkoxyalkyl group and an alkoxyalkoxyalkyl group. When the substituent of the phenyl group is an alkoxyalkyl group, a group represented by -R ^c14 -O-R ^c15 is preferable. R ^c14 is an alkylene group having 1 to 10 carbon atoms and which may be linear or branched. R ^c15 is an alkyl group having 1 or more and 10 or less carbon atoms, which may be linear or branched. The number of carbon atoms in R ^c14 is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. The number of carbon atoms in R ^c15 is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When the substituent of the phenyl group is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, the alkoxy group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, 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 Examples include -octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Further, 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 group, ethoxyethoxy group, 2-methoxy-1-methylethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and Examples include methoxypropyloxy group.

When the substituent of the phenyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when the substituent of the phenyl group is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when the substituent of the phenyl group is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. It will be done.

When the substituent of the phenyl group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when the substituent of the phenyl group is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, and 2,2-dimethylpropanoyl group. Noyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, Examples include n-pentadecanoyl group and n-hexadecanoyl group. Specific examples when the substituent of the phenyl group is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group. group, 2,2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyl Examples include oxy group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When the substituent of the phenyl group is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when the substituent of the phenyl group is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, and an isobutyloxycarbonyl group. , sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n -heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxy Examples include carbonyl group and isodecyloxycarbonyl group.

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

When the substituent of the phenyl group is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or a combination of such monocycles, or a combination of such monocycles and benzene. It is a heterocyclyl group fused with a ring. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When the substituent that the phenyl group has is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When the substituent of the phenyl group is an amino group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. Cycloalkyl group, saturated aliphatic acyl group having 2 to 20 carbon atoms, saturated aliphatic acyloxy group having 2 to 20 carbon atoms, phenyl group which may have a substituent, even if it has a substituent Benzoyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms; Examples thereof include naphthylalkyl groups having 11 to 20 carbon atoms, which may be optionally substituted, and heterocyclyl groups. Specific examples of these suitable organic groups include those mentioned above for the substituents possessed by the phenyl group. Specific examples of amino groups substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group, and N-acetyl-N-acetyloxyamino group.

When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents of the phenyl group further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. alkoxy group, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 1 to 6 carbon atoms A monoalkylamino group having the following alkyl group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, etc. can be mentioned. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents contained in the phenyl group further have a substituent, the number of the substituents is not limited as long as it does not impede the purpose of the present invention, but it is 1 or more and 4 The following are preferred. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents of the phenyl group have a plurality of substituents, the plurality of substituents may be the same or different.

The substituent in the case where R ^c11 is a phenyl group which may have a substituent has been described above, and among these substituents, an alkyl group or an alkoxyalkyl group is preferable.

When R ^c11 is a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituents are not particularly limited as long as they do not impede the object of the present invention. When R ^c11 is a phenyl group that may have a substituent, the phenyl group that may have a substituent is o- A tolyl group is preferred.

When R ^c11 is a carbazolyl group which may have a substituent, the type of the substituent is not particularly limited as long as it does not impede the object of the present invention. Examples of suitable substituents that the carbazolyl group may have on carbon atoms include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 3 to 10 carbon atoms. cycloalkyl group, cycloalkoxy group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, 2 to 20 carbon atoms Saturated aliphatic acyloxy group, phenyl group which may have a substituent, phenoxy group which may have a substituent, phenylthio group which may have a substituent, phenylcarbonyl which may have a substituent group, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a carbon atom number of 7 or more which may have a substituent 20 or less phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthylcarbonyl group, optionally substituted naphthoyl group group, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a substituent a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. group, halogen, nitro group, and cyano group.

When R ^c11 is a carbazolyl group that may have a substituent, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a carbon Cycloalkyl group having 3 to 10 atoms, saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have a substituent, substituent a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent group, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a naphthylalkyl group which may have a substituent Examples include a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

Specific examples of substituents that the carbazolyl group may have include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, Regarding the phenylalkyl group which may optionally have a substituent, the naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with one or two organic groups, R ^c11 is substituted. This is the same as the example of the substituent that the phenyl group has when it is a phenyl group that may have a group.

In R ^c11 , examples of substituents when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; Alkoxy group having a number of 1 to 6; Saturated aliphatic acyl group having 2 to 7 carbon atoms; Alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy group having 2 to 7 carbon atoms; Phenyl group; naphthyl group; benzoyl group; naphthoyl group; benzoyl 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 ; halogen; nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents contained in the carbazolyl group further have a substituent, the number of the substituents is not limited as long as it does not impede the purpose of the present invention, but is 1 or more and 4 or less. is preferred. When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c12 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent.

When R ^c12 is an alkyl group having 1 or more and 10 or less carbon atoms which may have a substituent, the alkyl group may be a straight chain or a branched chain. In this case, the number of carbon atoms in the alkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less.

In R ^c12 , the substituent that the alkyl group or phenyl group has is not particularly limited as long as it does not impede the object of the present invention.
Examples of suitable substituents that the alkyl group may have on carbon atoms include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. The following cycloalkoxy groups, saturated aliphatic acyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, saturated aliphatic acyloxy groups having 2 to 20 carbon atoms, and having substituents. phenyl group which may have a substituent, phenoxy group which may have a substituent, phenylthio group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl which may have a substituent group, a benzoyloxy group that may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms that may have a substituent, a naphthyl group that may have a substituent, a benzoyloxy group that may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthoyl group which may have a substituent A naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, an amino substituted with one or two organic groups group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, and the like.
Examples of suitable substituents that a phenyl group may have on a carbon atom include, in addition to the groups exemplified above as suitable substituents that an alkyl group may have on a carbon atom, Examples include 1 or more and 20 or less alkyl groups.

Specific examples of substituents that an alkyl group or phenyl group may have include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents Regarding phenylalkyl groups which may have R, naphthylalkyl groups which may have substituents, heterocyclyl groups which may have substituents, and amino groups substituted with one or two organic groups, R This is the same as the example of the substituent that the phenyl group has when ^c11 is a phenyl group that may have a substituent.

In R ^c12 , examples of substituents when the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents of the alkyl group or phenyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; ; Alkoxy group having 1 to 6 carbon atoms; Saturated aliphatic acyl group having 2 to 7 carbon atoms; Alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy having 2 to 7 carbon atoms Group; phenyl group; naphthyl group; benzoyl group; naphthoyl group; group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group benzoyl group substituted with; 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; piperazine-1 -yl group; halogen; nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituents of the alkyl group or the phenyl group further have a substituent, the number of the substituents is not limited to the extent that it does not impede the purpose of the present invention, but 1 The number is preferably 4 or less. When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

When R ^c12 is a carbazolyl group that may have a substituent, the type of substituent that the carbazolyl group has is not particularly limited as long as it does not impede the object of the present invention. Suitable examples of the substituent that the carbazolyl group may have are the same as the examples of the substituent when R ^c11 is a carbazolyl group that may have a substituent.

又は、下記式（ｃ３）：

で表される基が好ましい。 In view of the reactivity of the compound represented by formula (c1), R ^c12 is the following formula (c2):

Or the following formula (c3):

A group represented by is preferable.

In formula (c2), R ^c16 and R ^c17 are each a monovalent organic group, and b is 0 or 1. In formula (c3), R ^c18 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A ^c1 is S or O, and c is 0 It is an integer greater than or equal to 4 and less than or equal to 4.

R ^c16 in formula (c2) can be selected from various organic groups as long as the object of the present invention is not impaired. Suitable examples of R ^c16 include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and a carbon atom. An alkoxycarbonyl group having 2 to 20 atoms, a phenyl group that may have a substituent, a benzoyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a phenyl group that may have a substituent, a phenylalkyl group having from 7 to 20 carbon atoms which may optionally have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent; Examples include a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^c16 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c17 in formula (c2) is not particularly limited as long as it does not impede the object of the present invention, and can be selected from various organic groups. Specific examples of groups suitable as R ^c17 include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group that may have a substituent, a naphthyl group that may have a substituent, and a substituted A heterocyclyl group which may have a group is mentioned. Among these groups, R ^c17 is more preferably a phenyl group which may have a substituent, and a naphthyl group which may have a substituent, and particularly preferably a 2-methylphenyl group and a naphthyl group.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c16 or R ^c17 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Alkoxy group, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 1 to 6 carbon atoms A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, etc. Can be mentioned. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c16 or R ^c17 further has a substituent, the number of the substituents is not limited as long as it does not impede the purpose of the present invention, but is 1 or more and 4 or less. is preferred. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c16 or R ^c17 has a plurality of substituents, the plurality of substituents may be the same or different.

When R ^c18 in formula (c3) is an organic group, R ^c18 can be selected from various organic groups as long as the object of the present invention is not impaired. In formula (c3), preferable examples when R ^c18 is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms; Saturated aliphatic acyl group; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; 1 to 6 carbon atoms A benzoyl group substituted with a group selected from the following alkyl groups, morpholin-1-yl groups, piperazin-1-yl groups, and phenyl groups; Monos having an alkyl group having 1 to 6 carbon atoms Alkylamino group; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; cyano group; 2-methylphenylcarbonyl group; 4 -(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group can be mentioned.

In R ^c18 , substituted with a group selected from the group consisting of benzoyl group; naphthoyl group; alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group. benzoyl group; nitro group is preferred; benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group is more preferred.

Further, in formula (c3), c 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 c is 1, the bonding position of R ^c18 is preferably at the para position with respect to the bond between the phenyl group to which R ^c18 is bonded and the sulfur atom.

R ^c13 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. When it is a phenyl group which may have a substituent, the substituent which the phenyl group may have is the same as when R ^c11 is a phenyl group which may have a substituent. R ^c13 is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.

Among the compounds represented by the above formula (c1), preferred compounds include the compound represented by the following formula (c4).

In the above formula (c4), a, R ^c12 and R ^c13 are as described above. R ^c19 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, and d is an integer of 0 to 4.

In the above formula (c4), R ^c19 is not particularly limited as long as it does not impede the object of the present invention, and when it is an organic group, it is appropriately selected from various organic groups. Preferred examples of R ^c19 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, Phenoxy group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, benzoyl group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthyl group which may have a substituent oxycarbonyl group, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, amino group, one or two organic groups. Examples include substituted amino groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups. When s is an integer from 2 to 4, R ^c19 may be the same or different. Moreover, the number of carbon atoms of a substituent does not include the number of carbon atoms of a substituent that the substituent further has.

When R ^c19 is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Further, when R ^c19 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^c19 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group. , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples include n-decyl group and isodecyl group. Further, when R ^c19 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^c19 is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Further, when R ^c19 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^c19 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, 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, and isodecyloxy group. Further, when R ^c19 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.

When R ^c19 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples when R ^c19 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^c19 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c19 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c19 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanoyl group Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples when R ^c19 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n Examples include -dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^c19 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c19 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples include isodecyloxycarbonyl group.

When R ^c19 is a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Further, when R ^c19 is a naphthylalkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples when R ^c19 is a phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. Specific examples when R ^c19 is a naphthyl alkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. . When R ^c19 is a phenylalkyl group or a naphthyl alkyl group, R ^c19 may further have a substituent on the phenyl group or naphthyl group.

When R ^c19 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or such monocycles are fused together, or such monocycles are fused with a benzene ring. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^c19 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c19 is an amino group substituted with 1 or 2 organic groups, suitable 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 20 carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, 7 to 20 carbon atoms which may have a substituent phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and heterocyclyl group etc. Specific examples of these suitable organic groups are the same as R ^c19 . Specific examples of amino groups substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butyl Amino 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, naphthyl Amino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-deca Examples include noylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c19 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, alkyl group having 1 to 6 carbon atoms Examples include a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c19 further has a substituent, the number of the substituent is not limited as long as it does not impede the object of the present invention, but it is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c19 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c19 , alkyl groups with 1 to 6 carbon atoms and 1 carbon atom are used because they are chemically stable, have little steric hindrance, and are easy to synthesize oxime ester compounds. A group selected from the group consisting of an alkoxy group having 6 or more carbon atoms and a saturated aliphatic acyl group having 2 or more carbon atoms and 7 or less carbon atoms is preferable, an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms is more preferable, and a methyl group is particularly preferable. .

Regarding the position where R ^c19 is bonded to the phenyl group, the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is the 1st position, and the methyl group is the 2nd position of the phenyl group to which R ^c19 is bonded. The 4th or 5th position is preferred, and the 5th position is more preferred. Further, d is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

R ^c13 in the above formula (c4) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. Specific examples of R ^c13 are as described above for formula (c1). R ^c13 in formula (c4) is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.

Among the oxime ester compounds, preferred examples of compounds included in formula (c1) but not included in formula (c4) include the following compounds.

Further, among the oxime ester compounds represented by formula (c4) which are particularly suitable as oxime ester compounds, particularly suitable compounds include compounds of the following formula.

Further, from the viewpoint of the sensitivity of the resin composition and the transparency of the cured product, an oxime ester compound represented by the following formula (1) is particularly preferred as the oxime ester compound.

（式（１）中、Ｒ^ｃ１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ２及びＲ^ｃ３は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ２とＲ^ｃ３とは相互に結合して環を形成してもよく、Ｒ^ｃ４は１価の有機基であり、Ｒ^ｃ５は、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｎ１は０以上４以下の整数であり、ｎ２は０又は１である。）

(In formula (1), R ^c1 is a hydrogen atom, a nitro group, or a monovalent organic group, and R ^c2 and R ^c3 are a chain alkyl group that may have a substituent, and a chain alkyl group that has a substituent, respectively. R ^c2 and R ^c3 may be bonded to each other to form a ring, R ^c4 is a monovalent organic group, and R ^c5 is a hydrogen atom. an atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n1 is an integer of 0 to 4, and n2 is 0 or 1.)

In formula (1), R ^c1 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^c1 is bonded to a different 6-membered aromatic ring from the 6-membered aromatic ring bonded to the group represented by -(CO) _n2 - on the fluorene ring in formula (1). In formula (1), the bonding position of R ^c1 to the fluorene ring is not particularly limited. When the compound represented by formula (1) has one or more R ^c1 , one of the one or more R ^c1 is a fluorene ring because the compound represented by formula (1) is easy to synthesize. It is preferable to bond to the 2nd position in the middle. When there is a plurality of R ^c1 , the plurality of R ^c1 may be the same or different.

When R ^c1 is an organic group, R ^c1 is not particularly limited as long as it does not impede the object of the present invention, and is appropriately selected from various organic groups. Suitable examples when R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a group having a substituent. phenyl group which may have a substituent, phenoxy group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy which may have a substituent group, a phenylalkyl group that may have a substituent, a naphthyl group that may have a substituent, a naphthoxy group that may have a substituent, a naphthoyl group that may have a substituent, Naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

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

When R ^c1 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^c1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, 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, and isodecyloxy group. Further, when R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.

When R ^c1 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 ^c1 being a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and the like.

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

When R ^c1 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 when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl group. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples include isodecyloxycarbonyl group.

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

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a fused monocyclic ring with a benzene ring. It is a heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of monocycles constituting the condensed ring is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It will be done. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^c1 is a heterocyclyl group.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, suitable 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, phenyl group which may have a substituent, benzoyl group which may have a substituent, 7 to 20 carbon atoms which may have a substituent The following phenylalkyl groups, optionally substituted naphthyl groups, optionally substituted naphthoyl groups, optionally substituted naphthylalkyl groups having 11 to 20 carbon atoms, and heterocyclyl groups Examples include groups. Specific examples of these suitable organic groups are the same as R ^c1 . Specific examples of amino groups substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, alkyl group having 1 to 6 carbon atoms Examples include a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further has a substituent, the number of the substituents is not limited as long as it does not impede the object of the present invention, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c1 is preferably a nitro group or a group represented by R ^c10 -CO-, as these tend to improve sensitivity. R ^c10 is not particularly limited as long as it does not impede the purpose of the present invention, and can be selected from various organic groups. Examples of groups suitable as R ^c10 include alkyl groups having 1 to 20 carbon atoms, phenyl groups that may have substituents, naphthyl groups that may have substituents, and Examples include heterocyclyl groups which may be optional. Among these groups, 2-methylphenyl group, thiophen-2-yl group, and α-naphthyl group are particularly preferred as R ^c10 .
Further, it is preferable that R ^c1 is a hydrogen atom because transparency tends to be good. Note that transparency tends to be better when R ^c1 is a hydrogen atom and R ^c4 is a group represented by the below-mentioned formula (1a) or (1b).

In formula (1), R ^c2 and R ^c3 are each a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ^c2 and R ^c3 may be bonded to each other to form a ring. Among these groups, R ^c2 and R ^c3 are preferably chain alkyl groups which may have a substituent. When R ^c2 and R ^c3 are chain alkyl groups which may have substituents, the chain alkyl groups may be either straight chain alkyl groups or branched chain alkyl groups.

When R ^c2 and R ^c3 are chain alkyl groups without substituents, 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, particularly 1 or more and 6 or less. preferable. Specific examples when R ^c2 and R ^c3 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. , n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group. Further, when R ^c2 and R ^c3 are alkyl groups, the alkyl groups may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^c2 and R ^c3 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, 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. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as it does not impede the object of the present invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom, and bromine atom are preferred. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples when R ^c1 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, biphenylyl group, anthryl group, and phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples when R ^c1 is a heterocyclyl group. When R ^c1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and 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 a substituent, 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 ^c2 and R ^c3 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c2 and R ^c3 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as when R ^c2 and R ^c3 are chain alkyl groups.

When R ^c2 and R ^c3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is a phenyl group or a group formed by combining multiple benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing multiple benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, It is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, biphenylyl group, anthryl group, and phenanthryl group.

When R ^c2 and R ^c3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples include a tetracyclododecyl group and an adamantyl group.

When R ^c2 and R ^c3 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or a combination of such monocycles, or a combination of such monocycles and a benzene ring. is a fused heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of monocycles constituting the condensed ring is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It will be done.

R ^c2 and R ^c3 may be bonded to each other to form a ring. The group formed by the ring formed by R ^c2 and R ^c3 is preferably a cycloalkylidene group. When R ^c2 and R ^c3 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ^c2 and R ^c3 is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be fused with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring. ring, pyrazine ring, pyrimidine ring, and the like.

Among the R ^c2 and R ^c3 explained above, a group represented by the formula -A ⁰¹ -A ⁰² is exemplified as a preferable group. In the formula, A ⁰¹ is a linear alkylene group, and A ⁰² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in the linear alkylene group of A ⁰¹ is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A ⁰² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, and a fluorine atom, a chlorine atom, or a bromine atom is more preferable. When A ⁰² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, preferably linear. When A ⁰² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ^c2 and R ^c3 have as substituents. When A ⁰² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R ^c2 and R ^c3 have as substituents.

Preferred specific examples of R ^c2 and R ^c3 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n - Cyanoalkyl groups such as pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group phenyl groups, such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl group 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 -heptyl group, and alkoxycarbonylalkyl groups such as 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n- Pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n- Butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

As R ^c2 and R ^c3 , preferred groups among the above include 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.

As with R ^c1 , examples of suitable organic groups for R ^c4 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents. phenyl group which may have a substituent, phenoxy group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group, optionally substituted phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoxy group, optionally substituted naphthoyl group, Naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, substituted Examples include a heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ^c1 . Further, as R ^c4 , a cycloalkylalkyl group, a phenoxyalkyl group that may have a substituent on the aromatic ring, and a phenylthioalkyl group that may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group included in R ^c1 may have.

Among organic groups, R ^c4 is an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a phenylthio group which may have a substituent on an aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is the most preferable. preferable. Among the phenyl groups which may have substituents, methylphenyl is preferred, and 2-methylphenyl 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, 2-(4-chlorophenylthio)ethyl group is preferred.

Furthermore, as R ^c4 , a group represented by -A ⁰³ -CO-O-A ⁰⁴ is also preferable. A ⁰³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁰⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ⁰³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ⁰³ 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, particularly preferably 1 or more and 4 or less.

Suitable examples of A ⁰⁴ 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 ^A04 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group. Examples include phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, and β-naphthylmethyl group.

Preferred specific examples of the group represented by -A ⁰³ -CO-O-A ⁰⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, and 3-phenoxycarbonyl-n-propyl group.

（式（１ａ）及び式（１ｂ）中、Ｒ^ｃ７及びＲ^ｃ８はそれぞれ有機基であり、ｎ３は０以上４以下の整数であり、Ｒ^ｃ７及びＲ^ｃ８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ７とＲ^ｃ８とが互いに結合して環を形成してもよく、ｎ４は１以上８以下の整数であり、ｎ５は１以上５以下の整数であり、ｎ６は０以上（ｎ５＋３）以下の整数であり、Ｒ^ｃ９は有機基である。） Although R ^c4 has been described above, R ^c4 is preferably a group represented by the following formula (1a) or the following formula (1b).

(In formula (1a) and formula (1b), R ^c7 and R ^c8 are each an organic group, n3 is an integer from 0 to 4, and R ^c7 and R ^c8 are present at adjacent positions on the benzene ring. In ^the case ^of ) is the following integer, and R ^c9 is an organic group.)

Examples of organic groups for R ^c7 and R ^c8 in formula (1a) are the same as R ^c1 . R ^c7 is preferably an alkyl group or a phenyl group. When R ^c7 is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, it is most preferable that R ^c7 is a methyl group. When R ^c7 and R ^c8 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by formula (1a) in which R ^c7 and R ^c8 form a ring include naphthalen-1-yl group and 1,2,3,4- Examples include tetrahydronaphthalen-5-yl group. In the above formula (1a), n3 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (1b), R ^c9 is an organic group. Examples of the organic group include the same groups as the organic group explained for R ^c1 . Among the organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less. Preferred examples of R ^c9 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like, and among these, a methyl group is more preferred.

In the above formula (1b), n5 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (1b), n6 is 0 or more and (n5+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (1b), n4 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 (1), R ^c5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that R ^c5 may have when it is an alkyl group include a phenyl group and a naphthyl group. Preferred examples of the substituent that R ^c1 may have when it is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (1), preferred examples of R ^c5 include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. Among these, methyl group or phenyl group is more preferred.

Preferred specific examples of the compound represented by formula (1) include the following PI-43 to PI-83.

The content of the photopolymerization initiator (C) is preferably 0.5% by mass or more and 30% by mass or less based on the mass (total solid content) of the resin composition excluding the mass of the solvent (S) described below, and 1 More preferably % by mass or more and 20% by mass or less. By setting the content of the photopolymerization initiator (C) within the above range, a resin composition with good curability can be obtained.

A photoinitiation aid may be combined with the photopolymerization initiator (C). Examples of photoinitiation aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropion Examples include acids, thiol compounds such as methyl 3-mercaptopropionate, pentaerythol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiation aids can be used alone or in combination of two or more.

・Organic solvent (S)
The second resin composition may typically contain an organic solvent (S) for the purpose of adjusting coating properties. As the organic solvent (S), the same organic solvent as the organic solvent explained for the first resin composition can be used.

The amount of the organic solvent (S) to be used can be appropriately determined depending on the use of the resin composition. An example of the amount of the organic solvent (S) to be used is such that the solid content concentration of the resin composition is in the range of 1% by mass or more and 50% by mass or less.

-Other components The resin composition may contain various other additives other than the above-mentioned components, if necessary. Specifically, dispersion aids, fillers, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, thermal polymerization inhibitors, antifoaming agents, surfactants and the like are exemplified.

Further, the second resin composition may also contain an epoxy group-containing cyclic siloxane compound (A-II) that has not reacted with the (meth)acrylic resin (A-I). The resin composition preferably does not contain an epoxy group-containing cyclic siloxane compound, since it is easy to form a cured product with a low dielectric constant. When the resin composition contains the epoxy group-containing cyclic siloxane compound (A-II), its content is preferably 40% by mass or less based on the mass of the resin composition excluding the mass of the organic solvent (S), It is more preferably 10% by mass or less, even more preferably 1% by mass or less.

≪Cured product and method for producing cured product≫
A cured product can be produced by heating and/or exposing the resin composition described above. When producing a cured product, whether to perform heating, exposure, or both heating and exposure is appropriately determined in consideration of the composition of the cured product composition. Since the cured product of the resin composition described above exhibits a low dielectric constant, it is suitably used as a material for films such as insulators in display panels for various image display devices.

The dielectric constant of the cured product is preferably 3.3 or less, more preferably 3.2 or less, and even more preferably 3.1 or less, as a value measured at a frequency of 0.1 MHz.
As a method for measuring the dielectric constant, a mercury probe method is preferably applied. An example of an apparatus capable of measuring the dielectric constant using the mercury probe method is SSM-495 (manufactured by Nippon Semi-Lab).
A preferred method for measuring the dielectric constant is to form a film-like cured product through the following steps 1) to 4), and then measure the dielectric constant of the formed cured product using a mercury probe method. There are several ways to do this.
1) A resin composition is applied onto a silicon wafer to form a coating film.
2) The formed coating film is heated at 100° C. for 120 seconds.
3) When the resin composition contains a photopolymerization initiator or a photosensitive curing agent, the coating film is optionally exposed to light at an exposure dose of 1 kJ/cm ² .
4) If necessary, the exposed coating film is heated at 230° C. for 20 minutes.

Although the shape of the cured product is not particularly limited, it is preferably in the form of a film. When the cured product is a film, its thickness is preferably 10 nm or more and 30,000 nm or less, more preferably 50 nm or more and 1,500 nm or less, and even more preferably 100 nm or more and 1,000 nm or less.

When the cured product is in the form of a film, it is preferable to heat and/or expose the coating film of the resin composition applied onto the substrate. The coating method is not particularly limited, and for example, a coating method using a contact transfer coating device such as a roll coater, reverse coater, or bar coater, or a non-contact coating device such as a spinner (rotary coating device) or a curtain flow coater may be used. Can be mentioned.

The coated film after the above coating is preferably dried (prebaked). The drying method is not particularly limited, and examples include (1) drying on a hot plate at a temperature of 80°C to 120°C, preferably 90°C to 100°C for 60 seconds to 120 seconds; (2) Examples include a method of leaving it at room temperature for several hours to several days, and (3) a method of placing it in a hot air heater or an infrared heater for several minutes to several hours to remove the solvent.
Note that the resin composition may be cured simultaneously with drying.

When heating a resin composition to form a cured product, the heating temperature and heating time are not particularly limited as long as curing progresses favorably and thermal deterioration or thermal decomposition does not occur in the cured product. The heating temperature is, for example, preferably 80°C or more and 300°C or less, more preferably 100°C or more and 280°C or less, and even more preferably 120°C or more and 250°C or less. The heating time is, for example, preferably 10 seconds or more and 12 hours or less, more preferably 1 minute or more and 6 hours or less, and more preferably 2 minutes or more and 3 hours or less.

When exposing a resin composition to form a cured product, the exposure conditions are not particularly limited as long as curing proceeds satisfactorily. Exposure is performed, for example, by irradiating active energy rays such as ultraviolet rays and excimer laser light. The energy dose to be irradiated is not particularly limited, but may be, for example, 3 mJ/cm ² or more and 2000 mJ/cm ² or less.

≪Method for producing patterned cured film≫
When using the above-mentioned first resin composition containing a photosensitive curing agent or the above-mentioned second resin composition as the resin composition, a patterned cured film can be formed by applying a photolithography method. Can be done.
in particular,
Coating the first resin composition containing the photosensitive curing agent or the second resin composition on the substrate to form a coating film;
positionally selectively exposing the coating film;
Developing the exposed coating film with a developer to pattern the coating film;
A patterned cured film is produced by a method comprising: heating the patterned coating.

The thickness of the patterned cured film is as described above for the cured film.
In the above method for producing a patterned cured film, the coating method is as described above for the method for producing a cured film. The exposure conditions are as described above for the method for producing a cured film. Position-selective exposure is performed, for example, through a negative photomask. Regarding the heating conditions after exposure, the heat curing conditions described above for the method for producing a cured film can be applied.

The developing method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. Specific examples of the developer include an organic solvent (S) that the resin composition may contain, an organic developer such as monoethanolamine, diethanolamine, triethanolamine, etc., and a developer with a concentration of 0.02% by mass, for example. Examples include basic aqueous solutions containing sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts, etc. in an amount of 10% by mass or less.
When the resin composition is the first resin composition containing a photosensitive curing agent, an organic solvent (S) that the resin composition may contain is preferable.
When the resin composition is the second resin composition, the developer is preferably an alkaline developer. As the alkaline developer, for example, a tetramethylammonium hydroxide aqueous solution having a concentration of 0.05% by mass or more and 10% by mass or less, preferably 0.05% by mass or more and 3% by mass or less is preferable.

The present invention will be explained in more detail below based on Examples, but the present invention is not limited by these Examples.

[Example 1]
After replacing the inside of a three-neck glass flask with a capacity of 300 mL with a nitrogen atmosphere, the internal temperature of the flask was brought to 80°C. Then, 5.18 g of diethylene glycol methyl ethyl ether (MEDG) was added into the flask.
Separately, in a glass sample bottle with a capacity of 300 mL, 12% by mass of methacrylic acid, 17% by mass of tricyclo[5.2.1.0 ^2,6 ]decanyl methacrylate, and 71% by mass of 3,4-epoxycyclohexylmethyl methacrylate. A polymerization solution was prepared by adding 29 g of a monomer mixture consisting of the following, 5 g of dimethyl-2,2'-azobis(2-methylpropionate) as a polymerization initiator, and 62 g of MEDG.
The obtained polymerization solution was dropped into a three-neck flask at 80°C over 2 hours, and then stirring was continued at 80°C for 2 hours to continue the polymerization reaction.
As a result, a MEDG solution (concentration 30% by mass) of (meth)acrylic resin (resin P1) having the following structural unit ratio was obtained. The numerical value at the bottom right of the parentheses is the ratio (mass %) of each structural unit.
Regarding the obtained (meth)acrylic resin, the molecular weight in terms of polystyrene was measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 9,000.

Next, 3 g of an epoxy group-containing cyclic siloxane compound C1 having the following structure and 1 g of 1-methylimidazole were added to the solution of the resin P1 obtained. Thereafter, the contents of the flask were stirred at 80° C. for 30 minutes to react the resin P1 with the epoxy group-containing cyclic siloxane compound to obtain the resin P2, which is a siloxane-modified (meth)acrylic resin.
FT-IR measurement confirmed the formation of ester bonds and hydroxyl groups due to the reaction between resin P1 and the epoxy group-containing cyclic siloxane compound.
Regarding the obtained resin P2, the molecular weight in terms of polystyrene was measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 13,000.

[Example 2, Comparative Example 1, and Comparative Example 2]
In Example 2, Comparative Example 1, and Comparative Example 2, dipentaerythritol hexaacrylate was used as the photopolymerizable monomer.

In Example 2, Comparative Example 1, and Comparative Example 2, a compound of the following formula was used as a photopolymerization initiator.

In Example 2, Comparative Example 1, and Comparative Example 2, IR1010 (manufactured by BASF Japan) was used as the antioxidant. 3-glycidoxypropyltrimethoxysilane was used as a silane coupling agent. BYK-310 (manufactured by BYK Chemie) was used as a surfactant. MEDG and propylene glycol monomethyl ether acetate (PGMEA) were used as organic solvents.

The curable resin compositions of Example 2, Comparative Example 1, and Comparative Example 2 were obtained by mixing the components listed in Table 1 below at the ratios (% by mass) listed in Table 1 below. . Using the obtained resin compositions of Example 2, Comparative Example 1, and Comparative Example 2, the dielectric constant of the cured product was measured and the light transmittance of the cured product was measured (wavelength 380~ 780 nm). These evaluation results are shown in Table 1.

<Relative permittivity measurement>
A resin composition was applied onto a silicon wafer using a spinner to form a coating film. The formed coating film was heated at 100° C. for 120 seconds and then further heated at 230° C. for 20 minutes to form a cured film with a thickness of 1 μm.
The dielectric constant of the formed cured film was measured using SSM-495 (manufactured by Nippon Semi-Lab) at a measurement frequency of 0.1 MHz.

<Light transmittance measurement>
A resin composition was applied onto a glass substrate using a spinner to form a coating film. The formed coating film was heated at 100° C. for 120 seconds. The heated coating film was exposed to light using an exposure device (TME-150PRO, manufactured by Topcon Corporation) at an exposure dose of 20 mW/cm ² . The exposed coating film was heated at 230° C. for 20 minutes to obtain a cured film with a thickness of 3 μm. The light transmittance (wavelength 380 to 780 nm) of the obtained cured film was measured using MCPD-3700 (manufactured by Otsuka Electronics Co., Ltd.).

According to Table 1, a siloxane-modified (meth)acrylic resin obtained by reacting a (meth)acrylic resin containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group with an epoxy group-containing siloxane compound. It can be seen that the resin composition of Example 2 containing resin P2 has a low dielectric constant and provides a transparent cured product.
On the other hand, the resin compositions of Comparative Examples 1 and 2, which contain a (meth)acrylic resin that has not been modified with an epoxy group-containing siloxane compound, or a combination of a (meth)acrylic resin and an epoxy group-containing siloxane compound, It can be seen that a cured product that is transparent but has a high dielectric constant can be obtained.

[Example 3]
The monomer mixture used in Example 1 was composed of 14% by mass of methacrylic acid, 17% by mass of tricyclo[5.2.1.0 ^2,6 ]decanyl methacrylate, and 3,4-epoxytricyclo[acrylic acid]. 5.2.1.0 ^2,6 ]decane-1-yl in an amount of 69% by mass. A MEDG solution (concentration 30% by mass) of a resin (resin P3) was obtained. The numerical value at the bottom right of the parentheses is the ratio (mass %) of each structural unit.
Regarding the obtained (meth)acrylic resin, the molecular weight in terms of polystyrene was measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 9,500.

Next, in the same manner as in Example 1, resin P3 was reacted with the epoxy group-containing cyclic siloxane compound used in Example 1 to obtain resin P4, which is a siloxane-modified (meth)acrylic resin.
FT-IR measurement confirmed the formation of ester bonds and hydroxyl groups due to the reaction between resin P3 and the epoxy group-containing cyclic siloxane compound.
Regarding the obtained resin P4, the molecular weight in terms of polystyrene was measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 125,000.

[Example 4, Comparative Example 3, and Comparative Example 4]
Example 4 and Comparative Example were prepared in the same manner as Example 2, Comparative Example 1, and Comparative Example 2 according to Table 2 below, except that resin P1 was changed to resin P3 and resin P2 was changed to resin P4. Curable resin compositions of Comparative Example 3 and Comparative Example 4 were obtained. Using the obtained resin compositions of Example 4, Comparative Example 3, and Comparative Example 4, the dielectric constant of the cured product was measured and cured in the same manner as in Example 2, Comparative Example 1, and Comparative Example 2. The light transmittance of the object was measured (wavelength: 380 to 780 nm). These evaluation results are shown in Table 2.

According to Table 2, a siloxane-modified (meth)acrylic resin obtained by reacting a (meth)acrylic resin containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group with an epoxy group-containing siloxane compound. It can be seen that the resin composition of Example 4 containing resin P4 has a low dielectric constant and provides a transparent cured product.
On the other hand, the resin compositions of Comparative Examples 3 and 4 containing a (meth)acrylic resin that has not been modified with an epoxy group-containing siloxane compound, or a combination of a (meth)acrylic resin and an epoxy group-containing siloxane compound, It can be seen that a cured product that is transparent but has a high dielectric constant can be obtained.

Claims (11)

Contains a siloxane-modified (meth)acrylic resin (A1) and a curing agent ,
The siloxane-modified (meth)acrylic resin (A1) is a (meth)acrylic resin (A-I) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group, and the following formula (a-I): A curable resin composition, which is a resin in which the epoxy group-containing cyclic siloxane compound (A-II) represented by the formula (A-II) has an ester bond and/or an ether bond .

(In formula (a-I), R ^a01 and R ^a02 represent a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x1 R ^a01 and x1 At least two of R ^a02 are monovalent groups containing an epoxy group.) Contains a siloxane-modified (meth)acrylic resin (A1), a photopolymerizable monomer (B), and a photopolymerization initiator (C),
The siloxane-modified (meth)acrylic resin (A1) is a (meth)acrylic resin (A-I) containing a structural unit derived from a (meth)acrylate having an alicyclic epoxy group, and the following formula (a-I): A curable resin which is a resin in which the epoxy group-containing cyclic siloxane compound (A-II) represented by the formula (A-II) has an ester bond and/or an ether bond, and further contains a structural unit having an alkali-soluble group. Composition.

(In formula (a-I), R ^a01 , and R ^a02 represents a monovalent group or alkyl group containing an epoxy group, x1 represents an integer of 3 or more, and x1 R ^a01 and x1 R ^a02 At least two of them are monovalent groups containing an epoxy group. ) Curable according to claim 1 or 2, wherein the amount of structural units derived from (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A-I) is 50% by mass or more. Resin composition. The siloxane-modified (meth)acrylic resin (A1) contains 100 parts by mass of the (meth)acrylic resin (A-I) and 1 part by mass or more and 50 parts by mass or less of the epoxy group-containing cyclic siloxane compound (A-II). The curable resin composition according to any one of claims 1 to 3, wherein is formed by an ester bond and/or an ether bond . The curable resin composition according to any one of claims 1 to 4 , wherein the (meth)acrylate having an alicyclic epoxy group contains a polycycloalkane skeleton. A method for producing a cured product, comprising heating and/or exposing the curable resin composition according to any one of claims 1 to 5. Coating the curable resin composition according to claim 2 on a substrate to form a coating film;
positionally selectively exposing the coating film;
Developing the exposed coating film with an alkaline developer to pattern the coating film;
heating the patterned coating film;
A method for producing a patterned cured film. A (meth)acrylic resin (AI) containing a structural unit derived from (meth)acrylate having an alicyclic epoxy group, and an epoxy group-containing cyclic siloxane compound (A-I) represented by the following formula (a-I). A curable siloxane-modified (meth)acrylic resin formed by bonding II) with an ester bond and/or an ether bond .

(In formula (a-I), R ^a01 and R ^a02 represent a monovalent group containing an epoxy group or an alkyl group, x1 represents an integer of 3 or more, and x1 R ^a01 and x1 At least two of R ^a02 are monovalent groups containing an epoxy group.) The curable siloxane-modified resin according to claim 8 , wherein the amount of structural units derived from (meth)acrylate having an alicyclic epoxy group in the (meth)acrylic resin (A-I) is 50% by mass or more. (meth)acrylic resin. A resin in which 100 parts by mass of the (meth)acrylic resin (A-I) and 1 part by mass or more and 50 parts by mass or less of the epoxy group-containing cyclic siloxane compound (A-II) form an ester bond and/or an ether bond. The curable siloxane-modified (meth)acrylic resin according to claim 8 or 9 . The curable siloxane-modified (meth)acrylic resin according to any one of claims 8 to 10 , wherein the (meth)acrylate having an alicyclic epoxy group contains a polycycloalkane skeleton.