JP2022062394A - Compound, polymerizable composition, cured product and method for producing cured product - Google Patents

Abstract

To provide a compound useful as a polymerizable component of a polymerizable composition, which can give a cured product capable of forming a fine pattern with high sensitivity and good insulation properties, and a polymerizable composition including the compound.SOLUTION: A compound consists of a compound represented by general formula (I) with an acid anhydride having a polymerizable group added thereto (where R1 and R10 independently represent a hydrogen atom or a methyl group, R2, R3, R4, R5, R6, R7, R8 and R9 independently represent a hydrogen atom, a C1 to 20 hydrocarbon group or the like, X1 and X2 independently represent a divalent C1 to 20 hydrocarbon group or the like, M1 is an indenyl group, a fluorenyl group or the like).SELECTED DRAWING: None

Description

The present invention relates to a compound having a structure in which acrylic acid or methacrylic acid is added to an epoxy compound having a specific structure, to which an acid anhydride having a polymerizable group is added.

The alkali-developable photosensitive resin composition contains an alkali-developable resin containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this alkali-developable photosensitive resin composition can be polymerized and cured by irradiating it with ultraviolet rays or electron beams, it is used for photocurable inks, photosensitive printing plates, printed wiring plates, various photoresists and the like. There is. Recently, with the progress of lightening, thinning, shortening, and increasing functionality of electronic devices, an alkali-developable photosensitive resin composition capable of forming fine patterns with high accuracy has been desired.

Patent Document 1 discloses a photopolymerizable unsaturated compound having a carboxyl group based on an epoxy acrylate and a photosensitive resin composition using the same.
Patent Document 2 describes a reaction product of an aromatic epoxy compound derived from bisphenols and (meth) acrylic acid, and further a) saturated dicarboxylic acid or its acid anhydride and b) saturated tetracarboxylic acid or its acid dianhydride. A photosensitive resin composition containing an unsaturated group-containing compound obtained by reacting with an anhydride is disclosed.
Patent Document 3 describes an esterification reaction product of an epoxy adduct obtained by adding an unsaturated monobasic acid to a novel epoxy compound having a benzo or naphthocycloalkane skeleton having a substituent and a polybasic acid anhydride. An alkali-developable photosensitive resin composition containing a photopolymerizable unsaturated compound is disclosed.
Patent Documents 4 and 5 disclose a photosensitive resin composition containing a carboxyl group-containing resin having a bisphenol fluorene skeleton.

Japanese Unexamined Patent Publication No. 05-339356 Japanese Unexamined Patent Publication No. 2006-003860 Japanese Unexamined Patent Publication No. 2012-241083 Japanese Unexamined Patent Publication No. 2017-090491 JP-A-2017-090493

The above-mentioned known alkali-developable photosensitive resin composition has insufficient sensitivity, resolution, adhesion, etc., and it is difficult to obtain an appropriate pattern shape and fine pattern.

An object of the present invention is to provide a compound useful as a polymerizable component of a highly sensitive polymerizable composition and a polymerizable composition using the compound.

As a result of diligent studies, the present inventor has a structure in which an acid anhydride having a polymerizable group is added to an epoxy acrylate compound having a structure in which acrylic acid or methacrylic acid is added to an epoxy compound having a specific structure. It has been found that the compound can achieve the above object, and the present invention has been reached.

That is, the present invention is a compound having a structure in which an acid anhydride having a polymerizable group is added to a compound represented by the following general formula (I).

（式中、Ｒ^１及びＲ^１０は、それぞれ独立に、水素原子又はメチル基を表し、
Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０の炭化水素基、又は炭化水素基中のメチレン基の１つ以上が－Ｏ－に置換された炭素原子数１～２０の基を表し、
Ｘ^１及びＸ^２は、それぞれ独立に、２価の炭素原子数１～２０の炭化水素基又は該炭化水素基中のメチレン基の１つ以上が－Ｏ－に置換された炭素原子数１～２０の基を表し、
Ｍ^１は下記式（ａ）、（ｂ）、（ｃ）又は（ｄ）で表される基を表す。）

(In the formula, R ¹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group. One or more of the methylene groups in the group represent a group having 1 to 20 carbon atoms substituted with —O—.
Each of X ¹ and X ² has a divalent hydrocarbon group having 1 to 20 carbon atoms or 1 or more carbon atoms in which one or more of the methylene groups in the hydrocarbon group is substituted with —O—. Represents 20 groups
M ¹ represents a group represented by the following formula (a), (b), (c) or (d). )

（式中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５、Ｒ^４６、Ｒ^４７、Ｒ^４８及びＲ^４９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０の炭化水素基、炭素原子数２～１０の複素環基、複素環を含有する炭素原子数３～２０の基又は炭化水素基中のメチレン基の１つ以上が下記＜群Ａ＞から選ばれる２価の基で置換された炭素原子数１～２０の基を表し、
＜群Ａ＞：－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^５１－、－ＮＲ^５１ＣＯ－、－Ｓ－
Ｒ^５１は、水素原子又は炭素原子数１～２０の炭化水素基を表し、分子中にＲ^５１が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５、Ｒ^４６、Ｒ^４７、Ｒ^４８及びＲ^４９は、炭化水素基中の水素原子の１つ以上がハロゲン原子、シアノ基、ニトロ基、水酸基、－ＯＲ^５２、－ＣＯＯＲ^５２、－ＣＯ－Ｒ^５２又は－ＳＲ^５２で置換された炭素原子数１～２０の基であってもよく、
Ｒ^５２は、水素原子又は炭素原子数１～２０の炭化水素基を表し、分子中にＲ^５２が複数存在する場合、それらは同一であっても異なっていてもよく、
Ｒ^２１とＲ^２２、Ｒ^２２とＲ^２３、Ｒ^２３とＲ^２４、Ｒ^２９とＲ^３０、Ｒ^３０とＲ^３１、Ｒ^３１とＲ^３２、Ｒ^３７とＲ^３８、Ｒ^３８とＲ^３９、Ｒ^３９とＲ^４０、Ｒ^４１とＲ^４２、Ｒ^４２とＲ^４３、Ｒ^４３とＲ^４４、Ｒ^４５とＲ^４６、Ｒ^４６とＲ^４７、Ｒ^４７とＲ^４８及びＲ^４８とＲ^４９は、互いに結合して水素原子及び炭素原子からなる炭素原子数３～１０の環を形成していてもよく、
Ｃｙは、炭素原子数３～１０のシクロアルキル基を表し、
＊は、（ａ）、（ｂ）、（ｃ）及び（ｄ）で表される基が隣接する基と結合する部位を意味する。）

(In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R. ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are independent hydrogen atoms and halogens, respectively. One or more of an atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group having 3 to 20 carbon atoms containing a heterocycle, or a methylene group in a hydrocarbon group. Represents a group having 1 to 20 carbon atoms substituted with a divalent group selected from the following <Group A>.
<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ^51- , -NR ⁵¹ CO-, -S-
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^51s are present in the molecule, they may be the same or different.
R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ . , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ have one or more hydrogen atoms in the hydrocarbon group. It may be a group having 1 to 20 carbon atoms substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵² , -COOR ⁵² , -CO-R ⁵² or -SR ⁵² .
R ⁵² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^52s are present in the molecule, they may be the same or different.
R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , R ³⁹ . And R ⁴⁰ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ and R ⁴⁸ and R ⁴⁹ are coupled to each other. It may form a ring consisting of a hydrogen atom and a carbon atom having 3 to 10 carbon atoms.
Cy represents a cycloalkyl group having 3 to 10 carbon atoms.
* Means the site where the group represented by (a), (b), (c) and (d) binds to an adjacent group. )

Further, the present invention is a polymerizable composition containing the above-mentioned compound (A) and a polymerization initiator (B).

The polymerizable composition containing the compound of the present invention has high sensitivity.

1 (a) and 1 (b) are diagrams showing a bonding angle (taper angle) between a pattern and a substrate.

Hereinafter, the compound of the present invention, the polymerizable composition, and the method for producing the compound will be described in detail based on preferred embodiments.
The compound of the present invention is an epoxy acrylate compound having a structure in which acrylic acid or methacrylic acid is added to an epoxy compound having a specific structure represented by the above general formula (I) (hereinafter, referred to as “compound (I)”. ), An acid anhydride having a polymerizable group (hereinafter referred to as “compound (II)”) is added to the compound.

In the above general formula (I), the number of carbon atoms 1 represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ (hereinafter referred to as “R ² etc.”). The hydrocarbon group of to 20 may be a group having 1 to 20 carbon atoms consisting of a carbon atom and a hydrogen atom, and is not particularly limited, but is an alkyl group having 1 to 20 carbon atoms and a carbon atom number. 2 to 20 alkenyl groups, 3 to 20 carbon atoms cycloalkyl groups, 4 to 20 carbon atoms cycloalkylalkyl groups, 6 to 20 carbon atoms aryl groups or 7 to 20 carbon atoms arylalkyl groups Is preferable because the sensitivity of the polymerizable composition of the present invention is excellent, and an alkyl group having 1 to 10 atoms, an alkenyl group having 2 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms is particularly preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, an isobutyl group, an amyl group, an isoamyl group, and t. -Amil group, hexyl group, heptyl group, isoheptyl group, t-heptyl group, n-octyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group. , N-Octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and other linear, branched and cyclic alkyl groups.

Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, a 2-hexenyl group and a 3-. Hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group, 4-dodecenyl group, 3- Examples thereof include linear and cyclic alkenyl groups such as a cyclohexenyl group, a 2,5-cyclohexadienyl-1-methyl group, and a 4,8,12-tetradecatorienylallyl group.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group, decahydronaphthyl group, octahydropentalene group, bicyclo [1.1.1 ] Examples include a pentanyl group and a tetradecahydroanthrasenyl group.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with the cycloalkyl group. For example, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclodecylmethyl group, 2-cyclobutylethyl group, 2-cyclopentyl. Ethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclodecylethyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexyl Examples thereof include butyl group, 4-cycloheptylbutyl group, 4-cyclooctylbutyl group, 4-cyclononylbutyl group, 4-cyclodecylbutyl group, 3-3-adamantylpropyl group and decahydronaphthylpropyl group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthrenyl group and the like, and these groups are the alkyl groups. Groups substituted with one or more of the above alkenyl group, carboxyl group, halogen atom, etc., such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc. Can be mentioned.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group, and examples thereof include benzyl and α-methylbenzyl. Examples thereof include α, α-dimethylbenzyl and phenylethyl.

In the above general formula (I), the methylene group in the hydrocarbon group represented by ^R2 or the like is substituted with —O— under the condition that the oxygen atoms are not adjacent to each other as a group having 1 to 20 carbon atoms. Is a group in which the methylene group in the group exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 or the like is replaced with —O— under the condition that the oxygen atoms are not adjacent to each other. ..

In the above general formula (I), the methylene group in the hydrocarbon group represented by ^R2 or the like is a group having 1 to 20 carbon atoms substituted with —O— under the condition that the oxygen atoms are not adjacent to each other. For example, methoxy group, methoxyethoxy group, methoxyethoxyethoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, isopentyloxy group, t-pentyloxy. Examples thereof include a group, a neopentyloxy group, a hexyloxy group, a cyclohexyloxy group, an isohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group and a decyloxy group.

In the above general formula (I), examples of the halogen atom represented by ^R2 and the like include fluorine, chlorine, bromine, iodine and the like.

In the above general formula (I), the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X ¹ and X ² is a hydrocarbon having 1 to 20 carbon atoms represented by R ² or the like. Examples thereof include a divalent group obtained by removing one hydrogen atom from the group exemplified.

In the above general formula (I), the methylene group in the hydrocarbon group represented by X ¹ and X ² is substituted with —O— under the condition that the oxygen atoms are not adjacent to each other, and the number of carbon atoms is 1 to 20. As the group, the methylene group in the group exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by X ¹ and X ² was replaced with —O— under the condition that the oxygen atoms were not adjacent to each other. Examples thereof include, for example, a group having 1 to 20 carbon atoms in which the methylene group in the hydrocarbon group represented by ^R2 or the like is substituted with —O— under the condition that the oxygen atoms are not adjacent to each other. A divalent group obtained by removing one hydrogen atom from the group exemplified as "."

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the above general formula (I) are independently hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, respectively. The compound is preferable because it has excellent stability, the sensitivity of the polymerizable composition containing the compound is excellent, and the production is easy. In particular, compounds in which R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the above general formula (I) are hydrogen atoms are preferable.

Further, the compounds in which X ¹ and X ² in the general formula (I) are alkylene groups having 1 to 20 carbon atoms are preferable because they have excellent stability and are easy to produce, and have 1 to 1 carbon atoms. The alkylene group of 4 is more preferable, and the methylene group is particularly preferable.

In the above formulas (a), (b), (c) and (d), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , The hydrocarbon groups and halogen atoms having 1 to 20 carbon atoms represented by R ⁴⁸ and R ⁴⁹ (hereinafter referred to as "R ²¹ etc.") have 1 to 20 carbon atoms represented by R ² and the like. It is the same as the hydrocarbon group and halogen atom of.

In the above formulas (a), (b), (c) and ⁽ d), the heterocyclic group represented by R21 or the like means a group obtained by removing one hydrogen atom from the heterocyclic compound.

The heterocyclic group is not particularly limited, and is, for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridadyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazil, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl. , Imidazolidine, benzoimidazolyl, triazolyl, frill, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolidine, oxazolidine, benzoxazolyl, isothiazolyl, isooxazolidine, indrill, morpholinyl, thiomorpholinyl, 2-pyrrolidinone. Examples thereof include -1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidine-3-yl and 2,4-dioxyoxazolidine-3-yl.

In the above formulas (a), (b), (c) and ⁽ d), the groups represented by R21 and the like, which contain a heterocycle and have 3 to 20 carbon atoms, are a heterocyclic group and a heterocyclic group. It means a group to which a group other than the above is bonded.

Examples of the group other than the heterocyclic group include a hydrocarbon group having 1 to 6 carbon atoms, and examples of the hydrocarbon group having 1 to 6 carbon atoms include a carbon atom represented by ^R2 and the like. Examples of the hydrocarbon groups having the number 1 to 20 include those having a predetermined number of carbon atoms among the divalent groups obtained by removing one hydrogen atom from the groups exemplified.

In addition, as for the groups other than the heterocyclic group, the hydrogen atom in the hydrocarbon group having 1 to 6 carbon atoms is a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR', -COOR', or -CO-R. It may be a group substituted with'or -SR', etc., and the methylene group in the hydrocarbon group is -O-, -CO-, -COO-, -OCO-, -NR "-, -NR" CO. It may be a group having 1 to 6 carbon atoms substituted with − or —S— or the like.
Here, R'and R'represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R'and R'are present in the compound, they are different even if they are the same. May be good. The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 or the like.

Examples of the group containing a heterocycle having 3 to 20 carbon atoms include a group having the following structure, specifically including a substituent and the like.

In the above formula, R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z is an alkylene group having 1 to 6 carbon atoms, and the hydrogen atom in the alkylene group is a halogen atom and cyano. A group substituted with a group, a nitro group, a hydroxyl group, -OR', -COOR', -CO-R' or -SR', or a methylene group in the alkylene group is -O-, -CO-, -COO- , -OCO-, -NR "-, -NR" represents a group substituted with CO- or -S-. * In the formula means that the group represented by these formulas is bonded to the adjacent group at the * part.
Here, R'and R'represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R'and R'are present in the compound, they are different even if they are the same. May be good. The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 or the like.

In the above formulas (a), (b), (c) and ⁽ d), one or more of the hydrogen atoms in the hydrocarbon group represented by R21 or the like are a halogen atom, a cyano group, a nitro group or a hydroxyl group. , -OR ⁵¹ , -COOR ⁵¹ , -CO-R ⁵¹ or -SR ⁵¹ substituted with 1 to 20 carbon atoms, the group having 1 to 20 carbon atoms is a hydrocarbon having 1 to 20 carbon atoms represented by ^R2 or the like. Examples thereof include a group in which one or more hydrogen atoms in the group exemplified as the group are substituted with the above group.
Here, R ⁵¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^51s are present in the compound, they may be the same or different. The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 or the like.
The number of carbon atoms in the group having the substituent defines the number of carbon atoms in the entire group.

In the above formulas (a), (b), (c) and ⁽ d), one or more of the methylene groups in the hydrocarbon group represented by R21 or the like are -O-, -CO-, -COO. -, -OCO-, -NR ^52- , -NR ⁵² The group having 1 to 20 carbon atoms substituted with CO- or -S- is the group having 1 to 20 carbon atoms represented by ^R2 or the like. Examples thereof include groups in which one or more of the methylene groups in the groups exemplified as hydrocarbon groups are substituted with the above groups.
Here, R ⁵² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵² are present in the compound, they may be the same or different. The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 or the like.
The number of carbon atoms in the group in which the methylene group is substituted in the above hydrocarbon group defines the number of carbon atoms in the entire group.

In the above equations (a), (b), (c) and (d), R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R. ³¹ and R ³² , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , R ³⁹ and R ⁴⁰ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ and R ⁴⁸ and R ⁴⁹ (hereinafter referred to as "R ²¹ and R ²² etc.") form 3 to 10 carbon atoms consisting of hydrogen atoms and carbon atoms formed by bonding with each other. The rings include, for example, 5- to 7-membered aliphatic rings, aromatic rings and heterocycles such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring and lactam ring. Examples thereof include fused rings such as a naphthalene ring, an anthracene ring, a fluorene ring, an acenaphthene ring, an indan ring, and a tetraline ring.

In the above formula (d), the cycloalkyl group having 3 to 10 carbon atoms is preferably a cyclohexyl group because it is easy to produce and has excellent storage stability.

The compound (I) in which M ¹ in the general formula (I) is a group represented by the formula (a), the formula (c) or the formula (d) has a high sensitivity and a fine pattern having excellent insulating properties. It is preferable because a cured product capable of forming the above can be obtained. Among them, the compound which is the group represented by the formula (a) is more preferable because the obtained cured product has excellent insulating properties, and the compound which is the group represented by the formula (c) is the obtained cured product. It is more preferable because it has excellent heat resistance.

The compound of the present invention is a compound having a structure in which an acid anhydride having a polymerizable group (compound (II)) is added to the compound (I).
The polymerizable group means a group capable of causing a polymerization reaction by a radical, an acid, a base, or the like, and may be an addition reaction between groups of the same type, or an addition reaction or two different groups. It may be one that undergoes a condensation reaction. Examples of the polymerizable group include radically polymerizable groups such as an acrylic group, a methacrylic group, a styrenyl group and a vinyl group, a hydroxyl group, an epoxy group, a mercapto group, an allyl group, an isocyanate group, an amino group and an alkoxysilyl group. ..

Examples of the acid anhydride structure in the compound (II) include aliphatic acid anhydrides such as succinic acid anhydride and maleic acid anhydride, and aromatic acid anhydrides such as trimellitic acid anhydride and phthalic acid anhydride. Corresponds to acid anhydrides having an alicyclic structure such as tetrahydrophthalic acid anhydride, nagic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydrous. The structure to be used is mentioned.

Examples of the compound (II) include 2-hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, and dipenta with respect to the carboxyl group of trimellitic acid anhydride or hexahydrotrimellitic acid anhydride. Examples thereof include those obtained by subjecting an alcohol compound having a polymerizable group such as erithitol pentaacrylate to a condensation reaction.

The compound (II) in which the polymerizable group is a radically polymerizable group is preferable, and the compound (II) is particularly preferable in terms of an acrylic group and a methacrylic group. The compound (II) having the above-mentioned polymerizable group is preferable because the obtained polymerizable composition has excellent sensitivity and the produced cured product has excellent chemical resistance.

Compound (II) having a cyclic structure is preferable, a condensed ring is preferable, and a fused ring containing no aromatic ring is particularly preferable. The compound (II) is preferable because the obtained cured product has excellent insulating properties.

Compound (II) having an alicyclic structure is preferable because the obtained cured product has excellent chemical resistance.

Examples of the acid anhydride having a polymerizable group include, but are not limited to, the following compounds (II-1) to (II-13).

The compound of the present invention may be a compound having a structure to which acid dianhydride is further added. Such a compound is preferable because it can be made into a compound having a desired alkali developability by adjusting the acid value.

Examples of the acid dianhydride include 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, and 2,3,5-tricarboxycyclopentylacetic dianhydride. , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, pyromellitic acid anhydride, 2,2'-3,3'-benzophenone tetracarboxylic acid anhydride, 5- (2,5-di) Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,3'-4,4'-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimeritate, meso- Butane-1,2,3,4-tetracarboxylic acid anhydride and the like can be mentioned.

The compound (I) can be produced by a known production method, for example, the production method described in International Publication No. 2008/139924. Specifically, an epoxy obtained by reacting a bisphenol compound such as 1,1-bis (4-hydroxyphenyl) -3-phenylindan and 9,9-bis (4-hydroxyphenyl) fluorene with epichlorohydrin. It can be produced by adding acrylic acid or methacrylic acid to the compound.

The compound of the present invention can be produced by carrying out a reaction of adding the compound (II) to the compound (I). The reaction may be carried out by a known method, and can be carried out, for example, by the method described in JP-A-2007-183495. Specifically, the compound (I) and the compound (II) can be produced by heating and reacting in a solvent such as propylene glycol monomethyl ether acetate.
The above reaction is considered to be mainly a reaction for forming an ester bond between the hydroxyl group in the above compound (I) and the acid anhydride group in the above compound (II), but may include other reaction forms. , The compound having a structure in which the compound (II) is added to the compound (I) means a general term for reaction products.

In the present invention, the structure in which 0.1 to 0.8 mol of the compound (II) is added to 1 mol of the compound (I) is excellent in the sensitivity of the obtained polymerizable composition and is insulating. It is preferable because a cured product capable of forming a fine pattern having excellent properties can be obtained, and a structure having 0.2 to 0.6 mol added is particularly preferable. In other words, a cured product having excellent adhesion and heat resistance has a structure in which 0.05 to 0.4 mol of the compound (II) is added to 1 mol of the hydroxyl group in the compound (I). It is preferable because it can be obtained, and it is particularly preferable that the structure has 0.1 to 0.3 mol added.

When the compound (I) has a structure to which acid dianhydride is added, the structure may be such that 0.2 to 1.0 mol of acid dianhydride is added to 1 mol of the compound (I). The obtained polymerizable composition is preferable because of its high alkaline developability, and a structure in which 0.3 to 0.8 mol is added is particularly preferable. In other words, a cured product having excellent adhesion and heat resistance can be obtained by having a structure in which 0.1 to 0.5 mol of acid dianhydride is added to 1 mol of the hydroxyl group in the compound (I). Therefore, it is preferable to have a structure in which 0.15 to 0.4 mol is added, and it is particularly preferable.

The reaction of adding the acid dianhydride to the above-mentioned compound (I) can be carried out in the same manner as the above-mentioned reaction of adding the above-mentioned compound (II) to the above-mentioned compound (I). Further, the reaction of adding the compound (II) to the compound (I) to the compound (I) and the reaction of adding the acid dianhydride to the compound (I) may be carried out at the same time.

The acid value of the compound of the present invention is preferably in the range of 70 to 150 mg · KOH / g because it is excellent in alkaline developability of the obtained polymerizable composition, and is preferably in the range of 80 to 110 mg · KOH / g. Is particularly preferred.

When the weight average molecular weight Mw of the compound of the present invention is in the range of 2,000 to 15,000, the obtained polymerizable composition has excellent sensitivity and a cured product capable of forming a fine pattern having excellent insulating properties. It is preferable because it can be obtained, and it is particularly preferable that it is in the range of 3,000 to 10,000.

The molecular weight distribution (Mw / Mn) of the compound of the present invention is preferably in the range of 1.0 to 3.0 because of high resolution, and particularly preferably in the range of 1.5 to 2.5.

For the weight average molecular weight and molecular weight distribution, for example, GPC measurement of the polymer was performed using a GPC apparatus (LC-2000plus series) manufactured by JASCO Corporation, and polystyrene standard (for example, TSKgel standard manufactured by Tosoh Corporation) was used. It can be calculated from the calibration curve created by (polystyrene). For example, it can be suitably measured under the following conditions.
Solvent: THF
Solvent flow rate: 1.0 ml / min
Columns: KF-803, KF-802 (column for organic solvent-based GPC, for standard analysis, Shodex)
Column temperature: 40 ° C

The polymerizable composition of the present invention contains a compound (A) having a structure in which the compound (II) is added to the compound (I) and a polymerization initiator (B). With such a configuration, a polymerizable composition having excellent sensitivity and a cured product patterned with high accuracy can be obtained.

Since the content of the compound (A) is excellent in sensitivity, it is preferably 10 to 70 parts by mass, preferably 30 to 60 parts by mass, based on 100 parts by mass of the solid content of the polymerizable composition. More preferred.
The solid content of the above-mentioned polymerizable composition is the total amount of the components excluding the solvent described later from the polymerizable composition.

Since the compound (A) is a polymerizable compound having an ethylenically unsaturated bond, the polymerization initiator (B) may be any radical initiator used for polymerizing the compound having an ethylenically unsaturated bond. , Conventionally known compounds can be used. Specifically, for example, benzoyl peroxide, 2,2'-azobisisobutyronitrile, benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethylketal, 1-benzyl-1- Dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1-chlor-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone, 4-Benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoyl propane, 2-hydroxy-2- (4'-isopropyl) benzoyl propane, 4-butyl benzoyl trichloromethane, 4-phenoxy benzoyl dichloromethane , Methyl benzoyl halide, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2-methyl-1- [4-( Methylthio) phenyl] -2-morpholinopropane-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystylyl) -s-triazine, 2- (p-butoxystylyl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridin, 9,10-dimethylbenzphenazine, benzophenone / Mihilersketone, hexaarylbiimidazole / mercaptobenzimidazole, Thioxanthone / amine, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, and JP-A-2000-80068, JP-A-2001-233842, JP-A-2005-97141, JP-A-2006-516246. Examples thereof include the compounds described in Japanese Patent No. 3860170, Japanese Patent No. 3798008, and WO2006 / 018973.

It is preferable that the polymerization initiator (B) is a compound having an oxime ester group because the obtained polymerizable composition has excellent sensitivity and a cured product patterned with high accuracy can be obtained.

It is preferable that the polymerization initiator (B) is a compound having a carbazole skeleton because the obtained polymerizable composition has excellent sensitivity and a cured product patterned with high accuracy can be obtained.

The polymerization initiator (B) is preferably a compound having an electron-withdrawing group because a cured product having excellent insulating properties can be obtained. In particular, it is preferable that the electron-withdrawing group is a nitro group.

The content of the polymerization initiator (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the compound (A) and the polymerizable compound (D) described later. It is preferable because the sensitivity of the polymerizable composition is excellent, and it is more preferably 1 to 5 parts by mass.

The polymerizable composition may further contain a colorant (C). Examples of the colorant (C) include pigments and dyes. As the pigment and the dye, an inorganic color material or an organic color material can be used, respectively. These can be used alone or in combination of two or more. Here, the pigment means a colorant that is insoluble in a general solvent, and includes those that are insoluble in a solvent among inorganic or organic coloring materials and those in which an inorganic or organic dye is raked.

Examples of the pigment include carbon black obtained by a furnace method, a channel method or a thermal method, carbon black such as acetylene black, ketjen black or lamp black, carbon black prepared or coated with an epoxy resin, and carbon black. Was previously dispersed in a resin in a solvent and coated with a resin of 20 to 200 mg / g, the carbon black was subjected to an acidic or alkaline surface treatment, the average particle size was 8 nm or more, and the DBP oil absorption amount was 90 ml / 100 g or less. Carbon black, carbon black, graphite carbon black, graphite, activated carbon, carbon fiber, carbon nanotubes, carbon whose total oxygen content calculated from CO and CO ₂ in the volatile matter at 950 ° C is 9 mg or more per 100 m ² of surface area. Microcoils, carbon nanohorns, carbon aerogels, fullerene, aniline black, pigment black 7, titanium black, lactam black, perylene black and other black pigments, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese-based, fe Russian compound, phosphate ultramarine blue, dark blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber, rake Examples thereof include organic or inorganic pigments such as pigments.
Among the above pigments, it is preferable to use a black pigment because it has a high light-shielding property.

As the pigment, a commercially available product can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97. , 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223. , 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110. , 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62 and 64 Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50 and the like.

Examples of the dye include nitroso compound, nitro compound, azo compound, diazo compound, xanthene compound, quinoline compound, anthraquinone compound, coumarin compound, cyanine compound, phthalocyanine compound, isoindolinone compound, isoindrin compound, quinacridone compound and antanthrone. Examples thereof include a metal complex compound of a compound, a perinone compound, a perylene compound, a diketopyrrolopyrrole compound, a thioindigo compound, a dioxazine compound, a triphenylmethane compound, a quinophthalone compound, a naphthalenetetracarboxylic acid, an azo dye, and a cyanine dye.

In the polymerizable composition of the present invention, the content of the colorant (C) is not particularly limited, but is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the compound (A). It is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass. When the content of the colorant (D) is within the above range, the polymerizable composition has excellent storage stability without aggregation of the colorant, and the cured product of the polymerizable composition has a high light-shielding property. It is preferable because it becomes.
For example, in the case of forming a cured product having a thickness of 1 to 3 μm, the content of the colorant (C) is not particularly limited, but is preferable with respect to 100 parts by mass of the compound (A). It is 10 to 500 parts by mass, more preferably 10 to 300 parts by mass, and further preferably 10 to 200 parts by mass.

The polymerizable composition may further contain a polymerizable compound (D) other than the compound (A). Examples of the polymerizable compound include -2-hydroxyethyl acrylate, -2-hydroxypropyl acrylate, isobutyl acrylate, -N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, and acrylate. Methoxyethyl, dimethylaminoethyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, -2-hydroxyethyl methacrylate, -2-hydroxypropyl methacrylate, butyl methacrylate, tertiary butyl methacrylate, Examples thereof include cyclohexyl methacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tricyclodecanemethylol diacrylate.

The content of the polymerizable compound (D) increases the sensitivity of the polymerizable composition, and a cured product having excellent chemical resistance can be obtained. Therefore, the content of the polymerizable compound (D) is 5 to 80% by mass with respect to 100 parts by mass of the compound (A). The amount is preferably 10 to 70 parts by mass, more preferably 10 to 70 parts by mass.

The polymerizable composition of the present invention may further contain the epoxy compound (E). Examples of the epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether and heptyl. Glycyzyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether , Benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy- Examples thereof include monofunctional epoxy compounds such as 4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide and propylene oxide.

Further, polyfunctional epoxy compounds such as bisphenol type epoxy compounds and glycidyl ethers can also be used, and examples of the bisphenol type epoxy compounds include alkylidene bisphenol polyglycidyl ether type epoxy resins and hydrogenated bisphenol type epoxy compounds. Examples include bisphenol type epoxy compounds.

Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,8-octanediol diglycidyl ether. , 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol di Diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri ( Examples thereof include glycidyl oxymethyl) methane and 1,1,1,1-tetra (glycidyl oxymethyl) methane.

A solvent (F) can be further added to the polymerizable composition of the present invention. The solvent is a component that is liquid at 1 atm and 25 ° C. and is not classified into the compound (A), the polymerization initiator (B), the colorant (C) and the polymerizable compound (D). As the solvent, a solvent capable of dissolving or dispersing each of the above components (compound (A), polymerization initiator (B), colorant (C), polymerizable compound (D), etc.) is usually used. Can be used. For example, ketone solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2- Ethereal solvents such as diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and Ester-based solvents such as texanol; cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene. Ether ester solvents such as glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; benzene, toluene and BTX-based solvent such as xylene; aliphatic hydrocarbon-based solvent such as hexane, heptane, octane and cyclohexane; terpene-based hydrocarbon oil such as terepine oil, D-lymonen and pinen; mineral spirit, swazole # 310 (above, Cosmo Matsuyama) Petroleum); and Solbesso # 100 (above, Exxon Chemical); and other paraffinic solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane and other halogenated aliphatic hydrocarbon solvents; chlorobenzene. Harmonized aromatic hydrocarbon solvents such as carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl. Examples thereof include sulfoxide and water, and these solvents can be used as one kind or a mixed solvent of two or more kinds.

Among these, ketone solvents, ester solvents, ether ester solvents and the like, particularly cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate and propylene glycol monomethyl ether acetate (PGMEA), etc. are the compounds (A) and polymerization initiators (PGMEA). B) is preferable because it has good solubility.

The content of the solvent in the polymerizable composition of the present invention is not particularly limited, but is preferably 20 to 98% by mass, more preferably 60 to 95% by mass in the polymerizable composition. When the content of the solvent is within the above range, the polymerizable composition is excellent in storage stability without agglomeration of the colorant, and it is preferable because the film thickness of the cured product can be easily controlled.

The polymerizable composition of the present invention is, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion accelerator; a filler; a defoaming agent; a dispersant. Conventional additives such as leveling agents; silane coupling agents; flame retardants can be added. These can be used alone or in admixture of two or more.

The polymerizable composition of the present invention is a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and dipping, soda glass, quartz glass, a semiconductor substrate, metal, paper, and plastic. It can be applied on a supporting substrate such as. Further, it is also possible to apply it once on a support substrate such as a film and then transfer it onto another support substrate, and there is no limitation on the application method thereof.

The cured product of the present invention means a product obtained by polymerizing the above-mentioned polymerizable composition. The polymerization method is not particularly limited, but it is preferable to polymerize by either light irradiation, heating, or both methods because of its high curability.

The light source used for curing the polymerizable composition of the present invention includes an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury steam arc lamp, a xenon arc lamp, a carbon arc lamp, and a metal halide. Uses electromagnetic energy with wavelengths from 2000 angstroms to 7000 angstroms obtained from lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., and high energy rays such as electron beams, X-rays, and radiation. However, preferred examples thereof include an ultrahigh pressure mercury lamp, a mercury steam arc lamp, a carbon arc lamp, a xenon arc lamp, and the like that emit light having a wavelength of 300 to 450 nm.

In the case of curing by heating, a method of prebaking at 70 to 100 ° C. for 100 seconds, removing the solvent, and then heating at 150 ° C. to 250 ° C. for 30 minutes to 1 hour to cure can be mentioned. If the curing temperature is lower than 150 ° C., sufficient curing may not occur, and if it is 250 ° C. or higher, coloring or decomposition of the cured film may occur.

The polymerizable composition and cured product of the present invention are used in a color display liquid crystal display panel such as a curable paint, a varnish, a curable adhesive, a printed substrate, and a display device (color television, PC monitor, mobile information terminal, digital camera, etc.). Color filter, color filter for various display applications, color filter of CCD image sensor, touch panel, electric light emission display device, plasma display panel, black partition of organic EL), powder coating, printing ink, printing plate, adhesive, gel coat , Photoresists for electronic engineering, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electrical and electronic components, For manufacturing three-dimensional objects by solder resist, magnetic recording material, micromechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, screen printing stencil, stereolithography. Materials, holographic recording materials, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and It can be used for various purposes such as a photoresist material for a visible laser direct image system, a photoresist material used for forming a dielectric layer in sequential lamination of printed circuit boards, and a protective film, and the application is not particularly limited. However, among the above-mentioned applications, it can be particularly preferably used for a display device.

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

[Example 1-1] Preparation of compound A-1 solution 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] 3-phenylindane (hereinafter, also referred to as compound a-1) 25. 0 g, 7.29 g of acrylic acid (hereinafter, also referred to as compound b-1), 0.065 g of dibutyl hydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 21.5 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 8.75 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter, also referred to as BPDA) as an acid dianhydride, an acid anhydride having a polymerizable group. As 1,3-dioxooctahydroisobenzofuran-5-carboxylic acid-2- (methacryloyloxy) ethyl (compound (II-1)) 4.62 g, dibutylhydroxytoluene 0.027 g, tetrabutylammonium chloride 0.180 g. , And 15.8 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to room temperature, 22.0 g of PGMEA was added to obtain the target compound A-1 as a PGMEA solution (concentration: 43.8% by mass). Compound A-1 had Mw = 5300, Mn = 2900, and an acid value (solid content) of 93 mg · KOH / g.
Compound A-1 is an acid anhydride having 0.30 BPDA, which is an acid dianhydride, and a polymerizable group for one hydroxyl group of the compound obtained by adding the compound b-1 to the compound a-1. It was obtained by reacting compound (II-1) at a ratio of 0.15.

[Example 1-2] Preparation of compound A-2 solution 25.0 g of compound a-1, 7.29 g of compound b-1, 0.065 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and PGMEA21. 5 g was charged and stirred at 120 ° C. for 15 hours. The reaction mixture was cooled to room temperature, 8.75 g of BPDA as an acid dianhydride, and 1,3-dioxo1,3-dihydroisobenzofuran-5-carboxylic acid-2- (methacryloyl) as an acid anhydride having a polymerizable group. Oxy) ethyl (Compound (II-2)) 4.53 g, dibutyl hydroxytoluene 0.027 g, tetrabutylammonium chloride 0.180 g, and PGMEA 15.8 g were added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to room temperature, 21.9 g of PGMEA was added to obtain the target compound A-2 as a PGMEA solution (concentration: 43.8% by mass). Compound A-2 had Mw = 5200, Mn = 2900, and an acid value (solid content) of 93 mg · KOH / g.
Compound A-2 is an acid anhydride having 0.30 BPDA, which is an acid dianhydride, and a polymerizable group for one hydroxyl group of the compound obtained by adding compound b-1 to compound a-1. It was obtained by reacting compound (II-2) at a ratio of 0.15.

[Example 1-3] Preparation of compound A-3 solution 25.0 g of compound a-1, 7.29 g of compound b-1, 0.0650 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and PGMEA21. 5 g was charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 8.75 g of BPDA as an acid dianhydride and 7.09 g of pentaerythritol-triacrylate-monoacid anhydride (compound (II-6)) as an acid anhydride having a polymerizable group. 0.032 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 17.9 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to room temperature, 23.1 g of PGMEA was added to obtain the target compound A-3 as a PGMEA solution (concentration: 43.8% by mass). Compound A-3 had Mw = 5400, Mn = 2900, and an acid value (solid content) of 89 mg · KOH / g.
Compound A-3 is an acid anhydride having 0.30 BPDA, which is an acid dianhydride, and a polymerizable group for one hydroxyl group of the compound obtained by adding compound b-1 to compound a-1. It was obtained by reacting compound (II-6) at a ratio of 0.15 pieces.

[Example 1-4] Preparation of compound A-4 solution 9,9-bis (4-glycidyloxyphenyl) fluorene (hereinafter, also referred to as compound a-2) 25.0 g, compound b-1 7.95 g , 0.066 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 22.0 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction mixture was cooled to room temperature, and BPDA was 9.55 g as an acid dianhydride, 5.04 g of the compound (II-1) as an acid anhydride having a polymerizable group, 0.029 g of dibutylhydroxytoluene, and tetrabutylammonium chloride. 0.180 g and 16.9 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to room temperature, 22.9 g of PGMEA was added to obtain the target compound A-4 as a PGMEA solution (concentration: 44.6% by mass). Compound A-4 had Mw = 5500, Mn = 2900, and an acid value (solid content) of 97 mg · KOH / g.
Compound A-4 is an acid anhydride having 0.30 BPDA, which is an acid dianhydride, and a polymerizable group for one hydroxyl group of the compound obtained by adding compound b-1 to compound a-2. It was obtained by reacting compound (II-1) at a ratio of 0.15.

[Example 1-5] Preparation of compound A-5 solution 25.0 g of compound a-2, 7.29 g of compound b-1, 0.065 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 22. 0 g was charged and stirred at 120 ° C. for 15 hours. The reaction mixture was cooled to room temperature, and BPDA was 9.55 g as an acid dianhydride, compound (II-2) was 4.94 g as an acid anhydride having a polymerizable group, 0.029 g of dibutylhydroxytoluene, and tetrabutylammonium chloride. 0.180 g and 16.8 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to room temperature, 22.8 g of PGMEA was added to obtain the target compound A-5 as a PGMEA solution (concentration: 43.8% by mass). Compound A-5 had Mw = 5400, Mn = 2900, and an acid value (solid content) of 98 mg · KOH / g.
Compound A-5 is an acid anhydride having 0.30 BPDA, which is an acid dianhydride, and a polymerizable group for one hydroxyl group of the compound obtained by adding compound b-1 to compound a-2. It was obtained by reacting compound (II-2) at a ratio of 0.15.

[Example 1-6] Preparation of compound A-6 solution 4,4-bis [4- (2,3-epoxypropyloxy) phenyl] (biphenyl-4-yl) cyclohexylmethane (hereinafter, also referred to as compound a-3). 25.0 g, 6.56 g of compound b-1, 0.063 g of dibutyl hydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 21.0 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction mixture was cooled to room temperature, 7.88 g of BPDA as an acid dianhydride, 4.16 g of the compound (II-1) as an acid anhydride having a polymerizable group, 0.024 g of dibutylhydroxytoluene, and tetrabutylammonium chloride. 0.180 g and 14.6 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. After cooling to room temperature, 21.0 g of PGMEA was added to obtain the target compound A-6 as a PGMEA solution (concentration: 44.6% by mass). Compound A-6 had Mw = 5200, Mn = 2600, and an acid value (solid content) of 88 mg · KOH / g.
Compound A-6 is an acid anhydride having 0.30 BPDA, which is an acid dianhydride, and a polymerizable group for one hydroxyl group of the compound obtained by adding compound b-1 to compound a-3. It was obtained by reacting compound (II-1) at a ratio of 0.15.

[Example 1-7] Preparation of compound A-7 solution 25.0 g of compound a-1, 7.29 g of compound b-1, 0.065 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and PGMEA21. 5 g was charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 6.2 g of compound (II-1), 6.0 g of succinic anhydride, 0.024 g of dibutylhydroxytoluene, and 0.180 g of tetrabutylammonium chloride were added as acid anhydrides having a polymerizable group. , And 19.0 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 3 hours. Further, 12.5 g of compound a-1 was added, and the mixture was stirred at 90 ° C. for 90 minutes and at 120 ° C. for 4 hours. Further, 5.0 g of succinic anhydride was added, the mixture was stirred at 100 ° C. for 2 hours, cooled to room temperature, 38.5 g of PGMEA was added, and the target compound A-7 was added to a PGMEA solution (concentration: 44.6% by mass). ). Compound A-7 had Mw = 4800, Mn = 2000, and an acid value (solid content) of 76 mg · KOH / g.
Compound A-7 polymerizes with 0.2 compound (II-1), which is an acid anhydride having a polymerizable group, for one hydroxyl group of the compound obtained by adding compound b-1 to compound a-3. The acid anhydride having no group was added at a ratio of 0.6, the epoxy group of compound a-3 was reacted at a ratio of 0.5, and 0.5 of the acid anhydride was further reacted. It was obtained.

[Production Example 1] Preparation of compound A-8 solution 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] 3-phenylindane 100 g, acrylic acid 30 g, 2,6-di-tert-butyl 0.26 g of -p-cresol, 0.71 g of tetrabutylammonium bromide, and 86.0 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The reaction mixture is cooled to room temperature, 56.0 g of PGMEA, 35.0 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 0.24 g of tetra-n-butylammonium bromide are added, and the temperature is 120 ° C. The mixture was stirred for 4 hours. Further, 9.1 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, and then 83.5 g of PGMEA was added. Then, the target compound A-8 was obtained as a PGMEA solution (concentration: 45.0% by mass). Compound A-8 had Mw = 5300, Mn = 2100, and an acid value (solid content) of 99.7 mgKOH / g.

[Production Example 2] Preparation of compound A-9 solution 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0. 273 g, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The reaction mixture is cooled to room temperature, 44.5 g of PGMEA, 28.6 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 0.24 g of tetra-n-butylammonium bromide are added, and the temperature is 120 ° C. The mixture was stirred for 4 hours. Further, 7.4 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, 65.0 g of PGMEA was added. Then, the target compound A-9 was obtained as a PGMEA solution (concentration: 45.0% by mass). Compound A-9 had Mw = 5100, Mn = 2170, and an acid value (solid content) of 103.9 mg · KOH / g.

[Manufacturing Example 3] Carbon Black No. Production of No. 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a peroxodisulfuric acid sodium deionized aqueous solution (concentration 2.0 N) were mixed and stirred at 60 ° C. for 10 hours. After filtration, the obtained slurry was neutralized with sodium hydroxide, treated by diafiltration, and the obtained solid was dried at 75 ° C. overnight to obtain carbon black No. 1 was obtained as a black powder.

[Manufacturing Example 4] Carbon Black No. Production of No. 2 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 400 ml of sulfolane were mixed, 15 g of amide sulfate was added, and the mixture was stirred at 140 to 150 ° C. for 10 hours. The obtained slurry was neutralized with lithium hydroxide, treated by diafiltration, and the obtained solid was dried at 75 ° C. overnight to obtain carbon black No. 2 was obtained as a black powder.

[Production Example 5] Surface-treated carbon black dispersion liquid No. Preparation of No. 1 Carbon Black No. 20 g of 1 was weighed, 4.45 g of the compound A-8 solution obtained in Production Example 1, 3 g of DISPERBYK-161, and 72.55 g of PGMEA were weighed and treated with a bead mill to obtain carbon black dispersion No. 1 (concentration 20% by mass) was obtained.

[Production Example 6] Surface-treated carbon black dispersion liquid No. Preparation of 2 Carbon black No. 20 g of 2 was weighed, 4.45 g of the compound A-8 solution obtained in Production Example 1, 3 g of DISPERBYK-161, and 72.55 g of PGMEA were weighed and treated with a bead mill to obtain carbon black dispersion No. 2 (concentration 20% by mass) was obtained.

[Examples 2-1 to 2-9, Comparative Examples 1 to 2]
Each component was mixed at the ratios (parts by mass) shown in Tables 1 and 2 to prepare a polymerizable composition, and the sensitivity, minimum contact line width, volume resistance and taper angle were evaluated by the following methods. The results are shown in Tables 1 and 2.
Each component in the table is as follows.

A-1: Compound A-1 solution (concentration 43.8% by mass)
A-2: Compound A-2 solution (concentration 43.8% by mass)
A-3: Compound A-3 solution (concentration 43.8% by mass)
A-4: Compound A-4 solution (concentration 44.6% by mass)
A-5: Compound A-5 solution (concentration 43.8% by mass)
A-6: Compound A-6 solution (concentration 44.6% by mass)
A-7: Compound A-7 solution (concentration 44.6% by mass)
A-8: Compound A-8 solution (concentration 45.0% by weight)
A-9: Compound A-9 solution (concentration 45.0% by weight)
B-1: Compound B1 (compound having the following structure)
B-2: Compound B2 (compound having the following structure)
C-1: Surface-treated carbon black dispersion liquid No. 1 (concentration 20% by mass)
C-2: Surface-treated carbon black dispersion No. 2 (concentration 20% by mass)
D-1: Kayarad DPHA (polyfunctional acrylic compound; manufactured by Nippon Kayaku Co., Ltd.)
E-1: EP-4100 (bisphenol A type liquid epoxy compound; manufactured by ADEKA Corporation)
F-1: PGMEA (solvent)
G-1: KBM-403 (silane coupling agent having an epoxy group; manufactured by Shin-Etsu Chemical Co., Ltd.)

<Sensitivity>
The polymerizable compositions of Examples and Comparative Examples were spin-coated (1300 rpm, 50 seconds) on a glass substrate and dried. After exposure using a predetermined mask prebaked at 100 ° C. for 100 seconds and using an ultrahigh pressure mercury lamp as a light source, the mixture was immersed in a 0.04% KOH aqueous solution at 23 ° C. for 30 seconds for development, and washed well with water. After washing and drying with water, the pattern was fixed by baking at 230 ° C. for 30 minutes.
In the evaluation of sensitivity, A is defined as having an exposure amount of 40 mJ / cm ² and good fixing of the developed pattern, and an exposure amount of 40 mJ / cm ² due to poor fixing of the developed pattern and an exposure amount of 80 mJ / cm. In cm ² , the one in which the pattern fixing after development was good was defined as B, and in cm 2, the one requiring exposure of 100 mJ / cm ² or more was designated as C. A polymerizable composition having a sensitivity of A can be preferably used as a black matrix, a polymerizable composition having a sensitivity of B can be used as a black matrix, and a polymerizable composition having a sensitivity of C can be used as a black matrix. Difficult to do.

<Minimum contact line width>
The polymerizable compositions of Examples and Comparative Examples were spin-coated on a glass substrate (10 cm × 10 cm) and heated at 100 ° C. for 100 seconds to form a 1.0 μm coating film on the surface of the glass substrate. Then, using a proximity exposure machine manufactured by Microtech, exposure was performed at an exposure amount of 40 mJ / cm ² (Gap 100 μm) through a negative mask on which a pattern of 1 to 20 μm was formed. The exposed film was developed with a 0.04 mass% KOH aqueous solution at 23 ° C. for 40 seconds, and then calcined at 230 ° C. for 30 minutes. By observing with an optical microscope, the photomask pattern having the smallest number among the photomask patterns in which the cured film is in close contact with the glass substrate was set as the minimum contact line width. When the minimum contact line width is 6 μm or less, it can be preferably used as a high-definition black matrix.

<Volume resistance>
The polymerizable compositions of Examples and Comparative Examples were applied to a Cr-glass substrate, prebaked at 90 ° C. for 90 seconds, and dried. An aluminum electrode was produced by exposing a Cr portion of several mm on the end face portion of the coated substrate, post-baking the coated substrate at 230 ° C. for 30 minutes, and then depositing aluminum on the coating film using a vacuum vapor deposition machine. The resistance value was measured at a voltage of 10 V using ADVANTEST R8340 ULTRA HIGH RESISTANCE METER. When the volume resistance is 1.0 × 10 ¹³ Ω · cm or more, it is preferable as a black matrix.

<Taper angle>
The polymerizable compositions of Examples and Comparative Examples were spin-coated on a glass substrate (10 cm × 10 cm) at 900 rpm for 5 seconds and heated at 100 ° C. for 100 seconds to form a 1.0 μm coating film on the surface of the glass substrate. I let you. Then, using a proximity exposure machine manufactured by Microtech, exposure was performed at an exposure amount of 40 mJ / cm ² (Gap 100 μm) through a negative mask on which a pattern of 6 μm was formed. The exposed film is developed with a 0.04 mass% KOH aqueous solution at 23 ° C. for 40 seconds, then fired at 230 ° C. for 30 minutes, and the bonding angle (taper angle) between the pattern and the substrate is measured with a scanning electron microscope. ) Was measured. This taper angle corresponds to the angle θ in FIGS. 1A and 1B. If the taper angle is acute, it means that there is no undercut in the pattern, and if the taper angle is obtuse, it means that there is undercut in the pattern. If there is an undercut in the pattern, the contrast will decrease, resulting in a defect.

From the results shown in Tables 1 and 2, it was confirmed that the polymerizable composition using the compound of the present invention has excellent sensitivity, excellent insulating properties, and can form a fine pattern having an appropriate pattern shape. Was done.

Claims (11)

A compound having a structure in which an acid anhydride having a polymerizable group is added to a compound represented by the following general formula (I).

(In the formula, R ¹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ independently have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group. One or more of the methylene groups in the group represent a group having 1 to 20 carbon atoms substituted with —O— under the condition that the oxygen atoms are not adjacent to each other.
In each of X ¹ and X ² , each of the divalent hydrocarbon groups having 1 to 20 carbon atoms or one or more methylene groups in the hydrocarbon groups is -O under the condition that the oxygen atoms are not adjacent to each other. Represents a group with 1 to 20 carbon atoms substituted with −
M ¹ represents a group represented by the following formula (a), (b), (c) or (d). )

(In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R. ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are independent hydrogen atoms and halogens, respectively. One or more of an atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group having 3 to 20 carbon atoms containing a heterocycle, or a methylene group in a hydrocarbon group. Represents a group having 1 to 20 carbon atoms substituted with a divalent group selected from the following <Group A>.
<Group A>: -O-, -CO-, -COO-, -OCO-, -NR ^51- , -NR ⁵¹ CO-, -S-
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^51s are present in the molecule, they may be the same or different.
R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ . , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ have one or more hydrogen atoms in the hydrocarbon group. It may be a group having 1 to 20 carbon atoms substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵² , -COOR ⁵² , -CO-R ⁵² or -SR ⁵² .
R ⁵² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^52s are present in the molecule, they may be the same or different.
R ²¹ and R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ , R ³⁹ . And R ⁴⁰ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ and R ⁴⁸ and R ⁴⁹ are coupled to each other. It may form a ring consisting of a hydrogen atom and a carbon atom having 3 to 10 carbon atoms.
Cy represents a cycloalkyl group having 3 to 10 carbon atoms.
* Means the site where the group represented by (a), (b), (c) and (d) binds to an adjacent group. ) The compound according to claim 1, wherein M ¹ in the general formula (I) is a group represented by the above formula (a). The compound according to claim 1, wherein M ¹ in the general formula (I) is a group represented by the above formula (c). The compound according to any one of claims 1 to 3, wherein the acid anhydride having a polymerizable group is an acid anhydride having a radically polymerizable group. The compound according to any one of claims 1 to 4, wherein the acid anhydride having a polymerizable group is an acid anhydride having an alicyclic structure. The compound according to any one of claims 1 to 5, further having a structure to which acid dianhydride is added. A polymerizable composition containing the compound (A) according to any one of claims 1 to 6 and the polymerization initiator (B). The polymerizable composition according to claim 7, further comprising a colorant (C). A cured product of the polymerizable composition according to claim 7 or 8. A display device containing the cured product according to claim 9. A method for producing a cured product, which comprises a step of irradiating or heating the polymerizable composition according to claim 7 or 8 with light.

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