JP7634985B2 - Compound, polymerizable composition and cured product - Google Patents

Description

The present invention relates to a compound having a structure in which a tetracarboxylic dianhydride is added to an epoxy acrylate compound, a polymerizable composition containing the compound, and a method for producing the compound.

The alkali-developable photosensitive resin composition contains an alkali-developable resin containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. This alkali-developable photosensitive resin composition can be polymerized and cured by exposure to ultraviolet light or electron beams, and is therefore used in photocurable inks, photosensitive printing plates, printed wiring boards, various photoresists, and the like. Recently, with the progress of making electronic devices lighter, thinner, shorter, smaller, and more functional, there is a demand for alkali-developable photosensitive resin compositions that can form fine patterns with high precision.

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 discloses a photosensitive resin composition containing an unsaturated group-containing compound obtained by further reacting a reaction product of an aromatic epoxy compound derived from a bisphenol with (meth)acrylic acid with a) a saturated dicarboxylic acid or an acid anhydride thereof, and b) a saturated tetracarboxylic acid or an acid dianhydride thereof.
Patent Document 3 discloses an alkali-developable photosensitive resin composition containing a photopolymerizable unsaturated compound that is an esterification reaction product between an epoxy adduct obtained by adding an unsaturated monobasic acid to a novel epoxy compound having a substituted benzo- or naphthocycloalkane skeleton, and a polybasic acid anhydride.
Patent Documents 4 and 5 disclose photosensitive resin compositions containing a carboxyl group-containing resin having a bisphenolfluorene skeleton.

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

The object of the present invention is to provide a compound that is excellent in adhesion and heat resistance and is useful as a polymerizable component of a polymerizable composition that can obtain an appropriate pattern shape or a fine pattern, and a polymerizable composition using the compound.

As a result of intensive research, the present inventors discovered that the above-mentioned object can be achieved by a compound having a structure in which a tetracarboxylic dianhydride having a fluorene structure or an indane structure 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 fluorene structure or an indane structure, and thus arrived at the present invention.

That is, the present invention relates to a compound having a structure in which at least one selected from the group consisting of tetracarboxylic dianhydrides represented by the following general formulas (IIa), (IIb), and (IIc) is added to an epoxy acrylate 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、炭素原子数１～２０の炭化水素基、又はハロゲン原子を表し、
Ｘ^１及びＸ^２は、それぞれ独立に、炭素原子数１～２０の２価の炭化水素基を表し、
Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｘ^１及びＸ^２は、炭化水素基中のメチレン基の１つ又は２つ以上が、酸素が隣り合わない条件で、－Ｏ－又は－Ｓ－で置換された炭素原子数１～２０の基であってもよく、
Ｍ^１は下記式（ａ）、（ｂ）又は（ｃ）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 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom;
^X1 and ^X2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms;
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X ¹ and X ² may each be a group having 1 to 20 carbon atoms in which one or more methylene groups in a hydrocarbon group are substituted with -O- or -S-, provided that no oxygen is adjacent to them;
^M1 represents a group represented by the following formula (a), (b) or (c):

（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及びＲ^４４は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、炭素原子数２～２０の複素環含有基又はハロゲン原子を表し、
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及びＲ^４４は、炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基、水酸基、－ＯＲ^５１、－ＣＯＯＲ^５１、－ＣＯ－Ｒ^５１又は－ＳＲ^５１で置換された炭素原子数１～２０の基であってもよく、
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、化合物中に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及びＲ^４４は、炭化水素基中のメチレン基の１つ又は２つ以上が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^５２－、－ＮＲ^５２ＣＯ－又は－Ｓ－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、化合物中に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及びＲ^４３とＲ^４４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い。
式中の＊は、（ａ）、（ｂ）及び（ｃ）で表される基が、＊部分で、隣接する基と結合することを意味する。）

(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 and R ⁴⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom;
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 and R ⁴⁴ may each represent a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵¹ , -COOR ⁵¹ , -CO-R ⁵¹ or -SR ⁵¹ ;
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵¹ are present in the compound, 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 and R ⁴⁴ may each be a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, -CO-, -COO-, -OCO-, -NR ⁵² -, -NR ⁵² CO- or -S-;
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;
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 , and R ⁴³ and R ⁴⁴ may be bonded to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms.
In the formula, * means that the groups represented by (a), (b), and (c) are bonded to adjacent groups at the * portion.

（式中、Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６４、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７１、Ｒ^７２、Ｒ^７３、Ｒ^７４、Ｒ^７５、Ｒ^７６、Ｒ^７７、Ｒ^７８、Ｒ^７９、Ｒ^８０、Ｒ^８１、Ｒ^８２、Ｒ^８３及びＲ^８４は、それぞれ独立に、水素原子、炭素原子数１～２０の炭化水素基、炭素原子数２～２０の複素環含有基又はハロゲン原子を表し、
Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６４、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７１、Ｒ^７２、Ｒ^７３、Ｒ^７４、Ｒ^７５、Ｒ^７６、Ｒ^７７、Ｒ^７８、Ｒ^７９、Ｒ^８０、Ｒ^８１、Ｒ^８２、Ｒ^８３及びＲ^８４は、炭化水素基中の水素原子の１つ又は２つ以上が、ハロゲン原子、シアノ基、ニトロ基、水酸基、－ＯＲ^９１、－ＣＯＯＲ^９１、－ＣＯ－Ｒ^９１又は－ＳＲ^９１で置換された炭素原子数１～２０の基であってもよく、
Ｒ^９１は、水素原子又は炭素原子数１～２０の炭化水素基を表し、化合物中にＲ^９１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^６１、Ｒ^６２、Ｒ^６３、Ｒ^６４、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７１、Ｒ^７２、Ｒ^７３、Ｒ^７４、Ｒ^７５、Ｒ^７６、Ｒ^７７、Ｒ^７８、Ｒ^７９、Ｒ^８０、Ｒ^８１、Ｒ^８２、Ｒ^８３及びＲ^８４は、炭化水素基中のメチレン基の１つ又は２つ以上が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ^９２－、－ＮＲ^９２ＣＯ－又は－Ｓ－で置換された炭素原子数１～２０の基であってもよく、
Ｒ^９２は、水素原子又は炭素原子数１～２０の炭化水素基を表し、化合物中にＲ^８２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^６１とＲ^６２、Ｒ^６２とＲ^６３、Ｒ^６３とＲ^６４、Ｒ^６５とＲ^６６、Ｒ^６６とＲ^６７、Ｒ^６７とＲ^６８、Ｒ^６９とＲ^７０、Ｒ^７０とＲ^７１、Ｒ^７１とＲ^７２、Ｒ^７４とＲ^７５、Ｒ^７７とＲ^７８、Ｒ^７８とＲ^７９、Ｒ^７９とＲ^８０、Ｒ^８１とＲ^８２、Ｒ^８２とＲ^８３及びＲ^８３とＲ^８４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、
Ｙ^１、Ｙ^２、Ｙ^３、Ｙ^４、Ｙ^５及びＹ^６は、それぞれ独立に、炭素原子数１～２０の炭化水素基を表し、
Ｙ^１とＹ^２は、直接、又はメチレン基、－Ｏ－若しくは－Ｓ－を介して互いに結合していてもよく、
Ｌ^１及びＬ^２は、それぞれ独立に、炭素原子数６～２０のアリール基を表す。）

(In the formula, R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom;
R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁹¹ , -COOR ⁹¹ , -CO-R ⁹¹ or -SR ⁹¹ ;
R ⁹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁹¹ are present in the compound, they may be the same or different;
R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ may each be a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, -CO-, -COO-, -OCO-, -NR ⁹² -, -NR ⁹² CO- or -S-;
R ⁹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^82s are present in the compound, they may be the same or different;
R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁹ and R ⁷⁰ , R ⁷⁰ and R ⁷¹ , R ⁷¹ and R ⁷² , R ⁷⁴ and R ⁷⁵ , R ⁷⁷ and R ⁷⁸ , R ⁷⁸ and R ⁷⁹ , R ⁷⁹ and R ⁸⁰ , R ⁸¹ and R ⁸² , R ⁸² and R ⁸³ , and R ⁸³ and R ⁸⁴ may be bonded to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
Y ¹ and Y ² may be bonded to each other directly or via a methylene group, -O- or -S-;
^L1 and ^L2 each independently represent an aryl group having 6 to 20 carbon atoms.

The present invention also relates to a polymerizable composition containing the above compound (A) and a polymerization initiator (B).

The polymerizable composition containing the compound of the present invention can give a cured product with excellent sensitivity, adhesion, and heat resistance, making it easy to form appropriate pattern shapes and fine patterns. Therefore, it is particularly useful as a polymerizable composition for solder resist and black matrix.

The compound, polymerizable composition, and method for producing the compound of the present invention will be described in detail below based on preferred embodiments.
The compound of the present invention is a compound having a structure in which at least one selected from tetracarboxylic acid dianhydrides having a fluorene structure or an indane structure represented by the above general formula (IIa), (IIb) and (IIc) (hereinafter referred to as "compound (IIa)", "compound (IIb)" and "compound (IIc)") is further added to an epoxy acrylate compound (hereinafter referred to as "compound (I)") having a structure in which an acrylic acid or methacrylic acid compound is added to an epoxy compound having a fluorene structure or an indane structure represented by the above general formula (I).

In the above general formula (I), the hydrocarbon group having 1 to 20 carbon atoms 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.") may be a group having 1 to 20 carbon atoms consisting of carbon atoms and hydrogen atoms, and is not particularly limited. However, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms is preferable because the sensitivity of the polymerizable composition of the present invention is excellent, and an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, 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 linear, branched and cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.

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

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, a decahydronaphthyl group, an octahydropentalene group, a bicyclo[1.1.1]pentanyl group, and a tetradecahydroanthracenyl 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 replaced with a cycloalkyl group. For example, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, a cyclodecylmethyl group, a 2-cyclobutylethyl group, a 2-cyclopentylethyl group, a 2-cyclohexylethyl group, a 2-cycloheptylethyl group, a 2-cyclooctylethyl group, a 2-cyclononylethyl group, a 2-cyclodecylethyl group, a 3-cyclobutylpropyl group, a 3-cyclopentylethyl group, a ... Examples of such groups include cyclopropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl 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 phenyl, tolyl, xylyl, ethylphenyl, biphenylyl, naphthyl, anthryl, and phenanthrenyl groups, as well as groups in which these groups are substituted with one or more of the above alkyl groups, alkenyl groups, carboxyl groups, or halogen atoms, such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, and 2,4,6-trimethylphenyl.

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 by an aryl group. Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl. 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 by an aryl group. Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

In the above general formula (I), examples of the group having 1 to 20 carbon atoms, represented by ^R2 etc., in which a methylene group in the hydrocarbon group is substituted with -O- or -S-, provided that no oxygen atoms are adjacent to each other, include groups in which a methylene group in the group exemplified as the hydrocarbon group having 1 to 20 carbon atoms, represented by ^R2 etc., is substituted with -O- or -S-, provided that no oxygen atoms are adjacent to each other.

In the above general formula (I), examples of groups in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms, represented by ^R2 or the like, is substituted with -O-, provided that the oxygen atoms are not adjacent to each other, include a methoxy group, a methoxyethoxy group, a methoxyethoxyethoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentyloxy group, a isopentyloxy group, a t-pentyloxy 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 group in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms, represented by ^R2 or the like, is substituted with -S- include groups in which a methylene group in the above hydrocarbon group is substituted with -O-, provided that the oxygen atoms are not adjacent to each other, and the like in which the oxygen atom is replaced with a sulfur atom.

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), examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by ^X1 and ^X2 include divalent groups in which one hydrogen atom has been removed from the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 etc.

In the above general formula (I), examples of the group having 1 to 20 carbon atoms, represented by ^X1 and ^X2 , in which a methylene group in the hydrocarbon group is substituted with -O- or -S-, provided that the oxygen atoms are not adjacent to each other, include groups in which a methylene group in the group exemplified as the hydrocarbon group having 1 to 20 carbon atoms, represented by ^X1 and ^X2, is substituted with -O- or -S-, provided that the oxygen atoms are not adjacent to each other, and examples thereof include divalent groups obtained by removing one hydrogen atom from the groups exemplified as the above "group in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms, represented by ^R2 , ^etc. , is substituted with -O-, provided that the oxygen atoms are not adjacent to each other" and the above "group in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms, represented by R2, etc., is substituted with -S-".

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 each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms are preferred because they are highly stable, the sensitivity of a polymerizable composition containing the compound is excellent, and 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 each a hydrogen atom or a methyl group are preferred.

Moreover, the compound in which X ¹ and X ² in the above general formula (I) are methylene groups is preferred because it has excellent stability and is easy to produce.

In the above formulas (a), (b) and (c), the hydrocarbon group having ^{1 to 20 carbon atoms and the halogen atom represented by 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 and R ⁴⁴ (hereinafter referred to as "R ²¹ etc.") are the same as the hydrocarbon group having 1 to 20 carbon atoms and the halogen atom represented by the above R ² etc.

In the above formulas (a), (b) and (c), R The heterocycle-containing group having 2 to 20 carbon atoms, represented by ²¹ , etc., is not particularly limited, and examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, and 2,4-dioxyoxazolidin-3-yl. Specific examples thereof, including substituents, include groups having the following structures:

(In the above formulae, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. * in the formulae means that the groups represented by these formulae are bonded to an adjacent group at the * portion.)

The heterocycle-containing group having 2 to 20 carbon atoms may have a substituent such as a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR', -COOR', -CO-R' or -SR', and may have a bond such as -O-, -CO-, -COO-, -OCO-, -NR"-, -NR"CO- or -S-.
Here, ^R'1 and R" represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of ^R51 and ^R52 are present in the compound, they may be the same or different. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is the same as the above-mentioned hydrocarbon group having 1 to 20 carbon atoms represented by ^R2, etc.

In the above formulas (a), (b) and (c), examples of the group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group represented by R ²¹ etc. have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵¹ , -COOR ⁵¹ , -CO-R ⁵¹ or -SR ⁵¹ include groups in which one or more hydrogen atoms in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ² etc. have been substituted with the above groups.
Here, R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵¹ are present in the compound, they may be the same or different. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is the same as the above-mentioned hydrocarbon group having 1 to 20 carbon atoms represented by R ² , etc.
The number of carbon atoms in the group having the above substituents defines the total number of carbon atoms in the group.

In the above formulas (a), (b) and (c), examples of the group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group represented by R ²¹ etc. have been substituted with -O-, -CO-, -COO-, -OCO-, -NR ⁵² -, -NR ⁵² CO- or -S- include groups in which one or more methylene groups in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ² etc. have been 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 above-mentioned hydrocarbon group having 1 to 20 carbon atoms is the same as the above-mentioned hydrocarbon group having 1 to 20 carbon atoms represented by R ² , etc.
The number of carbon atoms in the group in which the methylene group in the above-mentioned hydrocarbon group is substituted defines the number of carbon atoms in the entire group.

In the above formulas (a), (b) and (c), 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 and R ⁴³ and R ⁴⁴ (hereinafter referred to as “R ²¹ and R ²² , etc.) are bonded to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms, examples of which include 5- to 7-membered aliphatic rings, aromatic rings and heterocyclic rings such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring and a lactam ring, as well as condensed rings such as a naphthalene ring, an anthracene ring, a fluorene ring, an acenaphthene ring, an indane ring and a tetralin ring.

Compounds in which M ¹ in the above general formula (I) is a group represented by formula (a) or formula (b) are preferred because they give cured products with excellent adhesion and heat resistance, and compounds in which M 1 is a group represented by formula (a) are more preferred because they are stable and easy to produce. In particular, compounds in which R ²¹ to R ²⁴ in formula (a) are hydrogen atoms are preferred.

Compounds in which R ²⁵ or R ²⁶ in formula (a) is an aryl group having 6 to 20 carbon atoms are preferred because they give cured products with excellent heat resistance. Compounds in which R ²⁵ or R ²⁶ in formula (a) is a phenyl group are particularly preferred because they have the above-mentioned effects, as well as excellent stability and ease of production.

That is, a compound in which M ¹ in the above general formula (I) is formula (a), R ²¹ to R ²⁴ in formula (a) are hydrogen atoms, and R ²⁵ or R ²⁶ is an aryl group having 6 to 20 carbon atoms is preferred. In particular, a compound in which M ¹ in the above general formula (I) is formula (a), R ²¹ to R ²⁴ in formula (a) are hydrogen atoms, and R ²⁵ or R ²⁶ is a phenyl group is preferred because it gives a cured product with excellent adhesion and heat resistance.

A compound in which M ¹ in the above general formula (I) is a group represented by formula (c) is preferred because it gives a cured product with excellent adhesion and heat resistance. A compound in which R ³⁷ to R ⁴⁴ in formula (c) are hydrogen atoms is particularly preferred because it is stable and easy to produce.

Examples of the above compound (I) include, but are not limited to, the following compounds (I-1) to (I-53).

In the present invention, the above compounds (I-1) and (I-44) are particularly preferred because they are highly stable, easy to produce, and give cured products with excellent heat resistance.

In the above general formulae (IIa), (IIb) and (IIc), the hydrocarbon group having ^{1 to 20 carbon atoms, the heterocyclic ring-containing group having 2 to 20 carbon atoms and the halogen atom represented by R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69} , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R 74 , R ^{75 , R 76} , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R ⁸³ and R ⁸⁴ (hereinafter referred to as "R ⁶¹ etc.") are the same as the hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic ring-containing group having 2 to 20 carbon atoms and the halogen atom represented by the above R 21 etc.

In the above general formulae (IIa), (IIb) and (IIc), examples of the group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁹¹ , -COOR ⁹¹ , -CO-R ⁹¹ or -SR ⁹¹ include groups in which one or ^more hydrogen atoms in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by the above R 2 etc. have been substituted with the above groups.
Here, R ⁹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁹¹ are present in the compound, they may be the same or different. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is the same as the above-mentioned hydrocarbon group having 1 to 20 carbon atoms represented by R ² , etc.

In the above general formulas (IIa), (IIb) and (IIc), examples of the group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group have been substituted with -O-, -CO-, -COO-, -OCO-, -NR ⁹² -, -NR ⁹² CO- or -S- include groups in which one or more methylene groups in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ² etc. have been substituted with the above groups.
Here, R ⁹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁹² are present in the compound, they may be the same or different. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms is the same as the above-mentioned hydrocarbon group having 1 to 20 carbon atoms represented by R ² , etc.

In the above general formulae (IIa), (IIb) and (IIc), examples ^of the ring ^{having 3} to ^{10 carbon atoms consisting of hydrogen atoms and carbon atoms formed by R 61 and R 62 , R 62 and R 63 , R 63 and R 64 , R 65 and R 66 , R 66 and R 67 , R 67 and R 68 , R 69 and R 70 , R 70 and R 71 , R 71} and R ⁷² , R ⁷⁴ and R ⁷⁵ , R ⁷⁷ and R 78 , R ⁷⁸ and R ⁷⁹ , R ⁷⁹ and R ⁸⁰ , R ⁸¹ and R 82 , R 82 and R ⁸³ and R 83 and R 84 bonding to each other include the above R ²¹ and R ²² , etc. are bonded to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms.

In the above general formulas (IIa), (IIb) and (IIc), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by ^Y1 , ^Y2 , ^Y3 , ^Y4 , ^Y5 and ^Y6 include groups in which two hydrogen atoms have been removed from the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 etc.

In the above general formula (IIc), examples of the aryl group having 6 to 20 carbon atoms represented by ^L1 and ^L2 include groups in which one hydrogen atom has been removed from the groups exemplified as the aryl group having 6 to 20 carbon atoms represented by ^R2, etc.

The compound in which R ⁶¹ to R ⁶⁸ in the above general formula (IIa) are hydrogen atoms, the compound in which R ⁶⁹ to R ⁷² in the above general formula (IIb) are hydrogen atoms, and the compound in which R ⁷⁷ to R ⁸⁴ in the above general formula (IIc) are hydrogen atoms are preferred because they are highly stable and easy to produce.

Compounds in which either or both of R ⁷³ and R ⁷⁴ in the above general formula (IIb) are aryl groups having 6 to 20 carbon atoms are preferred because they give cured products with excellent heat resistance. Compounds in which R ⁷³ or R ⁷⁴ is a phenyl group are particularly preferred because they are stable and easy to produce.

Compounds in which ^Y1 and ^Y2 in the above general formula (IIa), ^Y3 and ^Y4 in the above general formula (IIb), and ^Y5 and ^Y6 in the above general formula (IIc) are aryl groups having 6 to 20 carbon atoms are preferred because they give cured products with excellent heat resistance, and compounds in which Y1 and ^Y2 , Y3 and ^{Y4 ,} and ^Y5 and ^Y6 are benzene rings are more preferred, and compounds in which Y1 and ^Y2 , Y3 and Y4, and Y5 and Y6 are unsubstituted benzene rings are particularly preferred because they are stable and easy to produce.

A compound in which ^Y1 and ^Y2 in the above general formula (IIa) are bonded to each other directly or via a methylene group, -O-, or -S- is preferred because it gives a cured product having excellent heat resistance, and a compound in which ^Y1 and ^Y2 are bonded to each other via -O- is more preferred because it has excellent stability and is easy to produce.

Compounds in which L ¹ and L ² in the above general formula (IIc) are phenylene groups are preferred because they are highly stable, easy to produce, and give cured products with excellent heat resistance.

Examples of the compound (IIa) include 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis(3,4-dicarboxyphenyl)1,2-benzofluorene dianhydride, 9,9-bis(3,4-dicarboxyphenyl)2,3-benzofluorene dianhydride, 9,9-bis(3,4-dicarboxyphenyl)3,4-benzofluorene dianhydride, and spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone.

In the present invention, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone are particularly preferred because they are stable, easy to manufacture, and give cured products with excellent heat resistance.

Examples of the compound (IIb) include 1,1-bis(3,4-dicarboxyphenyl)indan dianhydride, 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindan dianhydride, 1,1-bis(3,4-dicarboxyphenyl)-3,3'-diphenylindan dianhydride, 1,1-bis(3,4-dicarboxyphenyl)-3,3'-dimethylindan dianhydride, and 1,1-bis(3,4-dicarboxyphenyl)-3,3'-methylphenylindan dianhydride.

In the present invention, 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride is particularly preferred because it is stable, easy to manufacture, and produces a cured product with excellent heat resistance.

Examples of the compound (IIc) include 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]1,2-benzofluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]2,3-benzofluorene dianhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]3,4-benzofluorene dianhydride.

In the present invention, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride is particularly preferred because it is stable, easy to manufacture, and produces a cured product with excellent heat resistance.

The compound of the present invention is a compound having a structure in which at least one selected from the above compounds (IIa), (IIb) and (IIc) is added to the above compound (I), and due to this structure, a cured product having excellent adhesion and heat resistance can be obtained.

The compound (I) can be produced by a known production method, for example, the production method described in WO 2008/139924. Specifically, it can be produced by adding acrylic acid or methacrylic acid to an epoxy compound obtained by reacting a bisphenol compound such as 1,1-bis(4-hydroxyphenyl)-3-phenylindane or 9,9-bis(4-hydroxyphenyl)fluorene with epichlorohydrin.

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

In the present invention, a structure in which 0.1 to 1.0 moles of the above compounds (IIa), (IIb) and (IIc) are added in total to 1 mole of the above compound (I) is preferred because a cured product having excellent adhesion and heat resistance can be obtained, and a structure in which 0.3 to 0.8 moles are added is particularly preferred. In other words, a structure in which 0.05 to 0.5 moles of the above compounds (IIa), (IIb) and (IIc) are added in total to 1 mole of hydroxyl groups in the above compound (I) is preferred because a cured product having excellent adhesion and heat resistance can be obtained, and a structure in which 0.15 to 0.4 moles are added is particularly preferred.

The compound of the present invention may further have a structure in which a dicarboxylic acid monoanhydride is added to the above compound (I). Such a compound is preferable because it can be made into a compound having the desired alkaline developability by adjusting the acid value.

The dicarboxylic acid monoanhydride means a compound having one structure in the molecule in which two carboxyl groups are dehydrated and condensed. The compound of the present invention having a structure in which a dicarboxylic acid monoanhydride is added to the compound (I) has excellent heat resistance and alkaline developability, so that it is preferable that the total of the compounds (IIa), (IIb) and (IIc) is added in an amount of 1 to 3 per 1 unit of dicarboxylic acid monoanhydride, and it is particularly preferable that the total of the compounds (IIa), (IIb) and (IIc) is added in an amount of 1.5 to 2.5 per 1 unit of dicarboxylic acid monoanhydride.

Examples of the dicarboxylic acid monoanhydride include succinic anhydride, maleic anhydride, trimellitic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylhimic anhydride, and methylhexahydrophthalic anhydride.
In the present invention, it is preferable to use one or more selected from succinic anhydride, 1,2,3,6-tetrahydrophthalic anhydride and hexahydrophthalic anhydride because they have excellent alkaline developability.

The reaction of adding the dicarboxylic acid monoanhydride to the compound (I) can be carried out in the same manner as the reaction of adding the compound (IIa), the compound (IIb) or the compound (IIc) to the compound (I). In addition, the reaction of adding the compound (IIa), the compound (IIb) or the compound (IIc) to the compound (I) and the reaction of adding the dicarboxylic acid monoanhydride to the compound (I) may be carried out simultaneously.

The acid value of the compound of the present invention is preferably in the range of 70 to 150 mg KOH/g, since the resulting polymerizable composition has excellent alkaline developability, and is particularly preferably in the range of 80 to 110 mg KOH/g.

The weight average molecular weight Mw of the compound of the present invention is preferably in the range of 2,000 to 15,000, since a cured product with excellent heat resistance can be obtained, and is particularly preferably 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 this increases the resolution, and is particularly preferably in the range of 1.5 to 2.5.

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

The acrylic group equivalent of the compound of the present invention is preferably within the range of 300 to 700 g/eq, since the sensitivity of the polymerizable composition containing the compound is excellent, and is particularly preferably within the range of 400 to 600.

The polymerizable composition of the present invention contains a compound (A) having a structure in which at least one selected from the compound (IIa), the compound (IIb) and the compound (IIc) is added to the compound (I), and a polymerization initiator (B).

The content of the compound (A) is preferably 10 to 70 parts by mass, and more preferably 30 to 60 parts by mass, per 100 parts by mass of the solid content of the polymerizable composition, since a cured product having excellent adhesion and heat resistance can be obtained.
The solid content of the polymerizable composition is the total amount of components excluding the solvent described below 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 in the polymerization of a compound having an ethylenically unsaturated bond, and a conventionally known compound may be used. Specifically, for example, benzoyl peroxide, 2,2'-azobisisobutyronitrile, benzophenone, phenyl biphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzil, benzil dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4'-morpholinobenzoyl)propane, 2-morpholyl-2-(4'-methylmercapto)benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl azothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl ... diethylthioxanthone, 1-chloro-4-propoxythioxanthone, nthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'-isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis(9'-acridinyl)heptane, 9-n-butyl-3,6-bis(2'-morpholinoisobutyroyl)carbazole, 2-methyl-1-[4-(methylthio)phenyl]-2 -morpholinopropan-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-butoxystyryl)-s-triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethyl Examples include rubenzphenazine, benzophenone/Michler's ketone, hexaarylbiimidazole/mercaptobenzimidazole, thioxanthone/amine, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and compounds described in JP-A-2000-80068, JP-A-2001-233842, JP-A-2005-97141, JP-T-2006-516246, Japanese Patent No. 3860170, Japanese Patent No. 3798008, and WO2006/018973.

The polymerizable composition may further contain a polymerizable compound (C) 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, methoxyethyl acrylate, dimethylaminoethyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tricyclodecane dimethylol diacrylate.

The content of the polymerizable compound (C) is preferably 5 to 80 parts by mass, and more preferably 10 to 70 parts by mass, per 100 parts by mass of the compound (A), because this increases the sensitivity of the polymerizable composition and results in a cured product with excellent chemical resistance.

The content of the polymerization initiator (B) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the compound (A) and the polymerizable compound (C) because the sensitivity of the polymerizable composition of the present invention is excellent, and more preferably 1 to 5 parts by mass.

The polymerizable composition may further contain a colorant (D). Examples of the colorant (D) include pigments and dyes. As the pigments and dyes, inorganic or organic colorants can be used. 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 inorganic or organic colorants that are insoluble in solvents, and inorganic or organic dyes that have been made into lakes.

Examples of the pigment include carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin; the above carbon black previously dispersed in a resin in a solvent and coated with 20 to 200 mg/g of resin; the above carbon black subjected to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less; and a total oxygen amount calculated from CO and _CO2 in the volatile matter at 950° C. that is greater than or equal to 100 m of surface area. ^Examples of the pigment include organic or inorganic pigments such as carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black, and perylene black, which are typified by black pigments, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, synthetic iron black, amber, and lake pigments, which are 9 mg or more per 2.
Among the above pigments, it is preferable to use a black pigment because of its high light-shielding property.

Commercially available pigments can be used as the pigments. 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.

Examples of the dyes include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthranthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, azo dyes, and metal complex compounds of cyanine dyes.

In the polymerizable composition of the present invention, the content of the colorant (D) is not particularly limited, but is preferably 10 to 500 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 10 to 200 parts by mass, relative to 100 parts by mass of the compound (A). 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 light-shielding property of the cured product of the polymerizable composition is high, which is preferable.
For example, when forming a cured product having a thickness of 1 to 3 μm, the content of the colorant (D) is not particularly limited, but is preferably 10 to 500 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 10 to 200 parts by mass, relative to 100 parts by mass of the compound (A).

A solvent can be further added to the polymerizable composition of the present invention. The solvent is a component that is liquid at 25°C under 1 atmosphere and is not classified as compound (A), polymerization initiator (B), polymerizable compound (C), or colorant (D). As the solvent, a solvent that can dissolve or disperse each of the above components (compound (A), polymerization initiator (B), polymerizable compound (C), colorant (D), etc.) can usually be used as needed. For example, ketone-based solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and 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 glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. ether ester solvents such as butyl acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; paraffin solvents such as mineral spirits, Swazol #310 (all manufactured by Cosmo Matsuyama Oil); and Solvesso #100 (all manufactured by Exxon Chemical). Agents include halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and water, and these solvents can be used alone or in combination of two or more.

Among these, ketone solvents, ester solvents and ether ester solvents, particularly cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate and propylene glycol monomethyl ether acetate, are preferred because they have good solubility for compound (A) and polymerization initiator (B).

The content of the above-mentioned solvent in the polymerizable composition of the present invention is not particularly limited, but is preferably 20 to 98% by mass, and 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 has excellent storage stability without aggregation of the colorant, and it is preferable because it is easy to control the film thickness of the cured product.

The polymerizable composition of the present invention can be applied to a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, or plastic by known means such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, or immersion. In addition, once applied to a support substrate such as a film, it can also be transferred to another support substrate, and there is no limitation on the application method.

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 or heating, since these have high curability.

Light sources used in curing the polymerizable composition of the present invention include electromagnetic wave energy having a wavelength of 2000 angstroms to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide 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. Preferred examples include ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm.

When curing by heating, one method is to pre-bake at 70-100°C for 100 seconds, remove the solvent, and then heat and cure at 150°C-250°C for 30 minutes to 1 hour. If the curing temperature is lower than 150°C, sufficient curing may not occur, and if it is 250°C or higher, the cured film may become discolored or decompose.

The polymerizable composition and cured product of the present invention can be used in a wide variety of applications, including curable paints, varnishes, curable adhesives, printed circuit boards, display devices (color filters in liquid crystal display panels for color displays in color televisions, PC monitors, mobile information terminals, digital cameras, etc., color filters for various display applications, color filters in CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, and black partition walls in organic EL), powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, 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, solder resists, and magnetic recording materials. It can be used in a variety of applications, including materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials and protective films used to form dielectric layers in the sequential lamination of printed circuit boards, and there are no particular limitations on its applications, but it is particularly suitable for use in display devices among the above applications.

The present invention will be described in more detail below by showing examples, but the present invention is not limited to these examples.

[Synthesis Example 1]
3-Phenyl-1-indanone (0.10 mol), phthalic acid (0.60 mol), 3-mercaptopropionic acid (0.010 mol), sulfuric acid (0.020 mol), and toluene (1.1 mol) were charged into a reaction vessel and heated and stirred at 80° C. for 5 hours. The reaction solution was washed with water, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product obtained was purified in a silica gel column using an ethyl acetate/hexane solvent, and further recrystallized with toluene to obtain crystals. The obtained crystals were dried at 170° C. under reduced pressure for 6 hours to obtain the target product, 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindan dianhydride.

[Example 1]
The following epoxy compound 1 (1.00 mol), acrylic acid (2.04 mol), dibutylhydroxytoluene (0.0105 mol), tetrabutylammonium chloride (0.0100 mol), and 3.26 mol of propylene glycol monomethyl ether acetate (PGMAc) were charged into a reaction vessel, stirred at 120° C. for 15 hours, and then cooled to room temperature to obtain epoxy acrylate compound 1 as a PGMAc solution.
To the obtained epoxy acrylate compound 1 solution, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (0.592 mol), 1,2,3,6-tetrahydrophthalic anhydride (0.340 mol), dibutylhydroxytoluene (0.0105 mol), tetrabutylammonium chloride (0.0100 mol) and PGMAc (2.74 mol) were added, and the mixture was stirred at 110° C. for 5 hours. The mixture was cooled to room temperature, and PGMAc (3.53 mol) was added to obtain the target compound 1 as a PGMAc solution (content: 43.3% by mass). The molecular weight of compound 1 was Mw=5800, Mn=2600, and the acid value (solid content) was 89.6 mg KOH/g.
Compound 1 has a structure in which 0.296 tetracarboxylic dianhydride and 0.170 dicarboxylic monoanhydride are added to one hydroxyl group of epoxy acrylate compound 1. Compound 1 is obtained by adding 1.74 tetracarboxylic dianhydride to 1 dicarboxylic monoanhydride in molar ratio.

[Example 2]
Compound 2 was obtained as a PGMAc solution (content: 44.2 mass%) in the same manner as in Example 1, except that 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Compound 2 had a molecular weight of Mw=5900, Mn=2500, and an acid value (solid content) of 88.5 mg KOH/g.

[Example 3]
Compound 3 was obtained as a PGMAc solution (content: 44.1 mass%) in the same manner as in Example 1, except that epoxy compound 2 was used instead of epoxy compound 1. Compound 3 had a molecular weight of Mw = 6000 and Mn = 2600, and an acid value (solid content) of 90.8 mg KOH/g.

[Example 4]
Compound 4 was obtained as a PGMAc solution (content: 44.5% by mass) in the same manner as in Example 2, except that epoxy compound 2 was used instead of epoxy compound 1. Compound 4 had a molecular weight of Mw = 5,800 and Mn = 2,500, and an acid value (solid content) of 91.2 mg KOH/g.

[Example 5]
Compound 5 was obtained as a PGMAc solution (content: 44.7% by mass) in the same manner as in Example 1, except that succinic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 5 had a molecular weight of Mw=5600 and Mn=2300, and an acid value (solid content) of 91.3 mg KOH/g.

[Example 6]
Compound 6 was obtained as a PGMAc solution (content: 44.6% by mass) in the same manner as in Example 1, except that 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and succinic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 6 had a molecular weight of Mw=5600 and Mn=2400, and an acid value (solid content) of 90.8 mg KOH/g.

[Example 7]
Compound 7 was obtained as a PGMAc solution (content: 44.6% by mass) in the same manner as in Example 3, except that succinic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 7 had a molecular weight of Mw=5600 and Mn=2400, and an acid value (solid content) of 90.8 mg KOH/g.

[Example 8]
Compound 8 was obtained as a PGMAc solution (content: 44.6% by mass) in the same manner as in Example 3, except that 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and succinic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 8 had a molecular weight of Mw=5600 and Mn=2400 and an acid value (solid content) of 90.6 mg KOH/g.

[Example 9]
Compound 9 was obtained as a PGMAc solution (content: 44.1% by mass) in the same manner as in Example 1, except that hexahydrophthalic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 9 had a molecular weight of Mw=5900 and Mn=2500, and an acid value (solid content) of 88.2 mg KOH/g.

[Example 10]
Compound 10 was obtained as a PGMAc solution (content: 44.1% by mass) in the same manner as in Example 1, except that 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and hexahydrophthalic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 10 had a molecular weight of Mw=5700 and Mn=2500 and an acid value (solid content) of 89.8 mg KOH/g.

[Example 11]
Compound 11 was obtained as a PGMAc solution (content: 44.5% by mass) in the same manner as in Example 3, except that hexahydrophthalic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 11 had a molecular weight of Mw=5600 and Mn=2400, and an acid value (solid content) of 90.5 mg KOH/g.

[Example 12]
Compound 12 was obtained as a PGMAc solution (content: 44.1% by mass) in the same manner as in Example 3, except that 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and hexahydrophthalic anhydride was used instead of 1,2,3,6-tetrahydrophthalic anhydride. Compound 12 had a molecular weight of Mw=5900 and Mn=2600 and an acid value (solid content) of 90.3 mg KOH/g.

[Example 13]
Compound 13 was obtained as a PGMAc solution (content: 44.0 mass%) in the same manner as in Example 1, except that 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Compound 13 had a molecular weight of Mw=5900, Mn=2500, and an acid value (solid content) of 81.2 mg KOH/g.

[Example 14]
Compound 14 was obtained as a PGMAc solution (content: 44.3% by mass) in the same manner as in Example 1, except that the following spirofluorene dianhydride (spiro[11H-difuro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetrone) was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Compound 14 had a molecular weight of Mw = 5500, Mn = 2300, and an acid value (solid content) of 89.0 mg KOH/g.

[Comparative Example 1]
Comparative compound 1 was obtained as a PGMAc solution (content: 44.1% by mass) in the same manner as in Example 1, except that 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. The molecular weight of comparative compound 1 was Mw = 5900, Mn = 2500, and the acid value (solid content) was 90.3 mg KOH/g.

[Comparative Example 2]
Comparative compound 2 was obtained as a PGMAc solution (content: 44.2 mass%) in the same manner as in Comparative Example 1, except that epoxy compound 2 was used instead of epoxy compound 1. Comparative compound 2 had a molecular weight of Mw = 5800 and Mn = 2600, and an acid value (solid content) of 92.8 mg KOH/g.

[Evaluation example]
To 20.3 parts of each compound obtained in the above Examples and Comparative Examples, 4.61 parts of trimethylolpropane triacrylate, 0.790 parts of NCI-831 (ADEKA Corporation) as a photopolymerization initiator, 16.9 parts of MA100 (carbon black, manufactured by Mitsubishi Chemical Corporation) as a coloring material, and 57.4 parts of PGMAc were added and thoroughly stirred to obtain a polymerizable composition.
The above polymerizable compositions were each applied onto a glass substrate and prebaked at 90° C. for 90 seconds to a thickness of about 2 μm, and then irradiated with 40 mJ/cm ² light from a high-pressure mercury lamp using a specified photomask. Next, the substrate was developed with a 2.4% TMAH aqueous solution (tetraammonium hydroxide aqueous solution) for 30 seconds and washed with water. After that, the substrate was heated at 230° C. for 30 minutes to fix the pattern, and an evaluation sample was prepared.

The evaluation samples were subjected to the following evaluations. The evaluation results are shown in Table 1.
<Adhesion>
The patterns after development were observed, and those that showed no pattern peeling even with a line width of 5 μm were rated as A, those that showed no pattern peeling even with a line width of 10 μm were rated as B, and those that showed pattern peeling even with a line width of 10 μm were rated as C. Those that showed no pattern peeling even with a small line width indicate excellent adhesion, and are therefore preferred.
<Heat resistance>
The pattern shape was observed before and after heating at 230°C for 30 minutes, and those that showed little change in shape before and after heating and maintained a rectangular shape were rated as A, those that showed a change in shape and became closer to a trapezoid were rated as B, and those that showed a large change in shape and became closer to a bowl shape were rated as C. Shapes A and B mean that the pattern shape was not melted by heating and have excellent heat resistance, and those rated as A have particularly high heat resistance.
<Sensitivity>
Development was performed at exposure doses of 40 mJ/ ^cm2 , 60 mJ/ ^cm2 , and 80 mJ/ ^cm2 , and the minimum exposure dose at which a pattern was obtained was 40 mJ/ ^cm2 , which was designated A, the minimum exposure dose at which a pattern was obtained was 60 mJ/ ^cm2 , which was designated B, and the minimum exposure dose at which a pattern was obtained was 80 mJ/ ^cm2 , which was designated C. The lower the exposure dose at which a pattern can be formed, the better the sensitivity.

From the results shown in Table 1, it was confirmed that the polymerizable composition using the compound of the present invention has good sensitivity and is particularly excellent in adhesion and heat resistance, and therefore it is possible to form an appropriate pattern shape or a fine pattern.

Claims (13)

A compound having a structure in which at least one selected from the group consisting of tetracarboxylic dianhydrides represented by the following general formulas (IIa), (IIb) and (IIc) is added to an epoxy acrylate 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 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom;
^X1 and ^X2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms;
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X ¹ and X ² may each be a group having 1 to 20 carbon atoms in which one or more methylene groups in a hydrocarbon group are substituted with -O- or -S-, provided that no oxygen is adjacent to them;
^M1 represents a group represented by the following formula (a) or (b):

(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 and R ³⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom;
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 and R ³⁶ may each represent a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁵¹ , -COOR ⁵¹ , -CO-R ⁵¹ or -SR ⁵¹ ;
R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁵¹ are present in the compound, 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 and R ³⁶ may each be a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, -CO-, -COO-, -OCO-, -NR ⁵² -, -NR ⁵² CO- or -S-;
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;
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 , and R ³¹ and R ³² may be bonded to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms.
In the formula, * means that the groups represented by (a) and (b ) are bonded to the adjacent group at the * portion.

(In the formula, R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom;
R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ may each be a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the hydrocarbon group have been substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ⁹¹ , -COOR ⁹¹ , -CO-R ⁹¹ or -SR ⁹¹ ;
R ⁹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁹¹ are present in the compound, they may be the same or different;
R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ may each be a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, -CO-, -COO-, -OCO-, -NR ⁹² -, -NR ⁹² CO- or -S-;
R ⁹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ⁹² are present in the compound, they may be the same or different;
R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁹ and R ⁷⁰ , R ⁷⁰ and R ⁷¹ , R ⁷¹ and R ⁷² , R ⁷⁴ and R ⁷⁵ , R ⁷⁷ and R ⁷⁸ , R ⁷⁸ and R ⁷⁹ , R ⁷⁹ and R ⁸⁰ , R ⁸¹ and R ⁸² , R ⁸² and R ⁸³ , and R ⁸³ and R ⁸⁴ may be bonded to each other to form a ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms;
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ each independently represent a hydrocarbon group having 1 to 20 carbon atoms;
Y ¹ and Y ² may be bonded to each other directly or via a methylene group, -O- or -S-;
^L1 and ^L2 each independently represent an aryl group having 6 to 20 carbon atoms. The compound according to claim 1, wherein Y ¹ and Y ² in formula (IIa), Y ³ and Y ⁴ in formula (IIb), and Y ⁵ and Y ⁶ in formula (IIc) are an aryl group having 6 to 20 carbon atoms. The compound according to claim 1 or 2 , which has a structure in which the tetracarboxylic dianhydride represented by the general formula (IIa) is added to the epoxy acrylate compound represented by the general formula (I). The compound according to claim 1 or 2 , having a structure in which the tetracarboxylic dianhydride represented by the general formula (IIb) is added to the epoxy acrylate compound represented by the general formula (I). The compound according to claim 1 or 2 , which has a structure in which the tetracarboxylic dianhydride represented by the general formula (IIc) is added to the epoxy acrylate compound represented by the general formula (I). The compound according to any one of claims 1 to 5 , further comprising a structure in which a dicarboxylic acid monoanhydride is added to the epoxy acrylate compound represented by the general formula (I). A polymerizable composition comprising the compound (A) according to any one of claims 1 to 6 , and a polymerization initiator (B). The polymerizable composition according to claim 7 , further comprising a polymerizable compound (C) other than the compound (A). The polymerizable composition according to claim 7 or 8 , further comprising a colorant (D). A cured product of the polymerizable composition according to any one of claims 7 to 9 . A display device comprising the cured product according to claim 10 . A method for producing the compound according to any one of claims 1 to 6, comprising a step of reacting an epoxy acrylate compound represented by the general formula ( I ) with a tetracarboxylic dianhydride represented by the general formula (IIa), (IIb) or (IIc). A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to any one of claims 7 to 9 with light or heating.