Compound, polymerizable composition and cured product

Abstract

To provide a compound useful as a polymerizable component of a polymerizable composition having excellent adhesion and heat resistance and providing a proper pattern shape and a fine pattern, and a polymerizable composition including the compound.SOLUTION: A compound has a structure in which a tetracarboxylic acid dianhydride having a fluorene structure or an indan structure is added to an epoxy acrylate compound represented by general formula (I) (where R1 and R10 independently represent a hydrogen atom or a methyl group, R2-R9 independently represent a hydrogen atom, a C1 to 20 hydrocarbon group, or a halogen atom, X1 and X2 independently represent a C1 to 20 divalent hydrocarbon group, M1 is a group having a fluorene structure or an indan structure).SELECTED DRAWING: None

Description

[Technical field]

[0001] 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. [Background technology]

[0002] 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 irradiation with ultraviolet light or electron beams, and is therefore used in photocurable inks, photosensitive printing plates, printed wiring boards, various photoresists, etc. Recently, with the progress of making electronic devices lighter, thinner, shorter, smaller, and more highly functional, there is a demand for an alkali-developable photosensitive resin composition that can form fine patterns with high accuracy.

[0003] 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. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 05-339356 [Patent Document 2] JP 2006-003860 A [Patent Document 3] JP 2012-241083 A [Patent Document 4] JP 2017-090491 A [Patent Document 5] JP 2017-090493 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a compound which is excellent in adhesion and heat resistance and is useful as a polymerizable component of a polymerizable composition which can obtain an appropriate pattern shape or a fine pattern, and a polymerizable composition using the compound. [Means for solving the problem]

[0006] As a result of intensive research, the present inventors have found 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 have arrived at the present invention.

[0007] That is, the present invention relates to a compound having a structure in which at least one selected from tetracarboxylic acid 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).

[0008] [ka] (In the formula, R 1 and R 10 each independently represents 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 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; X 1 and X 2 each independently represents 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 be a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O- or -S-, provided that no oxygen is adjacent to the methylene group; M 1 represents a group represented by the following formula (a), (b) or (c).

[0009] [ka] (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 44each independently represents 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 is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 51 , -COOR 51 , -CO-R 51 or -SR 51 may be a group having 1 to 20 carbon atoms substituted with R 51 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 51 When multiple are present, 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 , R41 , R 42 , R 43 and R 44 means that one or more of the methylene groups in the hydrocarbon group are -O-, -CO-, -COO-, -OCO-, -NR 52 -, -NR 52 may be a group having 1 to 20 carbon atoms substituted by -CO- or -S-, R 52 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 52 When multiple are present, 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 the adjacent group at the * portion.

[0010] [ka] (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 represents 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 is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 91 , -COOR 91 , -CO-R 91 or -SR 91 may be a group having 1 to 20 carbon atoms substituted with R 91 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 91 When multiple are present, they may be the same or different, R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R67 , 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 means that one or more of the methylene groups in the hydrocarbon group are -O-, -CO-, -COO-, -OCO-, -NR 92 -, -NR 92 may be a group having 1 to 20 carbon atoms substituted by -CO- or -S-, R 92 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 82 When multiple are present, 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 84may be bonded to each other to form a ring having 3 to 10 carbon atoms and composed of hydrogen atoms and carbon atoms, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 each independently represents 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-; L 1 and L 2 each independently represents an aryl group having 6 to 20 carbon atoms.

[0011] The present invention also relates to a polymerizable composition containing the above compound (A) and a polymerization initiator (B). Effect of the Invention

[0012] The polymerizable composition containing the compound of the present invention can give a cured product having excellent sensitivity, adhesion and heat resistance, and therefore can easily form a suitable pattern shape or a fine pattern. Therefore, the composition is particularly useful as a polymerizable composition for a solder resist or a black matrix. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 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 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)"), each of which is represented by the above general formula (I), is further added to an epoxy acrylate compound 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) (hereinafter referred to as "compound (I)").

[0014] In the above general formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 (Hereinafter referred to as “R 2 The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is not particularly limited as long as it is a group having 1 to 20 carbon atoms and consisting of carbon atoms and hydrogen atoms, but is preferably 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, because the sensitivity of the polymerizable composition of the present invention is excellent, and is particularly preferably 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.

[0015] 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 groups.

[0016] Examples of the alkenyl group having 2 to 20 carbon atoms include linear and cyclic alkenyl groups such as vinyl group, 2-propenyl group, 3-butenyl group, 2-butenyl group, 4-pentenyl group, 3-pentenyl group, 2-hexenyl group, 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-cyclohexenyl group, 2,5-cyclohexadienyl-1-methyl group, and 4,8,12-tetradecatrienyl allyl group.

[0017] The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples thereof 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.

[0018] The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted 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 aryl groups include a 3-cyclopropylpropyl group, a 3-cyclohexylpropyl group, a 3-cycloheptylpropyl group, a 3-cyclooctylpropyl group, a 3-cyclononylpropyl group, a 3-cyclodecylpropyl group, a 4-cyclobutylbutyl group, a 4-cyclopentylbutyl group, a 4-cyclohexylbutyl group, a 4-cycloheptylbutyl group, a 4-cyclooctylbutyl group, a 4-cyclononylbutyl group, a 4-cyclodecylbutyl group, a 3-3-adamantylpropyl group, and a decahydronaphthylpropyl group.

[0019] 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, as well as groups in which these groups are substituted with one or more of the alkyl groups, the alkenyl groups, carboxyl groups, halogen atoms, or the like, such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, and 2,4,6-trimethylphenyl.

[0020] The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of an alkyl group is replaced with 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 a hydrogen atom of an alkyl group is replaced with an aryl group. Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0021] In the above general formula (I), R 2 As the group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with -O- or -S- under the condition that no oxygen atom is adjacent to the methylene group, the above-mentioned R 2 and the like, in which a methylene group is substituted with -O- or -S-, provided that no oxygen atom is adjacent to the methylene group.

[0022] In the above general formula (I), R 2 Examples of groups in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms 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.

[0023] In the above general formula (I), R 2 Examples of the group in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms is substituted with -S- include groups in which a methylene group in the above-mentioned 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.

[0024] In the above general formula (I), R 2 Examples of the halogen atom represented by the formula (I) include fluorine, chlorine, bromine, and iodine.

[0025] In the above general formula (I), X 1 and X 2 As the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the above R 2 and the like, and divalent groups in which one hydrogen atom has been removed from the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms.

[0026] In the above general formula (I), X 1 and X 2 As the group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with -O- or -S- under the condition that no oxygen atom is adjacent to the methylene group, the above X 1 and X 2 and methylene groups in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms and represented by the formula: 2 "A group in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms is replaced with -O- under the condition that no oxygen atom is adjacent to the methylene group in the hydrocarbon group having 1 to 20 carbon atoms, represented by the formula (I) or the like" and the above "R 2 and the like, in which a methylene group in a hydrocarbon group having 1 to 20 carbon atoms is substituted with -S-, and the like.

[0027] R in the above general formula (I) 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 However, a compound in which each independently is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms is preferred because it has excellent stability, the sensitivity of a polymerizable composition containing the compound is excellent, and it is easy to produce. 2 , R 3 , R 4 , R 5 , R6 , R 7 , R 8 and R 9 is preferably a hydrogen atom or a methyl group.

[0028] In addition, X in the above general formula (I) 1 and X 2 Compounds in which is a methylene group are preferred because they are highly stable and easy to produce.

[0029] In the above formulas (a), (b) and (c), 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 The hydrocarbon group having 1 to 20 carbon atoms and the halogen atom represented by the above R 2 and the like are the same as the hydrocarbon group having 1 to 20 carbon atoms and the halogen atom.

[0030] In the above formulas (a), (b) and (c), R 21The heterocycle-containing group having 2 to 20 carbon atoms, represented by the formula (I) or (II), 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.

[0031] [ka] (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 group represented by these formulas is bonded to an adjacent group at the * portion.)

[0032] 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-. where R' 1 and R″ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 51 and R 52 When a plurality of R are present, they may be the same or different. 2 and the like.

[0033] In the above formulas (a), (b) and (c), R 21 In the hydrocarbon group, one or more of the hydrogen atoms are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 51 , -COOR 51 , -CO-R 51 or -SR 51 The group having 1 to 20 carbon atoms substituted with the above R 2 and the like, 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-mentioned groups, are substituted. Here, R 51 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 51 When a plurality of R are present, they may be the same or different. 2 and the like. The number of carbon atoms in the group having the above substituents defines the total number of carbon atoms in the group.

[0034] In the above formulas (a), (b) and (c), R 21 In the hydrocarbon group, one or more of the methylene groups are represented by -O-, -CO-, -COO-, -OCO-, -NR 52 -, -NR 52 The group having 1 to 20 carbon atoms substituted with -CO- or -S- includes the above-mentioned R 2 and the like, in which one or more methylene groups in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms, such as those represented by the above-mentioned groups, are substituted. Here, R 52 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 52 When a plurality of R are present, they may be the same or different. 2 and the like. 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.

[0035] 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 Examples of the ring having 3 to 10 carbon atoms composed of hydrogen atoms and carbon atoms formed by bonding together 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.

[0036] M in the above general formula (I) 1 Compounds in which R 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 R is a group represented by formula (a) are more preferred because they are stable and easy to produce. 21 ~R 24 is a hydrogen atom.

[0037] In addition, R in formula (a) 25 or R 26 A compound in which R is an aryl group having 6 to 20 carbon atoms is preferred because it gives a cured product with excellent heat resistance. 25 or R 26Compounds in which is a phenyl group are particularly preferred because they have the above effects, as well as excellent stability and ease of production.

[0038] That is, M in the above general formula (I) 1 is formula (a), and R in formula (a) 21 ~R 24 is a hydrogen atom, and R 25 or R 26 is an aryl group having 6 to 20 carbon atoms. 1 is formula (a), and R in formula (a) 21 ~R 24 is a hydrogen atom, and R 25 or R 26 A compound in which R is a phenyl group is preferred since it gives a cured product having excellent adhesion and heat resistance.

[0039] M in the above general formula (I) 1 A compound in which R is a group represented by formula (c) is preferred because it gives a cured product having excellent adhesion and heat resistance. 37 ~R 44 Compounds in which is a hydrogen atom are particularly preferred because they are highly stable and easy to produce.

[0040] Examples of the compound (I) include the following compounds (I-1) to (I-53), but the compound (I) is not limited to these compounds.

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] In the present invention, the above compounds (I-1) and (I-44) are particularly preferred since they are highly stable, can be easily produced, and give cured products having excellent heat resistance.

[0047] In the above general formulae (IIa), (IIb) and (IIc), 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 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 and the like, a hydrocarbon group having 1 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, and a halogen atom.

[0048] In the above general formulae (IIa), (IIb) and (IIc), one or more of the hydrogen atoms in the hydrocarbon group may be replaced by a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR 91 , -COOR 91 , -CO-R 91 or -SR 91The group having 1 to 20 carbon atoms substituted with the above R 2 and the like, 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-mentioned groups, are substituted. Here, R 91 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 91 When a plurality of R are present, they may be the same or different. 2 and the like.

[0049] In the above general formulae (IIa), (IIb) and (IIc), one or more of the methylene groups in the hydrocarbon group are -O-, -CO-, -COO-, -OCO-, -NR 92 -, -NR 92 The group having 1 to 20 carbon atoms substituted with -CO- or -S- includes the above-mentioned R 2 and the like, in which one or more methylene groups in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms, such as those represented by the above-mentioned groups, are substituted. Here, R 92 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 92 When a plurality of R are present, they may be the same or different. 2 and the like.

[0050] In the above general formulae (IIa), (IIb) and (IIc), 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 , R71 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 However, the ring having 3 to 10 carbon atoms and consisting of hydrogen atoms and carbon atoms formed by bonding together is not limited to 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.

[0051] In the above general formulae (IIa), (IIb) and (IIc), Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 The hydrocarbon group having 1 to 20 carbon atoms represented by the above R 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms include those groups in which two hydrogen atoms have been removed, such as those represented by the above-mentioned examples.

[0052] In the above general formula (IIc), L 1 and L 2 The aryl group having 6 to 20 carbon atoms represented by the above R 2 Examples of the aryl group having 6 to 20 carbon atoms include those in which one hydrogen atom has been removed from the groups exemplified as the aryl group having 6 to 20 carbon atoms, such as those represented by the above formulae.

[0053] R in the above general formula (IIa) 61 ~R 68 is a hydrogen atom, 69 ~R 72 is a hydrogen atom, and 77 ~R 84 Compounds in which is a hydrogen atom are preferred because they are highly stable and easy to produce.

[0054] R in the above general formula (IIb) 73 and R 74 A compound in which either or both of R are aryl groups having 6 to 20 carbon atoms is preferred because it gives a cured product with excellent heat resistance. 73 or R 74 Compounds in which is a phenyl group are particularly preferred because of their excellent stability and ease of production.

[0055] Y in the above general formula (IIa) 1 and Y 2 Y in the above general formula (IIb) 3 and Y 4 and Y in the above general formula (IIc) 5 and Y 6 Compounds in which Y is an aryl group having 6 to 20 carbon atoms are preferred because they give cured products with excellent heat resistance. 1 and Y 2 , Y 3 and Y 4 , and Y 5 and Y 6 Compounds in which R is a benzene ring are more preferred, and compounds in which R is an unsubstituted benzene ring are particularly preferred because of their excellent stability and ease of production.

[0056] Y in the above general formula (IIa) 1 and Y 2 A compound in which Y is bonded to each other directly or via a methylene group, -O- or -S- is preferred because it gives a cured product with excellent heat resistance. 1 and Y 2 However, a compound in which the two are bonded to each other via -O- is more preferred because it is more stable and easier to produce.

[0057] L in the above general formula (IIc) 1 and L 2 However, compounds having a phenylene group are preferred because they are stable, easy to produce, and give cured products with excellent heat resistance.

[0058] 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.

[0059] 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 produce, and give cured products with excellent heat resistance.

[0060] 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.

[0061] In the present invention, 1,1-bis(3,4-dicarboxyphenyl)-3-phenylindane dianhydride is particularly preferred because it has excellent stability, is easy to produce, and gives a cured product with excellent heat resistance.

[0062] 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.

[0063] In the present invention, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride is particularly preferred because it has excellent stability, is easy to produce, and gives a cured product with excellent heat resistance.

[0064] The compound of the present invention is a compound having a structure in which at least one selected from the above-mentioned compound (IIa), compound (IIb) and compound (IIc) is added to the above-mentioned compound (I). Due to this structure, a cured product having excellent adhesion and heat resistance can be obtained.

[0065] The compound (I) can be produced by a known production method, for example, the production method described in International Publication No. 2008 / 139924. Specifically, the compound 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-phenylindan or 9,9-bis(4-hydroxyphenyl)fluorene with epichlorohydrin.

[0066] 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 the hydroxyl group in compound (I) and the 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 general term for reaction products.

[0067] 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 excellent in 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 the hydroxyl group in the above compound (I) is preferred because a cured product excellent in adhesion and heat resistance can be obtained, and a structure in which 0.15 to 0.4 moles are added is particularly preferred.

[0068] The compound of the present invention may further have a structure in which a dicarboxylic acid monoanhydride is added to the above-mentioned 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.

[0069] The dicarboxylic acid monoanhydride means a compound having one structure in the molecule formed by dehydration condensation of two carboxyl groups. The compound of the present invention having a structure in which a dicarboxylic acid monoanhydride is added to the above compound (I) has excellent heat resistance and alkaline developability, and therefore, it is preferable that the above compounds (IIa), (IIb) and (IIc) are added in an amount such that the total of 1 to 3 parts by weight of the compound (IIa), (IIb) and (IIc) is added to 1 part by weight of the dicarboxylic acid monoanhydride, and it is particularly preferable that the above compounds (IIa), (IIb) and (IIc) are added in an amount such that the total of 1.5 to 2.5 parts by weight of the compound (IIa), (IIb) and (IIc) is added to 1 part by weight of the dicarboxylic acid monoanhydride.

[0070] 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.

[0071] 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). 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.

[0072] The acid value of the compound of the present invention is preferably in the range of 70 to 150 mg·KOH / g, and particularly preferably in the range of 80 to 110 mg·KOH / g, in order to provide an excellent alkaline developability of the resulting polymerizable composition.

[0073] The weight average molecular weight Mw of the compound of the present invention is preferably in the range of 2,000 to 15,000, in order to obtain a cured product having excellent heat resistance, and is particularly preferably in the range of 3,000 to 10,000.

[0074] The molecular weight distribution (Mw / Mn) of the compound of the present invention is preferably in the range of 1.0 to 3.0, since this leads to high resolution, and is particularly preferably in the range of 1.5 to 2.5.

[0075] The weight average molecular weight and the molecular weight distribution can be calculated from a calibration curve prepared by performing GPC measurement of the polymer using, for example, a GPC device (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℃

[0076] The acrylic group equivalent of the compound of the present invention is preferably within the range of 300 to 700 g / eq, and particularly preferably 400 to 600, since the polymerizable composition containing the compound has excellent sensitivity.

[0077] The polymerizable composition of the present invention contains compound (A) having a structure in which at least one selected from compound (IIa), compound (IIb), and compound (IIc) is added to compound (I), and a polymerization initiator (B).

[0078] 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.

[0079] Since the compound (A) is a polymerizable compound having an ethylenically unsaturated bond, the polymerization initiator (B) may be any radical initiator used for 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 a 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 of the compounds include rubenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the compounds described in JP-A Nos. 2000-80068, 2001-233842, 2005-97141, JP-T No. 2006-516246, Japanese Patent No. 3860170, 3798008, and WO2006 / 018973.

[0080] 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.

[0081] 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), since this increases the sensitivity of the polymerizable composition and gives a cured product with excellent chemical resistance.

[0082] The content of the polymerization initiator (B) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass in total of the compound (A) and the polymerizable compound (C) in order to provide an excellent sensitivity of the polymerizable composition of the present invention, and more preferably 1 to 5 parts by mass.

[0083] The polymerizable composition may further contain a colorant (D). Examples of the colorant (D) include pigments and dyes. As the pigments and dyes, inorganic colorants or organic colorants 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 inorganic or organic colorants that are insoluble in a solvent, and inorganic or organic dyes that have been made into lakes.

[0084] 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; carbon black having a total oxygen content calculated from CO and CO2 in the volatile matter at 950°C of 100% or less of surface area; 2 Examples of organic or inorganic pigments include 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, as well as black pigments, such as 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. Among the above pigments, it is preferable to use a black pigment because of its high light-shielding property.

[0085] As the pigment, commercially available products can 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.

[0086] Examples of the dye 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.

[0087] 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).

[0088] 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 atmospheric pressure and is not classified as the compound (A), the polymerization initiator (B), the polymerizable compound (C), or the colorant (D). As the solvent, a solvent that can dissolve or disperse each of the above components (compound (A), the polymerization initiator (B), the polymerizable compound (C), the colorant (D), etc.) can usually be used as necessary.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). 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.

[0089] Among these, ketone-based solvents, ester-based solvents and ether ester-based solvents, in particular cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate and propylene glycol monomethyl ether acetate, are preferred because they have good solubility for the compound (A) and the polymerization initiator (B).

[0090] 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 has excellent storage stability without aggregation of the colorant, and it is easy to control the film thickness of the cured product, which is preferable.

[0091] The polymerizable composition of the present invention can be applied onto a supporting substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, etc., by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing methods, immersion, etc. In addition, after being applied onto a supporting substrate such as a film, it can also be transferred onto another supporting substrate, and there is no limitation on the application method.

[0092] The cured product of the present invention means a product obtained by polymerizing the polymerizable composition. The polymerization method is not particularly limited, but it is preferable to polymerize the composition by either light irradiation or heating, since these methods have high curability.

[0093] Examples of light sources used when 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, and the like, 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, and the like that emit light with a wavelength of 300 to 450 nm.

[0094] When curing by heating, a method of pre-baking at 70 to 100° C. for 100 seconds, removing the solvent, and then curing by heating for 30 minutes to 1 hour at 150 to 250° C. If the curing temperature is lower than 150° C., sufficient curing may not occur, and if it is higher than 250° C., coloration or decomposition of the cured film may occur.

[0095] 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 electric and electronic components, solder resists, and magnetic recording materials. The photoresist composition 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 in forming dielectric layers in the sequential lamination of printed circuit boards, and there are no particular limitations on the applications. However, among the above applications, the photoresist composition can be particularly suitably used in display devices. EXAMPLES

[0096] The present invention will be described in more detail below with reference to examples, but the present invention will not be limited to these examples. It is not more limited.

[0097] [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. After washing the reaction solution with water, the solvent was distilled off under reduced pressure to obtain a crude product. The crude product obtained was purified on 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.

[0098] [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 and 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 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 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 dianhydrides and 0.170 dicarboxylic monoanhydrides are added to one hydroxyl group of epoxy acrylate compound 1. Compound 1 is obtained by adding 1.74 tetracarboxylic dianhydrides to 1 dicarboxylic monoanhydride in molar ratio.

[0099] [ka]

[0100] [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-phenylindan dianhydride was used instead of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. The molecular weight of compound 2 was Mw=5900, Mn=2500, and the acid value (solid content) was 88.5 mg KOH / g.

[0101] [Example 3] Compound 3 was obtained as a PGMAc solution (content: 44.1% by 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, Mn = 2600, and an acid value (solid content) of 90.8 mg KOH / g.

[0102] [ka]

[0103] [Example 4] Compound 4 was obtained as a PGMAc solution (content: 44.5 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 = 5800, Mn = 2500, and an acid value (solid content) of 91.2 mg KOH / g.

[0104] [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, Mn = 2300, and an acid value (solid content) of 91.3 mg KOH / g.

[0105] [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. The molecular weight of compound 6 was Mw=5600, Mn=2400, and the acid value (solid content) was 90.8 mg KOH / g.

[0106] [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, Mn = 2400, and an acid value (solid content) of 90.8 mg KOH / g.

[0107] [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. The molecular weight of compound 8 was Mw=5600, Mn=2400, and the acid value (solid content) was 90.6 mg KOH / g.

[0108] [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, Mn = 2500, and an acid value (solid content) of 88.2 mg KOH / g.

[0109] [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-phenylindan 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, Mn=2500, and an acid value (solid content) of 89.8 mg KOH / g.

[0110] [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, Mn = 2400, and an acid value (solid content) of 90.5 mg KOH / g.

[0111] [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-phenylindan 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, Mn=2600, and an acid value (solid content) of 90.3 mg KOH / g.

[0112] [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. The molecular weight of compound 13 was Mw=5900, Mn=2500, and the acid value (solid content) was 81.2 mg KOH / g.

[0113] [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. The molecular weight of compound 14 was Mw=5500, Mn=2300, and the acid value (solid content) was 89.0 mg KOH / g.

[0114] [ka]

[0115] [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.

[0116] [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, Mn = 2600, and an acid value (solid content) of 92.8 mg KOH / g.

[0117] [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 exposed to a high-pressure mercury lamp at 40 mJ / cm using a specified photomask. 2 The pattern was then fixed by heating at 230°C for 30 minutes to prepare a sample for evaluation.

[0118] 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. Patterns that did not peel off 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 more trapezoidal were rated as B, and those that showed a large change in shape and became more bowl-like were rated as C. Patterns rated as A or B mean that the pattern shape did not melt due to heating and have excellent heat resistance, with those rated as A being particularly heat resistant. <Sensitivity> Exposure dose 40mJ / cm 2 , 60mJ / cm 2 and 80 mJ / cm 2 The minimum exposure required to obtain a pattern was 40 mJ / cm 2 A: Minimum exposure is 60 mJ / cm 2B, minimum exposure 80mJ / cm 2 The one that can form a pattern with a smaller amount of exposure is rated as C. The lower the amount of exposure, the better the sensitivity.

[0119] [Table 1]

[0120] 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

1. 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). 【Chemistry 1】 (In the formula, R １ and R １０ each independently represents 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 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; X １ and X ２ each independently represents 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 be a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O- or -S-, provided that no oxygen is adjacent to them, M １ represents a group represented by the following formula (a) or (b): 【Chemistry 2】 (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 heterocyclic ring-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 is a hydrocarbon group in which one or more of the hydrogen atoms are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ５１ , -COOR ５１ , -CO-R ５１ Or -SR ５１ may be a group having 1 to 20 carbon atoms substituted with R ５１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ５１ When multiple are present, 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 is a hydrocarbon group in which one or more methylene groups are -O-, -CO-, -COO-, -OCO-, -NR ５２ --, --NR ５２ may be a group having 1 to 20 carbon atoms substituted by -CO- or -S-, R ５２ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ５２ When multiple are present, 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. 【Chemistry 3】 (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 represents 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 is a group in which one or more of the hydrogen atoms in the hydrocarbon group are replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR ９１ , -COOR ９１ , -CO-R ９１ Or -SR ９１ may be a group having 1 to 20 carbon atoms substituted with R ９１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ９１ When multiple are present, 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 One or more methylene groups in the hydrocarbon group are -O-, -CO-, -COO-, -OCO-, -NR ９２ --, --NR ９２ may be a group having 1 to 20 carbon atoms substituted by -CO- or -S-, R ９２ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ９２ When multiple are present, 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 composed of hydrogen atoms and carbon atoms, Y １ , Y ２ , Y ３ , Y ４ , Y ５ and Y ６ each independently represents 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—; L １ and L ２ each independently represents an aryl group having 6 to 20 carbon atoms.

2. Y in the above formula (IIa) １ and Y ２ , Y in the above formula (IIb) ３ and Y ４ And Y in the above formula (IIc) ５ and Y ６ The compound according to claim 1, wherein is an aryl group having 6 to 20 carbon atoms.

3. 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).

4. 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).

5. 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).

6. The compound according to any one of claims 1 to 5, further having a structure in which a dicarboxylic acid monoanhydride is added to the epoxy acrylate compound represented by the general formula (I) above.

7. A polymerizable composition comprising the compound (A) according to any one of claims 1 to 6, and a polymerization initiator (B).

8. The polymerizable composition according to claim 7 , further comprising a polymerizable compound (C) other than the compound (A).

9. The polymerizable composition according to claim 7 or 8, further comprising a colorant (D).

10. A cured product of the polymerizable composition according to any one of claims 7 to 9.

11. A display device comprising the cured product according to claim 10.

12. A method for producing the compound according to any one of claims 1 to 6, comprising reacting an epoxy acrylate compound represented by the general formula (I) with a tetracarboxylic dianhydride represented by the general formula (IIa), (IIb) or (IIc).

13. A method for producing a cured product, comprising a step of irradiating or heating the polymerizable composition according to any one of claims 7 to 9.

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