Compound, polymerizable composition, cured product, and method for producing the cured product

Abstract

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

Description

[Technical field]

[0001] The present invention relates to a compound having a structure in which an acid anhydride having a polymerizable group is added to a compound having a structure in which acrylic acid or methacrylic acid is added to an epoxy compound having a specific structure. [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] The above-mentioned known alkali-developable photosensitive resin compositions are insufficient in terms of sensitivity, resolution, adhesion, etc., and it has been difficult to obtain an appropriate pattern shape or a fine pattern.

[0006] An object of the present invention is to provide a compound useful as a polymerizable component of a highly sensitive polymerizable composition, and a polymerizable composition using said compound. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that the above object can be achieved by a compound having a structure in which an acid anhydride having a polymerizable group is added to an epoxy acrylate compound having a structure in which acrylic acid or methacrylic acid is added to an epoxy compound having a specific structure, and have arrived at the present invention.

[0008] That is, the present invention relates to a compound having a structure in which an acid anhydride having a polymerizable group is added to a compound represented by the following general formula (I).

[0009] [ka] (In the formula, R 1 and R 10each 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 halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which one or more methylene groups in a hydrocarbon group are substituted with -O-, X 1 and X 2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, M 1 represents a group represented by the following formula (a), (b), (c) or (d).

[0010] [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 , R 44 , R 45 , R 46 , R 47 , R 48 and R 49each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>, <Group A>: -O-, -CO-, -COO-, -OCO-, -NR 51 -, -NR 51 CO-, -S- R 51 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 and R 49 indicates that one or more hydrogen atoms in the hydrocarbon group are halogen atoms, cyano groups, nitro groups, hydroxyl groups, -OR 52 , -COOR 52 , -CO-R 52 or -SR 52 may be a group having 1 to 20 carbon atoms substituted with 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 , R 43 and R 44 , R 45 and R 46 , R 46 and R 47 , R 47 and R 48 and R 48 and R 49 may be bonded to each other to form a ring having 3 to 10 carbon atoms and composed of hydrogen atoms and carbon atoms, Cy represents a cycloalkyl group having 3 to 10 carbon atoms; * indicates the site where the groups represented by (a), (b), (c), and (d) are bonded to the adjacent group.)

[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 has high sensitivity. [Brief description of the drawings]

[0013] [Figure 1] 1(a) and (b) are diagrams showing the junction angle (taper angle) between a pattern and a substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] 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 an acid anhydride having a polymerizable group (hereinafter referred to as "compound (II)") is added to an epoxy acrylate compound (hereinafter referred to as "compound (I)") having a structure in which acrylic acid or methacrylic acid is added to an epoxy compound having a specific structure represented by the above general formula (I).

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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 replaced with -O- under the condition that no oxygen atom is adjacent, the above-mentioned R 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms include those in which a methylene group in the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms, such as those represented by the above, is substituted with -O-, provided that no oxygen atom is adjacent to the methylene group.

[0023] In the above general formula (I), R 2 Examples of groups having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with -O-, provided that the oxygen atoms are not adjacent to each other, such as those represented by the following formula (1), 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.

[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 2The 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- under the condition that no oxygen atom is adjacent to the methylene group, the above X 1 and X 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms and represented by the formula: 2 and the like, and divalent groups obtained by removing one hydrogen atom from the groups exemplified as "a group having 1 to 20 carbon atoms in which a methylene group in a hydrocarbon group is substituted with -O-, provided that no oxygen atoms are adjacent to each other."

[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 , R 6 , R 7 , R 8 and R 9 is a hydrogen atom.

[0028] In addition, X in the above general formula (I) 1 and X 2However, compounds having an alkylene group of 1 to 20 carbon atoms are preferred because they are stable and easy to produce, with alkylene groups having 1 to 4 carbon atoms being more preferred, and a methylene group being particularly preferred.

[0029] In the above formulas (a), (b), (c) and (d), R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 and R 49 (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), (c) and (d), R 21 The heterocyclic group, represented by the following formula: means a group in which one hydrogen atom has been removed from a heterocyclic compound.

[0031] The heterocyclic group is not particularly limited, but 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.

[0032] In the above formulas (a), (b), (c) and (d), R 21 The heterocyclic ring-containing group having 3 to 20 carbon atoms, represented by the following formula (I) or (II), means a group in which a heterocyclic group and a group other than a heterocyclic group are bonded to each other.

[0033] Examples of the group other than the heterocyclic group include a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms include the above-mentioned R 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms, represented by the above formulae, include divalent groups having a predetermined number of carbon atoms obtained by removing one hydrogen atom from the groups exemplified above.

[0034] The group other than the heterocyclic group may be a group in which a hydrogen atom in the above-mentioned hydrocarbon group having 1 to 6 carbon atoms is substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR', -COOR', -CO-R', -SR', or the like, or a group in which a methylene group in the hydrocarbon group is substituted with -O-, -CO-, -COO-, -OCO-, -NR"-, -NR"CO-, -S-, or the like. Here, R' and R" represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R' and R" are present in the compound, they may be the same or different. The hydrocarbon group having 1 to 20 carbon atoms is 2and the like.

[0035] Specific examples of the heterocyclic ring-containing group having 3 to 20 carbon atoms, including substituents, include groups having the following structures.

[0036] [ka]

[0037] In the above formulae, R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents an alkylene group having 1 to 6 carbon atoms, a group in which a hydrogen atom in the alkylene group is substituted with a halogen atom, a cyano group, a nitro group, a hydroxyl group, -OR', -COOR', -CO-R' or -SR', or a group in which a methylene group in the alkylene group is substituted with -O-, -CO-, -COO-, -OCO-, -NR"-, -NR"CO- or -S-. * in the formulae means that the group represented by these formulas is bonded to an adjacent group at the * portion. Here, R' and R" represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R' and R" are present in the compound, they may be the same or different. The hydrocarbon group having 1 to 20 carbon atoms is 2 and the like.

[0038] In the above formulas (a), (b), (c) and (d), R 21 One or more 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 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, are substituted with the above groups. Here, R 51 represents a hydrocarbon group having 1 to 20 carbon atoms, and R51 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.

[0039] In the above formulas (a), (b), (c) and (d), R 21 At least one of the methylene groups in the hydrocarbon group is -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, are substituted with the above groups. 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.

[0040] In the above formulas (a), (b), (c) and (d), R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 29 and R 30 , R 30 and R 31 , R 31 and R 32 , R 37 and R 38 , R 38 and R 39 , R 39 and R 40 , R 41and R 42 , R 42 and R 43 , R 43 and R 44 , R 45 and R 46 , R 46 and R 47 , R 47 and R 48 and R 48 and R 49 (Hereinafter referred to as “R 21 and R 22 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.

[0041] In the above formula (d), the cycloalkyl group having 3 to 10 carbon atoms is preferably a cyclohexyl group because it is easy to produce and has excellent storage stability.

[0042] M in the above general formula (I) 1 Compound (I) in which is a group represented by formula (a), formula (c) or formula (d) is preferred because it has high sensitivity and can give a cured product capable of forming a fine pattern with excellent insulating properties. Among them, the compound represented by formula (a) is more preferred because the cured product obtained has excellent insulating properties, and the compound represented by formula (c) is more preferred because the cured product obtained has excellent heat resistance.

[0043] The compound of the present invention is a compound having a structure in which an acid anhydride having a polymerizable group (compound (II)) is added to the above compound (I). The polymerizable group means a group capable of undergoing a polymerization reaction by a radical, an acid, a base, etc., and may be one in which the same kind of groups undergo an addition reaction with each other, or one in which two different kinds of groups undergo an addition reaction or a condensation reaction. Examples of the polymerizable group include radical polymerizable groups such as an acrylic group, a methacrylic group, a styrenyl group, and a vinyl group, a hydroxyl group, an epoxy group, a mercapto group, an allyl group, an isocyanate group, an amino group, and an alkoxysilyl group.

[0044] Examples of the acid anhydride structure in the compound (II) include structures corresponding to aliphatic acid anhydrides such as succinic anhydride and maleic anhydride, aromatic acid anhydrides such as trimellitic anhydride and phthalic anhydride, and acid anhydrides having an alicyclic structure such as tetrahydrophthalic anhydride, nadic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and cyclohexane-1,2,4-tricarboxylic anhydride.

[0045] Examples of the compound (II) include those obtained by subjecting the carboxyl group of trimellitic anhydride or hexahydrotrimellitic anhydride to a condensation reaction with an alcohol compound having a polymerizable group, such as 2-hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, or dipentaerythritol pentaacrylate.

[0046] Compound (II) in which the polymerizable group is a radical polymerizable group is preferred, and compound (II) in which the polymerizable group is an acrylic group or a methacrylic group is particularly preferred. Compound (II) in which the polymerizable group is the above group is preferred because the resulting polymerizable composition has excellent sensitivity and the resulting cured product has excellent chemical resistance.

[0047] Compound (II) having a cyclic structure is preferred, and the cyclic structure is preferably a condensed ring, particularly preferably a condensed ring not containing an aromatic ring, because the resulting cured product has excellent insulating properties.

[0048] The compound (II) having an alicyclic structure is preferred because the resulting cured product has excellent chemical resistance.

[0049] Examples of the acid anhydride having a polymerizable group include the following compounds (II-1) to (II-13), but are not limited to these compounds.

[0050] [ka]

[0051] [ka]

[0052] The compound of the present invention may further have a structure in which an acid dianhydride is added. Such a compound is preferable because it can be made into a compound having the desired alkaline developability by adjusting the acid value.

[0053] Examples of the acid dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,3'-4,4'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, and meso-butane-1,2,3,4-tetracarboxylic anhydride.

[0054] 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.

[0055] The compound of the present invention can be produced by carrying out an addition reaction of the above-mentioned compound (II) to the above-mentioned compound (I). The reaction can 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 above-mentioned compound (I) and the above-mentioned compound (II) 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 (II), but may include other reaction forms, and the compound having a structure in which compound (II) is added to compound (I) is a general term for reaction products.

[0056] In the present invention, a structure in which 0.1 to 0.8 mol of the compound (II) is added to 1 mol of the compound (I) is preferred because the resulting polymerizable composition has excellent sensitivity and a cured product capable of forming a fine pattern with excellent insulating properties is obtained, and a structure in which 0.2 to 0.6 mol is added is particularly preferred. In other words, a structure in which 0.05 to 0.4 mol of the compound (II) is added to 1 mol of the hydroxyl group in the compound (I) is preferred because a cured product with excellent adhesion and heat resistance is obtained, and a structure in which 0.1 to 0.3 mol is particularly preferred.

[0057] When the compound (I) has a structure in which an acid dianhydride is added, a structure in which 0.2 to 1.0 mol of the acid dianhydride is added to 1 mol of the compound (I) is preferred because the resulting polymerizable composition has high alkali developability, and a structure in which 0.3 to 0.8 mol is particularly preferred. In other words, a structure in which 0.1 to 0.5 mol of the acid dianhydride is added to 1 mol of the hydroxyl group in the 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 mol is particularly preferred.

[0058] The reaction of adding the acid dianhydride to the compound (I) can be carried out in the same manner as the reaction of adding the compound (II) to the compound (I) described above. In addition, the reaction of adding the compound (II) to the compound (I) and the reaction of adding the acid dianhydride to the compound (I) may be carried out simultaneously.

[0059] 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, since the resulting polymerizable composition has excellent alkaline developability.

[0060] 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 the resulting polymerizable composition has excellent sensitivity and a cured product capable of forming a fine pattern having excellent insulating properties can be obtained, and is particularly preferably in the range of 3,000 to 10,000.

[0061] 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.

[0062] 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℃

[0063] The polymerizable composition of the present invention contains a compound (A) having a structure in which the compound (II) is added to the compound (I) and a polymerization initiator (B). With such a constitution, the polymerizable composition has excellent sensitivity and can give a cured product patterned with high accuracy.

[0064] 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, because this provides excellent sensitivity. The solid content of the polymerizable composition is the total amount of components excluding the solvent described below from the polymerizable composition.

[0065] 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.

[0066] The polymerization initiator (B) is preferably a compound having an oxime ester group, since the resulting polymerizable composition has excellent sensitivity and a cured product that is patterned with high precision can be obtained.

[0067] The polymerization initiator (B) is preferably a compound having a carbazole skeleton, since the resulting polymerizable composition has excellent sensitivity and a cured product that is patterned with high precision can be obtained.

[0068] The polymerization initiator (B) is preferably a compound having an electron-withdrawing group, since a cured product having excellent insulating properties can be obtained. In particular, the electron-withdrawing group is preferably a nitro group.

[0069] 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 (D) described later, in order to provide an excellent sensitivity of the polymerizable composition of the present invention, and more preferably 1 to 5 parts by mass.

[0070] The polymerizable composition may further contain a colorant (C). Examples of the colorant (C) include pigments and dyes. As the pigments and dyes, inorganic colorants 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 a solvent, and inorganic or organic dyes that have been made into lakes.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] In the polymerizable composition of the present invention, the content of the colorant (C) is not particularly limited, but is preferably 10 to 500 parts by mass, 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 (C) 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).

[0075] The polymerizable composition may further contain a polymerizable compound (D) other than the compound (A). Examples of the polymerizable compound include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, 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.

[0076] The content of the polymerizable compound (D) 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.

[0077] The polymerizable composition of the present invention may further contain an epoxy compound (E). Examples of the epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propanediol, glycidyl ether ... Examples of monofunctional epoxy compounds include alkyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, and propylene oxide.

[0078] In addition, polyfunctional epoxy compounds such as bisphenol type epoxy compounds and glycidyl ethers can also be used. Examples of the bisphenol type epoxy compounds include alkylidene bisphenol polyglycidyl ether type epoxy resins as well as bisphenol type epoxy compounds such as hydrogenated bisphenol type epoxy compounds.

[0079] Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, and 1,1,1,1-tetra(glycidyloxymethyl)methane.

[0080] A solvent (F) may 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 the compound (A), the polymerization initiator (B), the colorant (C), or the polymerizable compound (D). As the solvent, a solvent that can dissolve or disperse each of the above components (the compound (A), the polymerization initiator (B), the colorant (C), the polymerizable compound (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.

[0081] 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 (PGMEA) are preferred because they have good solubility for the compound (A) and the polymerization initiator (B).

[0082] 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.

[0083] If necessary, the polymerizable composition of the present invention may contain conventional additives such as thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine, plasticizers, adhesion promoters, fillers, defoamers, dispersants, leveling agents, silane coupling agents, and flame retardants. These may be used alone or in combination of two or more.

[0084] 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.

[0085] 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 carry out polymerization by either light irradiation or heating, or both of them, because of high curability.

[0086] 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.

[0087] 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.

[0088] 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

[0089] 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.

[0090] [Example 1-1] Preparation of Compound A-1 Solution 25.0 g of 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]3-phenylindane (hereinafter also referred to as compound a-1), 7.29 g of acrylic acid (hereinafter also referred to as compound b-1), 0.065 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 21.5 g of PGMEA were charged and stirred at 120° C. for 15 hours. The reaction solution was cooled to room temperature, and 8.75 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA) as an acid dianhydride, 4.62 g of 1,3-dioxooctahydroisobenzofuran-5-carboxylate-2-(methacryloyloxy)ethyl (compound (II-1)) as an acid anhydride having a polymerizable group, 0.027 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 15.8 g of PGMEA were added, and the mixture was stirred at 110 ° C for 5 hours. The mixture was cooled to room temperature, and 22.0 g of PGMEA was added to obtain the target compound A-1 as a PGMEA solution (concentration 43.8 mass%). Compound A-1 had Mw = 5300, Mn = 2900, and acid value (solid content) 93 mg KOH / g. Compound A-1 was obtained by reacting one hydroxyl group of a compound obtained by adding compound b-1 to compound a-1 with 0.30 units of BPDA, which is an acid dianhydride, and 0.15 units of compound (II-1), which is an acid anhydride having a polymerizable group, in a ratio of 1 unit.

[0091] [ka]

[0092] [Example 1-2] Preparation of Compound A-2 Solution 25.0 g of compound a-1, 7.29 g of compound b-1, 0.065 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 21.5 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 8.75 g of BPDA as an acid dianhydride, 4.53 g of 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate-2-(methacryloyloxy)ethyl (compound (II-2)) as an acid anhydride having a polymerizable group, 0.027 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 15.8 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. The mixture was cooled to room temperature, and 21.9 g of PGMEA was added to obtain the target compound A-2 as a PGMEA solution (concentration 43.8% by mass). Compound A-2 had Mw = 5,200, Mn = 2,900, and acid value (solid content) of 93 mg KOH / g. Compound A-2 was obtained by reacting one hydroxyl group of a compound obtained by adding compound b-1 to compound a-1 with 0.30 units of BPDA, which is an acid dianhydride, and 0.15 units of compound (II-2), which is an acid anhydride having a polymerizable group, in a ratio of 1 unit.

[0093] [Example 1-3] Preparation of Compound A-3 Solution 25.0 g of compound a-1, 7.29 g of compound b-1, 0.0650 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 21.5 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 8.75 g of BPDA as an acid dianhydride, 7.09 g of pentaerythritol-triacrylate-mono acid anhydride (compound (II-6)) as an acid anhydride having a polymerizable group, 0.032 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 17.9 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. The mixture was cooled to room temperature, and 23.1 g of PGMEA was added to obtain the target compound A-3 as a PGMEA solution (concentration 43.8% by mass). Compound A-3 had Mw = 5400, Mn = 2900, and acid value (solid content) of 89 mg KOH / g. Compound A-3 was obtained by reacting one hydroxyl group of a compound obtained by adding compound b-1 to compound a-1 with 0.30 units of BPDA, which is an acid dianhydride, and 0.15 units of compound (II-6), which is an acid anhydride having a polymerizable group, in a ratio of 1 unit.

[0094] [Example 1-4] Preparation of Compound A-4 Solution 25.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene (hereinafter also referred to as compound a-2), 7.95 g of compound b-1, 0.066 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 22.0 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 9.55 g of BPDA as an acid dianhydride, 5.04 g of compound (II-1) as an acid anhydride having a polymerizable group, 0.029 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 16.9 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. The mixture was cooled to room temperature, and 22.9 g of PGMEA was added to obtain the target compound A-4 as a PGMEA solution (concentration 44.6% by mass). Compound A-4 had Mw = 5500, Mn = 2900, and acid value (solid content) of 97 mg KOH / g. Compound A-4 was obtained by reacting one hydroxyl group of a compound obtained by adding compound b-1 to compound a-2 with 0.30 units of BPDA, which is an acid dianhydride, and 0.15 units of compound (II-1), which is an acid anhydride having a polymerizable group, in a ratio of 1 unit.

[0095] [ka]

[0096] [Examples 1-5] Preparation of Compound A-5 Solution 25.0g of compound a-2, 7.29g of compound b-1, 0.065g of dibutylhydroxytoluene, 0.180g of tetrabutylammonium chloride, and 22.0g of PGMEA were charged and stirred at 120 ° C for 15 hours. The reaction solution was cooled to room temperature, and 9.55g of BPDA as an acid dianhydride, 4.94g of compound (II-2) as an acid anhydride having a polymerizable group, 0.029g of dibutylhydroxytoluene, 0.180g of tetrabutylammonium chloride, and 16.8g of PGMEA were added, and the mixture was stirred at 110 ° C for 5 hours. The mixture was cooled to room temperature, and 22.8g of PGMEA was added to obtain the target compound A-5 as a PGMEA solution (concentration 43.8% by mass). Compound A-5 had Mw = 5400, Mn = 2900, and acid value (solid content) 98 mg KOH / g. Compound A-5 was obtained by reacting one hydroxyl group of a compound obtained by adding compound b-1 to compound a-2 with 0.30 units of BPDA, which is an acid dianhydride, and 0.15 units of compound (II-2), which is an acid anhydride having a polymerizable group, in a ratio of 1 unit.

[0097] [Examples 1-6] Preparation of Compound A-6 Solution 25.0 g of 4,4-bis[4-(2,3-epoxypropyloxy)phenyl](biphenyl-4-yl)cyclohexylmethane (hereinafter also referred to as compound a-3), 6.56 g of compound b-1, 0.063 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 21.0 g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 7.88 g of BPDA as an acid dianhydride, 4.16 g of compound (II-1) as an acid anhydride having a polymerizable group, 0.024 g of dibutylhydroxytoluene, 0.180 g of tetrabutylammonium chloride, and 14.6 g of PGMEA were added, and the mixture was stirred at 110 ° C. for 5 hours. The mixture was cooled to room temperature, and 21.0 g of PGMEA was added to obtain the target compound A-6 as a PGMEA solution (concentration 44.6% by mass). Compound A-6 had Mw = 5200, Mn = 2600, and acid value (solid content) of 88 mg KOH / g. Compound A-6 was obtained by reacting one hydroxyl group of a compound obtained by adding compound b-1 to compound a-3 with 0.30 units of BPDA, which is an acid dianhydride, and 0.15 units of compound (II-1), which is an acid anhydride having a polymerizable group, in a ratio of 1 unit.

[0098] [ka]

[0099] [Examples 1-7] Preparation of Compound A-7 Solution 25.0g of compound a-1, 7.29g of compound b-1, 0.065g of dibutylhydroxytoluene, 0.180g of tetrabutylammonium chloride, and 21.5g of PGMEA were charged and stirred at 120 ° C. for 15 hours. The reaction solution was cooled to room temperature, and 6.2g of compound (II-1) as an acid anhydride having a polymerizable group, 6.0g of succinic anhydride, 0.024g of dibutylhydroxytoluene, 0.180g of tetrabutylammonium chloride, and 19.0g of PGMEA were added and stirred at 100 ° C. for 3 hours. Furthermore, 12.5g of compound a-1 was added and stirred at 90 ° C. for 90 minutes and at 120 ° C. for 4 hours. Further, 5.0 g of succinic anhydride was added and stirred at 100°C for 2 hours, cooled to room temperature, and 38.5 g of PGMEA was added to obtain the target compound A-7 as a PGMEA solution (concentration 44.6 mass%). Compound A-7 had Mw = 4800, Mn = 2000, and acid value (solid content) 76 mg KOH / g. Compound A-7 was obtained by adding 0.2 units of compound (II-1), which is an acid anhydride having a polymerizable group, and 0.6 units of an acid anhydride having no polymerizable group to one hydroxyl group of a compound obtained by adding compound b-1 to compound a-3, reacting the epoxy group of compound a-3 in a ratio of 0.5 units, and further reacting with 0.5 units of an acid anhydride.

[0100] [Production Example 1] Preparation of Compound A-8 Solution 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]3-phenylindane 100g, acrylic acid 30g, 2,6-di-tert-butyl-p-cresol 0.26g, tetrabutylammonium bromide 0.71g, and PGMEA 86.0g were charged and stirred at 120 ° C for 16 hours. The reaction solution was cooled to room temperature, PGMEA 56.0g, 3,3',4,4'-biphenyltetracarboxylic dianhydride 35.0g, and tetra-n-butylammonium bromide 0.24g were added, and the mixture was stirred at 120 ° C for 4 hours, 100 ° C for 3 hours, 80 ° C for 4 hours, 60 ° C for 6 hours, and 40 ° C for 11 hours, and then PGMEA 83.5g was added to obtain the target compound A-8 as a PGMEA solution (concentration 45.0 mass%). Compound A-8 had Mw=5,300, Mn=2,100, and an acid value (solid content) of 99.7 mg KOH / g.

[0101] [Production Example 2] Preparation of Compound A-9 solution 75.0g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 23.8g of acrylic acid, 0.273g of 2,6-di-t-butyl-p-cresol, 0.585g of tetrabutylammonium chloride, and 65.9g of PGMEA were charged and stirred at 120°C for 16 hours. The reaction solution was cooled to room temperature, and 44.5g of PGMEA, 28.6g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 0.24g of tetra-n-butylammonium bromide were added and stirred at 120°C for 4 hours. 7.4g of tetrahydrophthalic anhydride was further added, and the mixture was stirred at 120°C for 4 hours, 100°C for 3 hours, 80°C for 4 hours, 60°C for 6 hours, and 40°C for 11 hours, after which 65.0g of PGMEA was added to obtain the target compound A-9 as a PGMEA solution (concentration 45.0% by mass). Compound A-9 had Mw = 5100, Mn = 2170, and acid value (solid content) of 103.9 mg KOH / g.

[0102] [Production Example 3] Production of Carbon Black No. 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a deionized aqueous solution of sodium peroxodisulfate (concentration 2.0N) were mixed and stirred for 10 hours at 60° C. After filtration, the resulting slurry was neutralized with sodium hydroxide and treated by diafiltration. The resulting solid was dried overnight at 75° C. to obtain Carbon Black No. 1 as a black powder.

[0103] [Production Example 4] Production of Carbon Black No. 2 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 400 ml of sulfolane were mixed, 15 g of amidosulfuric acid was added, and the mixture was stirred for 10 hours at 140 to 150° C. The resulting slurry was neutralized with lithium hydroxide and treated by diafiltration, and the resulting solid was dried overnight at 75° C. to obtain Carbon Black No. 2 as a black powder.

[0104] [Production Example 5] Preparation of Surface-Treated Carbon Black Dispersion No. 1 20 g of carbon black No. 1, 4.45 g of the compound A-8 solution obtained in Production Example 1, 3 g of DISPERBYK-161, and 72.55 g of PGMEA were weighed out and processed in a bead mill to obtain carbon black dispersion No. 1 (concentration 20% by mass).

[0105] [Production Example 6] Preparation of Surface-Treated Carbon Black Dispersion No. 2 20 g of carbon black No. 2, 4.45 g of the compound A-8 solution obtained in Production Example 1, 3 g of DISPERBYK-161, and 72.55 g of PGMEA were weighed out and processed in a bead mill to obtain carbon black dispersion No. 2 (concentration 20% by mass).

[0106] [Examples 2-1 to 2-9, Comparative Examples 1 to 2] Polymerizable compositions were prepared by mixing the components in the ratios (parts by mass) shown in Tables 1 and 2, and the sensitivity, minimum contact line width, volume resistance, and taper angle were evaluated by the following methods. 1 and 2. The components in the table are as follows:

[0107] A-1: Compound A-1 solution (concentration 43.8% by mass) A-2: Compound A-2 solution (concentration 43.8% by mass) A-3: Compound A-3 solution (concentration 43.8% by mass) A-4: Compound A-4 solution (concentration 44.6% by mass) A-5: Compound A-5 solution (concentration 43.8% by mass) A-6: Compound A-6 solution (concentration 44.6% by mass) A-7: Compound A-7 solution (concentration 44.6% by mass) A-8: Compound A-8 solution (concentration 45.0% by weight) A-9: Compound A-9 solution (concentration 45.0% by weight) B-1: Compound B1 (compound having the following structure) B-2: Compound B2 (compound having the following structure) C-1: Surface-treated carbon black dispersion No. 1 (concentration 20% by mass) C-2: Surface-treated carbon black dispersion No. 2 (concentration 20% by mass) D-1: Kayarad DPHA (polyfunctional acrylic compound; manufactured by Nippon Kayaku Co., Ltd.) E-1: EP-4100 (bisphenol A type liquid epoxy compound; manufactured by ADEKA) F-1: PGMEA (solvent) G-1: KBM-403 (a silane coupling agent having an epoxy group; manufactured by Shin-Etsu Chemical Co., Ltd.)

[0108] [ka]

[0109] <Sensitivity> The polymerizable compositions of the Examples and Comparative Examples were spin-coated (1300 rpm, 50 seconds) on a glass substrate and dried. The substrate was pre-baked at 100°C for 100 seconds, exposed to light using a specified mask and an ultra-high pressure mercury lamp as a light source, then developed by immersing in a 0.04% KOH aqueous solution at 23°C for 30 seconds, and thoroughly washed with water. After washing and drying, the substrate was baked at 230°C for 30 minutes to fix the pattern. The sensitivity was evaluated at an exposure of 40 mJ / cm 2 The one that shows good pattern fixation after development is designated as A, and the exposure dose is 40 mJ / cm 2 The pattern did not fix properly after development, and the exposure was 80 mJ / cm 2 The one that shows good fixation of the pattern after development at 100 mJ / cm is designated as B, and 2 Those requiring the above exposure were rated as C. A polymerizable composition having a sensitivity of A can be preferably used as a black matrix, a polymerizable composition having a sensitivity of B can be used as a black matrix, and a polymerizable composition having a sensitivity of C is difficult to use as a black matrix.

[0110] <Minimum contact line width> The polymerizable compositions of the Examples and Comparative Examples were spin-coated onto a glass substrate (10 cm x 10 cm) and heated at 100°C for 100 seconds to form a coating film of 1.0 μm on the surface of the glass substrate. Thereafter, a proximity exposure machine manufactured by Microtec Corporation was used to expose the glass substrate to a 40 mJ / cm2 exposure light through a negative mask with a pattern of 1 to 20 μm. 2 The exposed film was developed with a 0.04% by mass KOH aqueous solution at 23°C for 40 seconds, and then baked at 230°C for 30 minutes. The photomask pattern with the smallest number among the photomask patterns in which the cured film was adhered to the glass substrate by optical microscope observation was determined as the minimum contact line width. When the minimum contact line width is 6 μm or less, it can be preferably used as a high-definition black matrix.

[0111] <Volume resistance> The polymerizable compositions of the Examples and Comparative Examples were applied to a Cr-glass substrate, prebaked at 90°C for 90 seconds, and dried. A Cr portion of several mm was exposed at the edge of the coated substrate, and the coated substrate was postbaked at 230°C for 30 minutes, after which aluminum was evaporated onto the coating film using a vacuum evaporation machine to produce an aluminum electrode. The resistance was measured at a voltage of 10 V using an ADVANTEST R8340 ULTRA HIGH RESISTANCE METER. The volume resistance was 1.0 x 1013 A resistivity of Ω·cm or more is preferable for use as a black matrix.

[0112] <Taper angle> The polymerizable compositions of the Examples and Comparative Examples were spin-coated onto a glass substrate (10 cm x 10 cm) at 900 rpm for 5 seconds and heated at 100°C for 100 seconds to form a coating film of 1.0 μm on the surface of the glass substrate. Thereafter, using a proximity exposure machine manufactured by Microtec, the coating film was exposed to light at a dose of 40 mJ / cm through a negative mask with a 6 μm pattern. 2 The exposed film was developed with a 0.04% by mass KOH aqueous solution at 23°C for 40 seconds, then baked at 230°C for 30 minutes, and the junction angle (taper angle) between the pattern and the substrate was measured using a scanning electron microscope. This taper angle corresponds to the angle θ in (a) and (b) of Figure 1. If the taper angle is acute, it means that there is no undercut in the pattern, and if the taper angle is obtuse, it means that there is an undercut in the pattern. If there is an undercut in the pattern, the contrast will decrease, resulting in a defect.

[0113] [Table 1]

[0114] [Table 2]

[0115] From the results shown in Tables 1 and 2, it was confirmed that the polymerizable composition using the compound of the present invention has excellent sensitivity and insulating properties, and is capable of forming a fine pattern having an appropriate pattern shape.

Claims

1. A compound having a structure in which an acid anhydride having a radical polymerizable group is added to a 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 halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, with no oxygen atom adjacent to them; X １ and X ２ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with -O-, with no oxygen atom adjacent to them; M １ represents a group represented by the following formula (a), (b) or (d): 【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 , R ３６ , R ４５ , R ４６ , R ４７ , R ４８ and R ４９ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, or a group having 1 to 20 carbon atoms in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>, <Group A>: -O-, -CO-, -COO-, -OCO-, -NR ５１ -, -NR ５１ CO-, -S- R ５１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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 ４５ , R ４６ , R ４７ , R ４８ and R ４９ represents that one or more of the hydrogen atoms in the hydrocarbon group is replaced with a halogen atom, a cyano group, a nitro group, a hydroxyl group, or an -OR ５２ , -COOR ５２ , -CO-R ５２ Or -SR ５２ may be a group having 1 to 20 carbon atoms substituted with 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 ４５ and R ４６ , R ４６ and R ４７ , R ４７ and R ４８ and R ４８ and R ４９ may be bonded to each other to form a ring having 3 to 10 carbon atoms and composed of hydrogen atoms and carbon atoms, Cy represents a cycloalkyl group having 3 to 10 carbon atoms; * indicates the site where the groups represented by (a), (b), and (d) are bonded to the adjacent group.

2. M in the above general formula (I) １ The compound according to claim 1 , wherein is a group represented by the above formula (a).

3. 3. The compound according to claim 1, wherein the acid anhydride having a polymerizable group is an acid anhydride having an alicyclic structure.

4. The compound according to any one of claims 1 to 3, further having a structure to which an acid dianhydride is added.

5. A polymerizable composition comprising the compound (A) according to any one of claims 1 to 4, and a polymerization initiator (B).

6. The polymerizable composition according to claim 5 , further comprising a colorant (C).

7. A cured product of the polymerizable composition according to claim 5 or 6.

8. A display device comprising the cured product according to claim 7.

9. A method for producing a cured product, comprising a step of irradiating the polymerizable composition according to claim 5 or 6 with light or heating.

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