Compounds, polymerization initiators, polymerizable compositions, cured products, color filters, and methods for producing cured products.

Abstract

The purpose of the present invention is to provide a polymerization initiator which has excellent sensitivity and good solubility in a solvent, while enabling the achievement of a cured product that has a high transmittance in the visible light region.　The present invention provides a compound which has a group represented by general formula (I) and a group represented by general formula (II) in a same molecule. In the formulae, each of R1, R2 and R4 independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having from 1 to 20 carbon atoms, a group obtained by substituting one or more methylene groups in the hydrocarbon group with a divalent group such as -O-, a heterocyclic group having from 2 to 10 carbon atoms, a heteroring-containing group having from 3 to 20 carbon atoms, or a group obtained by substituting one or more methylene groups in the heteroring-containing group with a divalent group such as -O-; n represents 0 or 1; and * represents a bonding hand.

Description

[Technical Field]

[0001] This invention relates to oxime ester compounds and polymerization initiators containing the same. [Background technology]

[0002] Polymerizable compositions are obtained by adding a polymerization initiator to an ethylenically unsaturated compound, and because they can be polymerized and cured by irradiation with energy rays (light), they are used in photocurable inks, photosensitive printing plates, various photoresists, and the like.

[0003] As polymerization initiators used in these polymerizable compositions, Patent Document 1 proposes an oxime ester photopolymerization initiator having a carbazole skeleton, and Patent Document 2 proposes a polymerization initiator having an oxime ester compound having a triarylamine skeleton. Furthermore, polymerizable compositions containing colorants such as color filters are required to be highly sensitive, and therefore the polymerization initiator in the resist needs to be at a high concentration. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2008 / 138732 [Patent Document 2] International Publication No. 2017 / 033880 [Overview of the project]

[0005] However, the oxime ester compounds proposed in Patent Documents 1 and 2 could not achieve a satisfactory level of sensitivity, solubility in solvents, and transparency of the resulting cured product.

[0006] Therefore, the problem that the present invention aims to solve is to provide a polymerization initiator that has excellent sensitivity, good solubility in solvents, and high transmittance in the visible light region of the resulting cured product. Specifically, the invention aims to provide an oxime ester compound useful as a polymerization initiator used in polymerizable compositions, and a polymerization initiator containing the same.

[0007] As a result of diligent research to solve the above problems, the present inventors have found that a compound having an oxime ester group and a diketonyl group can solve the above problems, and have completed the present invention.

[0008] In other words, the present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) within the same molecule.

[0009] [ka] In the formula, R 1 and R 2 Each of these independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups within the hydrocarbon group are substituted by a divalent group selected from Group A below, a heterocyclic group having 2 to 10 carbon atoms, or a heterocyclic-containing group having 3 to 20 carbon atoms, or a group in which one or more methylene groups within the heterocyclic-containing group are substituted by a divalent group selected from Group A below. n represents 0 or 1, * represents a bond, If a compound contains multiple groups represented by general formula (I), then multiple R groups exist. 1 , R 2 And n may be the same or different. <Group A>: -O-, -CO-, -COO-, -OCO-, -NR 3 -, -NR 3 CO-, -S- R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0010] [ka] In the formula, R 4 represents a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group B>, a heterocyclic group having 2 to 10 carbon atoms, or a heterocyclic group-containing group having 3 to 20 carbon atoms or a group in which one or more methylene groups in the heterocyclic group-containing group are substituted with a divalent group selected from the following <Group B>. * represents a bond. When a plurality of groups represented by the general formula (II) are present in the compound, the plurality of R 4 may be the same or different. <Group B>: -O-, -CO-, -COO-, -OCO-, -NR 5 -, -NR 5 CO-, -S- R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, the compound of the present invention, a polymerization initiator containing the same, a polymerizable composition containing the polymerization initiator, a cured product thereof, a color filter, and a method for producing a cured product will be described in detail based on preferred embodiments.

[0012] The compound of the present invention is a compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) in the same molecule.

[0013]

Chemical formula

[0014] [ka] In the formula, R 4 This represents a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group B>, a heterocyclic group having 2 to 10 carbon atoms, or a heterocyclic-containing group having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the heterocyclic-containing group are substituted with a divalent group selected from the following <Group B>, * represents a bond, If a compound contains multiple groups represented by general formula (II), then multiple R groups exist. 4 They may be the same or different. <Group B>: -O-, -CO-, -COO-, -OCO-, -NR 5 -, -NR 5 CO-, -S- R 5 This represents a hydrogen atom and a hydrocarbon group with 1 to 20 carbon atoms.

[0015] Examples of halogen atoms in the above general formula (I) include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] The hydrocarbon groups having 1 to 20 carbon atoms in the above general formulas (I) and (II) may be any group having 1 to 20 carbon atoms consisting of carbon atoms and hydrogen atoms, and are not particularly limited, but examples include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms.

[0017] Aliphatic hydrocarbon groups having 1 to 20 carbon atoms are hydrocarbon groups that do not contain aromatic hydrocarbon rings or heterocyclic rings, and may have substituents. A substituted aliphatic hydrocarbon group is a group in which one or more hydrogen atoms in the aliphatic hydrocarbon group are replaced by substituents.

[0018] Examples of unsubstituted aliphatic hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, and cycloalkylalkyl groups having 4 to 20 carbon atoms. Examples of substituted aliphatic hydrocarbon groups include groups in which one or more hydrogen atoms in the unsubstituted aliphatic hydrocarbon group are replaced by substituents, and examples of such substituents include halogen atoms, cyano groups, nitro groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, and isocyanate groups.

[0019] The alkyl groups having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Examples of branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, and isononyl.

[0020] The above alkenyl groups having 2 to 20 carbon atoms may be linear or branched. They may also be terminal alkenyl groups having an unsaturated bond at the end, or internal alkenyl groups having an unsaturated bond inside. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienylenylallyl.

[0021] Examples of cycloalkyl groups having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups are substituted with an alkyl group. Examples of saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl. Examples of alkyl groups that substitute hydrogen atoms in the ring of saturated monocyclic or saturated polycyclic alkyl groups include the groups exemplified above as alkyl groups having 1 to 20 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are substituted with an alkyl group include bornyl.

[0022] The above-mentioned cycloalkylalkyl groups having 4 to 20 carbon atoms refer to groups having 4 to 20 carbon atoms in which the hydrogen atoms of the alkyl group are substituted with cycloalkyl groups. The cycloalkyl group in a cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms in which the cycloalkyl group is monocyclic include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, and 2-cyclodecylethyl. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms in which the cycloalkyl group is polycyclic include 3-adamantylpropyl and 3-decahydronaphthylpropyl.

[0023] A hydrocarbon ring-containing group having 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon group or substituents. A substituent-containing aromatic hydrocarbon ring-containing group is a group in which one or more hydrogen atoms in the aromatic hydrocarbon ring-containing group are replaced by substituents.

[0024] Examples of unsubstituted aromatic hydrocarbon ring-containing groups include aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms. Examples of substituted aromatic hydrocarbon ring-containing groups include groups in which one or more hydrogen atoms in the above-mentioned unsubstituted aromatic hydrocarbon ring-containing group are substituted by substituents. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, or isocyanate groups.

[0025] The aryl group having 6 to 20 carbon atoms may be a monocyclic structure, a fused ring structure, or a structure in which two aromatic hydrocarbon rings are linked.

[0026] Examples of monocyclic aryl groups include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl. Examples of fused ring aryl groups include naphthyl, anthracenyl, phenanthryl, and pyrenyl.

[0027] An aryl group formed by linking two aromatic hydrocarbon rings may be formed by linking two monocyclic aromatic hydrocarbon rings, or by linking a monocyclic aromatic hydrocarbon ring with a fused ring aromatic hydrocarbon ring, or by linking two fused ring aromatic hydrocarbon rings. Examples of linking groups that connect two aromatic hydrocarbon rings include single bonds, sulfide groups (-S-), and carbonyl groups. Examples of aryl groups formed by linking two monocyclic aromatic hydrocarbon rings include biphenyl, diphenyl sulfide, and benzoylphenyl.

[0028] The above-mentioned arylalkyl groups having 7 to 20 carbon atoms are groups in which one or more hydrogen atoms in the alkyl group are replaced by an aryl group. Examples of arylalkyl groups having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl groups.

[0029] The heterocyclic group in the above general formulas (I) and (II) is a group obtained by removing one hydrogen atom from a heterocyclic compound.

[0030] Examples of heterocyclic groups having 2 to 10 carbon atoms include pyridyl group, quinolyl group, thiazolyl group, tetrahydrofuran group, dioxolanyl group, tetrahydropyranyl group, morpholylfuran group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group, piperazine group, pyrimidyl group, furyl group, thienyl group, benzoxazole-2-yl group, thiazole group, isothiazole group, oxazole group, isoxazole group, and morphonyl group.

[0031] The heterocyclic group having 2 to 10 carbon atoms may have substituents, such as halogen atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, -COOH, and -SO2H.

[0032] In the above general formulas (I) and (II), the heterocyclic group is a group in which a hydrogen atom in a hydrocarbon group is replaced by a heterocyclic group.

[0033] Examples of heterocyclic groups having 3 to 20 carbon atoms include groups in which one or more hydrogen atoms of an alkyl group are substituted with a heterocyclic group, and examples of such heterocyclic groups include those exemplified as heterocyclic groups having 2 to 10 carbon atoms.

[0034] The heterocyclic group having 3 to 20 carbon atoms may have an aromatic hydrocarbon ring, an aliphatic hydrocarbon group, or a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, -COOH, and -SO2H. Furthermore, the "3 to 20 carbon atoms" in the heterocyclic group containing 3 to 20 carbon atoms refers to the total number of carbon atoms in the heterocyclic group.

[0035] Furthermore, the heterocyclic group may be a link between a heterocyclic and a monocyclic aromatic hydrocarbon ring, or a link between a heterocyclic and a fused aromatic hydrocarbon ring. Examples of linking groups that connect two aromatic hydrocarbon rings include single bonds and carbonyl groups. Examples of heterocyclic group in which a heterocyclic and a monocyclic aromatic hydrocarbon ring are linked include benzothiophene.

[0036] In the above general formula (I), a group in which two or more methylene groups in the hydrocarbon group and the heterocyclic group are substituted with divalent groups selected from <Group A> above does not have a structure in which multiple divalent groups are adjacent to each other. The multiple divalent groups may be the same or different. The same applies to the group in the above general formula (II) in which two or more methylene groups in the hydrocarbon group and the heterocyclic group are substituted with divalent groups selected from <Group B> above.

[0037] In this invention, the number of carbon atoms in a group refers to the number of carbon atoms in the group after a substituent has replaced a hydrogen atom in the group. For example, if a hydrogen atom is substituted in an alkyl group having 1 to 20 carbon atoms, the number of carbon atoms, 1 to 20, refers to the number of carbon atoms after the hydrogen atom has been replaced, and not to the number of carbon atoms before the hydrogen atom was replaced. Furthermore, in this invention, the number of carbon atoms in a group in which a methylene group in a group with a predetermined number of carbon atoms is replaced by a divalent group defines the number of carbon atoms in the group before the substitution. For example, in the case of a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced by a divalent group, the number of carbon atoms, 1 to 20, refers to the number of carbon atoms in the alkyl group before the methylene group is replaced by the divalent group, and not the number of carbon atoms after the substitution.

[0038] Compounds in which n in the above general formula (I) is 1 are preferred because they have high sensitivity, excellent solubility in solvents, and the resulting cured product has excellent transparency.

[0039] In the above general formula (I), R 1 Compounds in which the group is a cycloalkylalkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms are preferred due to their high sensitivity, and compounds in which the group is a cycloalkylalkyl group having 4 to 10 carbon atoms or a phenyl group are particularly preferred.

[0040] In the above general formula (I), R 2 Compounds in which the group is an alkyl group having 1 to 10 carbon atoms are preferred due to their high sensitivity, compounds in which the group is an alkyl group having 1 to 4 carbon atoms are more preferred, and compounds in which the group is a methyl group are particularly preferred.

[0041] In the above general formula (I), R 2 However, compounds that are branched alkyl groups are preferred because they have excellent solubility in solvents.

[0042] In the above general formula (II), R 4 Compounds in which the group is an alkoxy group having 1 to 10 carbon atoms are preferred due to their high sensitivity, compounds in which the group is an alkoxy group having 1 to 4 carbon atoms are more preferred, and compounds in which the group is a methoxy group are particularly preferred.

[0043] The compounds of the present invention are preferably structured according to the following general formula (III) because they have high sensitivity and excellent solubility in solvents.

[0044] [ka] In the formula, A 1 This represents an aromatic ring with 6 to 20 carbon atoms. R 11 This represents the group represented by the general formula (I) above, R 12 This represents a group represented by the above general formula (II), a hydrocarbon group having 1 to 20 carbon atoms substituted with the above general formula (II), or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group C>, a heterocyclic group having 2 to 10 carbon atoms substituted with the above general formula (II), or a heterocyclic group having 3 to 20 carbon atoms substituted with the above general formula (II), or a group in which one or more methylene groups in the heterocyclic group are substituted with a divalent group selected from the following <Group C>, R 13 Each of these independently represents a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups within the hydrocarbon group are substituted by a divalent group selected from the following <Group C>, a heterocyclic group having 2 to 10 carbon atoms, or a heterocyclic-containing group having 3 to 20 carbon atoms, or a group in which one or more methylene groups within the heterocyclic-containing group are substituted by a divalent group selected from the following <Group C>. a represents an integer between 1 and 20, and if a is an integer greater than or equal to 2, there are multiple R values. 11 They may be the same or different. b represents an integer between 1 and 20, and if b is an integer greater than or equal to 2, there are multiple R values. 12 They may be the same or different. c represents an integer between 0 and 20, and if c is an integer greater than or equal to 2, there are multiple R values. 13 They may be the same or different. However, a+b+c is less than or equal to 20. <Group C>: -O-, -CO-, -COO-, -OCO-, -NR 14 -, -NR 14 CO-, -S- R 14 This represents a hydrogen atom and a hydrocarbon group with 1 to 20 carbon atoms.

[0045] Examples of aromatic rings with 6 to 20 carbon atoms in the above general formula (III) include aromatic hydrocarbon rings and aromatic heterocycles, specifically indole, carbazole, diphenyl sulfide, fluorene, triarylamine, coumarin, benzene, diphenyl, naphthalene, and anthracene.

[0046] The hydrocarbon groups having 1 to 20 carbon atoms, heterocyclic groups having 2 to 10 carbon atoms, and heterocyclic groups having 3 to 20 carbon atoms in the above general formula (III) are the same as the hydrocarbon groups having 1 to 20 carbon atoms, heterocyclic groups having 2 to 10 carbon atoms, and heterocyclic groups having 3 to 20 carbon atoms in the above general formula (I).

[0047] Compounds in which c in the above general formula (III) is an integer from 1 to 20 are preferred, and because they have excellent solubility in solvents, compounds having a branched alkyl group or cycloalkyl group with 3 to 20 carbon atoms in the molecule are preferred, R 13 Compounds in which one or more of the elements are branched alkyl groups or cycloalkyl groups having 3 to 20 carbon atoms are more preferred, compounds in which the elements are branched alkyl groups having 3 to 20 carbon atoms are even more preferred, and compounds in which the elements are branched alkyl groups having 3 to 10 carbon atoms are particularly preferred.

[0048] A in the above general formula (III) 1 However, compounds having a structure represented by the following general formula (IVα) or the following general formula (IVβ) are preferred because they have high sensitivity, and compounds having a structure represented by the following general formula (IVα) are particularly preferred.

[0049] [ka] The above general formula (IVα) is R in the above general formula (III) 11 , R 12 and R 13 This represents the structure when the group represented by is substituted with a hydrogen atom, and in the formula, X 1 This represents an oxygen atom, a sulfur atom, a selenium atom, CH2, CO, NH, or pH. X 2This represents a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CH2, CO, NH, or pH.

[0050] [ka] The above general formula (IVβ) is derived from the R in the above general formula (III). 11 , R 12 and R 13 This represents the structure when the group represented by is substituted with a hydrogen atom.

[0051] A 1 This is expressed by the above general formula (IVα), and X 1 NR 13 X 2 Compounds in which the bond is a single bond are particularly preferred due to their excellent sensitivity. Furthermore, R 13 Compounds in which the parent molecule is a branched alkyl group or cycloalkyl group having 3 to 20 carbon atoms are preferred due to their excellent solubility in solvents, more preferably a branched alkyl group having 3 to 20 carbon atoms, and particularly preferred a branched alkyl group having 3 to 10 carbon atoms.

[0052] Compounds in which a is an integer from 1 to 3 are preferred because they have excellent solubility and sensitivity in solvents, and compounds in which a is 1 are particularly preferred.

[0053] Compounds in which b is an integer from 1 to 3 are preferred because they have excellent solubility and sensitivity in solvents, and compounds in which b is 1 are particularly preferred.

[0054] Compounds in which c is an integer from 1 to 3 are preferred because they have excellent solubility and sensitivity in solvents, and compounds in which c is 1 are particularly preferred.

[0055] In the above general formula (IVα), R 11 and R 12 The substituent positions are X 1 Compounds that are in the para position relative to the binding site are preferred because they can be synthesized in high yield and have excellent storage stability.

[0056] The following compounds are preferred specific examples of the compounds of the present invention.

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] The compounds of the present invention can be produced by known methods. For example, the compound represented by the above general formula (III) can be produced by the method shown below.

[0065] When n in general formula (I) is 0, ketone compound 1 is obtained by reacting a known aromatic ring-containing compound with an acid chloride, ketone compound 1' is obtained by reacting ketone compound 1 with a chloride having a diketonyl group, and oxime compound 1 is obtained by reacting ketone compound 1' with hydroxylamine hydrochloride. Subsequently, a compound having both the group represented by general formula (I) and the group represented by general formula (II) in the same molecule can be produced by reacting oxime compound 1 with an acid anhydride or acid chloride in the presence of triethylamine (TEA). It can also be produced by the method described in Japanese Patent Publication No. 4223071.

[0066] [ka]

[0067] When n in general formula (I) is 1, ketone compound 2 is obtained by reacting a known aromatic ring-containing compound with an acid chloride, ketone compound 2' is obtained by reacting ketone compound 2 with a chloride having a diketonyl group, and oxime compound 2 is obtained by reacting ketone compound 2' with isobutyl nitrite. Subsequently, by reacting oxime compound 2 with an acid anhydride or acid chloride in the presence of TEA, a compound having both the group represented by general formula (I) and the group represented by general formula (II) in the same molecule can be produced.

[0068] [ka]

[0069] The compounds of the present invention described above are useful as polymerization initiators, specifically radical polymerization initiators, and in particular as photopolymerization initiators or thermal polymerization initiators. Furthermore, the compounds of the present invention can also be suitably used as base generators and sensitizers.

[0070] The polymerization initiator of the present invention contains at least one compound having both the group represented by general formula (I) and the group represented by general formula (II) within the same molecule. The content of the above compound in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass, because it provides high sensitivity and the resulting cured product has excellent transparency.

[0071] The polymerizable composition of the present invention contains the polymerization initiator (A) and the ethylenically unsaturated compound (B) of the present invention, and may also contain a combination of optional components such as a colorant (C), an alkali-developable compound (D), an inorganic compound, and a solvent.

[0072] The polymerization initiator (A) described above contains at least one compound having both the group represented by general formula (I) and the group represented by general formula (II) within the same molecule, and is useful as a radical polymerization initiator for ethylenically unsaturated compounds (B).

[0073] The polymerization initiator (A) described above may be used in combination with other polymerization initiators. The other polymerization initiators are not particularly limited as long as they generate radicals upon light irradiation or heating, and conventionally known compounds can be used. For example, oxime ester compounds, acetophenone compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds are preferred.

[0074] Examples of oxime ester compounds include compounds having a group represented by the above general formula (I), and because they have good sensitivity, they can be preferably used in the polymerizable composition of the present invention.

[0075] Acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, and 1-hydroxycycline. Examples include lohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

[0076] Examples of benzyl compounds include benzyl.

[0077] Examples of benzophenone compounds include benzophenone, o-methyl benzoylbenzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0078] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0079] Other polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyru-1-yl)]titanium.

[0080] Examples of commercially available radical initiators include ADEKA optomers N-1414, N-1717, N-1919, ADEKA Arcules NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by TRONLY); and others.

[0081] In the polymerizable composition described above, the content of polymerization initiator (A) is not particularly limited, but since the polymerizable composition exhibits excellent sensitivity to 100 parts by mass of a radical polymerizable compound having an ethylenically unsaturated group, it is preferably 0.1 to 70 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 1 to 5 parts by mass.

[0082] The ethylenically unsaturated compound (B) described above may be any compound having an ethylenically unsaturated bond and no acidic group. The ethylenically unsaturated compound (B) is not particularly limited, and those conventionally used in polymerizable compositions may be used, but examples include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; and unsaturated polybasic acids such as hydroxyethyl (meth)acrylate malate, hydroxypropyl (meth)acrylate malate, dicyclopentadiene malate, or polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups.(meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate-glycidyl, compounds No. A1 to No. A4 below, (meth)acrylate-methyl, (meth)acrylate-butyl, (meth)acrylate-isobutyl, (meth)acrylate-t-butyl, (meth)acrylate-cyclohexyl, (meth)acrylate-n-octyl, (meth)acrylate-isooctyl, (meth)acrylate-isononyl, (meth)acrylate-stearyl, (meth)acrylate-lauryl, (meth) Methoxyethyl acrylate, dimethylaminomethyl meth)acrylate, dimethylaminoethyl meth)acrylate, aminopropyl meth)acrylate, dimethylaminopropyl meth)acrylate, ethoxyethyl meth)acrylate, poly(ethoxy)ethyl meth)acrylate, butoxyethoxyethyl meth)acrylate, ethylhexyl meth)acrylate, phenoxyethyl meth)acrylate, tetrahydrofuryl meth)acrylate, vinyl meth)acrylate, allyl meth)acrylate, (meth)acrylate (T) Benzyl acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hex Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as (meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate;Acid anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhymic anhydride, etc.; (meth)acrylamide, methylenebis-( Amides of unsaturated monobasic acids and polyhydric amines such as meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl(meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, and 4-methoxystyrene Unsaturated aromatic compounds such as lene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzylmethyl ether, and vinylbenzylglycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl alcohols such as allyl alcohol and clotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; macromonomers having mono(meth)acryloyl groups at the ends of polymer molecular chains, such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, and polysiloxane;Examples include vinyl chlorides, vinylidene chlorides, divinyl succinates, diallyl phthalates, triallyl phosphates, triallyl isocyanurates, vinyl thioethers, vinylimidazoles, vinyl oxazolines, vinylcarbazoles, vinylpyrrolidones, vinylpyridines, vinyl urethane compounds of hydroxyl-containing vinyl monomers and polyisocyanate compounds, and vinyl epoxy compounds of hydroxyl-containing vinyl monomers and polyepoxy compounds.

[0083] Commercially available ethylenically unsaturated compounds (B) can also be used. Examples include Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), Aronics M-140, M-215, M-350 (manufactured by Toagosei Co., Ltd.), NK ester A-DPHA-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG, and HD-N (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0084] Ethylene-unsaturated compounds can be used individually or in combination of two or more types. When used in combination of two or more types, they may be copolymerized beforehand to form a copolymer.

[0085] [ka]

[0086] The polymerizable composition of the present invention may further contain a coloring agent (C) to form a colored polymerizable composition. Examples of coloring agents (C) include pigments, dyes, natural pigments, etc. These coloring agents (C) can be used individually or in combination of two or more.

[0087] Pigments include, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; antanthrone compounds; perinone compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; furnace process, channel Carbon black obtained by the ionization or thermal method, or carbon black such as acetylene black, Ketjen black, or lamp black; carbon black prepared or coated with epoxy resin; carbon black pre-dispersed in a solvent and adsorbed with 20-200 mg / g of resin; carbon black surface-treated with acid or alkali; carbon black with an average particle size of 8 nm or more and DBP oil absorption of 90 ml / 100 g or less; the total amount of oxygen calculated from CO and CO2 in the volatile matter at 950°C is such that the surface area of ​​the carbon black is 100 m². 2 Pigments containing 9 mg or more per unit; such as graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotubes, carbon microcoils, carbon nanohorns, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanides, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron(III) oxide, cadmium red, synthetic iron black, amber, and other organic or inorganic pigments can be used. These pigments can be used individually or in combination.

[0088] Commercially available pigments can be used as pigments, for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 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, Examples include 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

[0089] Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes, and these may be used in combination.

[0090] The content of the coloring agent (C) in the above polymerizable composition is preferably 5 to 350 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the radical polymerizable compound having an ethylenically unsaturated group, in order to obtain a good balance between curability and colorability.

[0091] The polymerizable composition according to the present invention may further contain an alkali-developable compound (D) to form an alkali-developable photosensitive resin composition. A composition containing both a colorant (C) and an alkali-developable compound (D) is also called a colored alkali-developable photosensitive resin composition.

[0092] The alkali-developable compound (D) is not particularly limited as long as it is a compound having an acidic group, but examples include the resin described in Japanese Patent Application Publication No. 2004-264414. The alkali-developable compound (D) may also have an ethylenically unsaturated bond. As the alkali-developable compound, polymers having a carboxyl group are preferred because they have excellent developability and compatibility with ethylenically unsaturated compounds.

[0093] Furthermore, as the alkali-developable compound (D), resins obtained by reacting the epoxy groups of epoxy compounds such as copolymers of acrylic acid esters, phenol and / or cresol novolac epoxy resins, polyphenylmethane-type epoxy resins having polyfunctional epoxy groups, and epoxy acrylate resins with an unsaturated monobasic acid, and then reacting them with a polybasic acid anhydride, can be used. The epoxy acrylate resin referred to here is obtained by reacting an epoxy compound with (meth)acrylic acid, and examples of such resins include Ripoxy SPC-1000, SPC-2000, SPC-3000 manufactured by Showa Denko Corporation, Dicklight UE-777 manufactured by DIC Corporation, and Yupika 4015 manufactured by Nippon Yupika Co., Ltd.

[0094] Furthermore, compounds having alkali developability are preferred because the resulting polymerizable composition exhibits excellent sensitivity, and therefore compounds having ethylenically unsaturated bonds are preferred. For similar reasons, among ethylenically unsaturated bonds, acrylic groups and methacrylic groups are preferred, with acrylic groups being particularly preferred.

[0095] A polymer having a carboxyl group is not particularly limited as long as it has a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"), but it may also have a structural unit having a crosslinkable group such as a methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, oxetanyl group, or isocyanate group (hereinafter referred to as "structural unit (U2)"), or a structural unit having a silyl group (hereinafter referred to as "structural unit (U3)"). The polymer having a carboxyl group may also have structural units other than the above structural units (U1) to (U3) (hereinafter referred to as "structural unit (U4)").

[0096] The structural unit (U1) is preferably derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (u1)").

[0097] Examples of compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids. Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; examples of dicarboxylic acids include maleic acid, fumaric acid, and citraconic acid; and examples of anhydrides of dicarboxylic acids include the anhydrides of the above-mentioned dicarboxylic acids.

[0098] Of these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, or maleic anhydride are preferred in terms of copolymerization reactivity and the solubility of the resulting copolymer in the developer. Compound (u1) can be used alone or as a mixture of two or more.

[0099] The structural unit (U2) is preferably derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter referred to as "compound (u2)").

[0100] The compound (u2) is preferably at least one selected from the group consisting of polymerizable unsaturated compounds having an epoxy group and polymerizable unsaturated compounds having an oxetanyl group.

[0101] Examples of polymerizable unsaturated compounds having an epoxy group include (meth)acrylate oxyranyl (cyclo)alkyl esters, α-alkylacrylate oxyranyl (cyclo)alkyl esters, and glycidyl ether compounds having a polymerizable unsaturated bond; examples of polymerizable unsaturated compounds having an oxetanyl group include (meth)acrylate esters having an oxetanyl group.

[0102] Regarding compound (u2), specific examples include oxyranyl (cyclo)alkyl esters of (meth)acrylate, such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2.6 Examples include decyl (meth)acrylate, etc.

[0103] Examples of α-alkylacrylate oxyranyl (cyclo)alkyl esters include α-ethylacrylate glycidyl, α-n-propylacrylate glycidyl, α-n-butylacrylate glycidyl, α-ethylacrylate 6,7-epoxyheptyl, and α-ethylacrylate 3,4-epoxycyclohexyl.

[0104] Examples of glycidyl ether compounds having polymerizable unsaturated bonds include o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether.

[0105] Examples of (meth)acrylic acid esters having an oxetanyl group include 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

[0106] Among these specific examples, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo[5.2.1.0 2.6 Decyl methacrylate, 3,4-epoxy tricyclo[5.2.1.0 2.6 Decyl acrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane, or 3-ethyl-3-methacryloyloxymethyloxetane are preferred from the viewpoint of polymerizability.

[0107] These compounds (u2) can be used individually or in combination of two or more.

[0108] Among the structural units (U2), structural units having a (meth)acryloyloxy group are preferred as crosslinking groups due to their good sensitivity.

[0109] Structural units having a (meth)acryloyloxy group are obtained by reacting a (meth)acrylic acid ester having an epoxy group with a carboxyl group in the polymer. The resulting structural unit having a (meth)acryloyloxy group is preferably represented by the following general formula (U).

[0110] [ka] In general formula (U), R 1000 and R 1001 Each is independently either a hydrogen atom or a methyl group. u is an integer from 1 to 6. 1002 is a divalent group represented by the following general formula (Uα) or the following general formula (Uβ), where * represents a bond.

[0111] [ka] In the general formula (Uα), R 1003 is a hydrogen atom or a methyl group. In general formulas (Uα) and (Uβ), * indicates a bond.

[0112] Regarding the structural unit represented by general formula (U), for example, when a copolymer having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate, the R in general formula (U) 1002 The general formula is (Uα). On the other hand, when a copolymer having a carboxyl group is reacted with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, the R in the general formula (U) 1002 This is the general formula (Uβ).

[0113] In the reaction between the carboxyl group in the polymer described above and an unsaturated compound such as a (meth)acrylic acid ester having an epoxy group, the unsaturated compound having an epoxy group is added to a solution of the polymer, preferably containing a polymerization inhibitor, in the presence of a suitable catalyst as needed, and stirred for a predetermined time under heating. Examples of catalysts include tetrabutylammonium bromide. Examples of polymerization inhibitors include p-methoxyphenol. The reaction temperature is preferably 70°C to 100°C. The reaction time is preferably 8 to 12 hours.

[0114] In the ratio of structural units of a polymer having a carboxyl group, the content of structural units having a (meth)acryloyloxy group as a crosslinkable group is preferably 10 mol% to 70 mol%, and more preferably 20 mol% to 50 mol%, of the total structural units of the polymer having a carboxyl group.

[0115] By having a ratio of structural units containing (meth)acryloyloxy groups within the above-mentioned range, heat resistance and development defects during development are reduced, and the generation of development residue can be suppressed.

[0116] The structural unit (U3) is preferably derived from a polymerizable unsaturated compound having a silyl group (hereinafter referred to as "compound (u3)").

[0117] Examples of compound (u3) include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane.

[0118] The above-mentioned compound (u3) can be used alone or as a mixture of two or more.

[0119] Structural unit (U4) is a structural unit other than those described above (U1) to (U3), and is preferably a structural unit derived from a polymerizable unsaturated compound other than those described above (u1) to (u3) (hereinafter referred to as "compound (u4)"). Examples of compound (u4) include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, aryl (meth)acrylates, aralkyl (meth)acrylates, dialkyl unsaturated dicarboxylic acid esters, (meth)acrylate esters having an oxygen-containing heterogeneous 5-membered ring or an oxygen-containing heterogeneous 6-membered ring, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds.

[0120] Examples of alkyl (meth)acrylate esters include methyl acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate.

[0121] As (meth)acrylate cycloalkyl esters, for example, (meth)acrylate cyclohexyl, (meth)acrylate 2-methylcyclohexyl, (meth)acrylate tricyclo[5.2.1.0 2,6 ] Decane-8-yl, (meth)acrylic acid 2-(tricyclo[5.2.1.0 2,6 Examples include decane-8-yloxyethyl and isobolonyl (meth)acrylate.

[0122] Examples of (meth)acrylate aryl esters include phenyl acrylate, and examples of (meth)acrylate aralkyl esters include benzyl (meth)acrylate.

[0123] Examples of unsaturated dicarboxylate dialkyl esters include diethyl maleate and diethyl fumarate.

[0124] Examples of (meth)acrylic acid esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring include tetrahydrofuran-2-yl (meth)acrylate, tetrahydropyran-2-yl (meth)acrylate, and 2-methyltetrahydropyran-2-yl (meth)acrylate.

[0125] Examples of vinyl aromatic compounds include styrene and α-methylstyrene.

[0126] Examples of conjugated diene compounds include 1,3-butadiene and isoprene.

[0127] Other polymerizable unsaturated compounds include, for example, 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

[0128] Of the compounds (u4) listed above, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo methacrylate [5.2.1.0 2,6 Decan-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, etc. are preferred.

[0129] Compound (u4) can be used alone or in combination of two or more compounds.

[0130] The preferred polymer having a carboxyl group according to the present invention can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) in the following proportions.

[0131] Furthermore, by reacting a (meth)acrylic acid ester having an epoxy group with the carboxyl group in the structural unit derived from compound (u1) in the obtained copolymer, a structural unit having a (meth)acryloyloxy group can be obtained.

[0132] Compounds (u1) to (u4) are preferably used within the following ranges. Compound (u1): Preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, and even more preferably 5 mol% to 15 mol% Compound (u2): Preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, and even more preferably 20 mol% to 30 mol% Compound (u3): Preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, and even more preferably 10 mol% to 30 mol% Compound (u4): Preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, and even more preferably 25 mol% to 50 mol%

[0133] A polymerizable composition containing a polymer having a carboxyl group, obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compounds (u1) to (u4) within the above range, is preferred because it achieves high resolution without impairing good coatability, and can provide a cured film with a highly balanced set of properties even for highly detailed patterns.

[0134] The weight-average molecular weight (Mw) of the polymer having carboxyl groups is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. By using a polymer having carboxyl groups with an Mw in this range, high resolution can be achieved without impairing good coatability, thus providing a cured film with a highly balanced set of properties, even for highly detailed patterns. Here, the method for measuring the weight-average molecular weight refers to the weight-average molecular weight (Mw) on a polystyrene basis, measured by gel permeation chromatography (GPC).

[0135] Polymers having carboxyl groups can be produced by polymerizing a mixture of polymerizable unsaturated compounds as described above, preferably in a suitable solvent, and preferably in the presence of a radical polymerization initiator.

[0136] Examples of solvents used in polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, and 3-methoxybutanol. These solvents can be used individually or in combination of two or more.

[0137] The radical polymerization initiators are not particularly limited, and examples include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis(2-methylpropionate), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used individually or in combination of two or more.

[0138] Among polymers having carboxyl groups, the polymer described in Japanese Patent Publication No. 2005-234362 is preferred, as is the polymer obtained by reacting the epoxy group of an epoxy compound represented by the following general formula (VI) with an unsaturated monobasic acid, and then with a polybasic acid anhydride.

[0139] [ka] In general formula (VI), X 21R represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO2-, -SS-, -SO-, -CO-, -OCO-, or a group represented by (VIα), (VIβ), or (VIγ) below, and the alkylidene group may be substituted with a halogen atom. 61 , and R 62 Each of these independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, R 61 , and R 62 If multiple instances of each exist, they may be the same or different. f is an integer between 0 and 4, g is an integer between 0 and 4, and m is an integer between 0 and 10. Any optical isomer can exist when m is not 0.

[0140] [ka] In the general formula (VIα), Z 1 Y represents a hydrogen atom, a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. 1 * represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom. The alkyl group, alkoxy group, and alkenyl group may also be substituted with a halogen atom. j represents an integer from 0 to 5, and * represents a bond.

[0141] [ka] In the general formula (VIβ), * represents a bond.

[0142] [ka] In the general formula (VIγ), Y 2 and Z 2 Each of these independently represents an alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an aryloxy group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an arylalkenyl group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms that may be substituted with a halogen atom, or a halogen atom. 2 The methylene group in the group represented by may be substituted with an unsaturated bond, -O- or -S-, Z 2 is adjacent to Z 2 The elements may form a ring, k represents an integer from 0 to 4, r represents an integer from 0 to 8, s represents an integer from 0 to 4, t represents an integer from 0 to 4, the sum of the number of s and t is an integer from 2 to 4, and * represents an associative hand.

[0143] Examples of unsaturated monobasic acids used to react with epoxy compounds include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, and dicyclopentadiene malate.

[0144] Examples of polybasic acid anhydrides to be treated after the treatment with an unsaturated monobasic acid include biphenyltetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, and methylhymic anhydride.

[0145] The reaction molar ratio of the epoxy compound, unsaturated monobasic acid, and polybasic acid anhydride is preferably as follows. Specifically, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, it is preferable that the ratio is such that 0.1 to 1.0 acid anhydride structures of the polybasic acid anhydride are added to one hydroxyl group of the epoxy adduct. The reaction of the epoxy compound, unsaturated monobasic acid, and polybasic acid anhydride can be carried out according to conventional methods.

[0146] Preferred examples of polymers having carboxyl groups include the following [polymer U1] and [polymer U2].

[0147] [Polymer U1] In a flask equipped with a condenser and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were charged. Subsequently, 55 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate, and 2 parts by mass of α-methylstyrene dimer as a molecular weight modifier were charged. While gently stirring, the temperature of the solution was raised to 80°C and maintained at this temperature for 4 hours, then raised to 100°C and maintained at this temperature for 1 hour to polymerize and obtain a solution containing the copolymer. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the copolymer-containing solution, and after stirring at 90°C for 30 minutes under an air atmosphere, 74 parts by mass of glycidyl methacrylate were added and the reaction was carried out at 90°C for 10 hours to obtain polymer U1 with a weight-average molecular weight Mw of 9000. Polymer U1 has structural units (U1), structural unit (U2), and structural unit (U4).

[0148] [Polymer U2] In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were charged. Then, 18 parts by mass of methacrylic acid, 25 parts by mass of tricyclo[5.2.1.02.6]decan-8-yl methacrylate, 5 parts of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane and 32 parts by mass of glycidyl methacrylate were charged, and the mixture was purged with nitrogen. The temperature of the solution was then slowly raised to 80°C while stirring. Polymerization was carried out by maintaining this temperature for 5 hours to obtain polymer U2 with a weight-average molecular weight Mw of 12000. Polymer U2 has structural units (U1), (U2), (U3), and (U4).

[0149] One embodiment of the polymerizable composition according to the present invention is the alkali-developable photosensitive resin composition of the present invention, which contains a polymerization initiator (A), an ethylenically unsaturated compound (B), and an alkali-developable compound (D) as essential components, and optionally contains a combination of inorganic compounds, solvents, and other components. Among the alkali-developable photosensitive resin compositions according to the present invention, those containing a coloring agent (C) are also referred to as the colored alkali-developable photosensitive resin composition according to the present invention. The ethylenically unsaturated compound (B) and the alkali-developable compound (D) may be the same compound, or they may be different, and they may be used individually or in combination of two or more.

[0150] To improve the developability of the (colored) alkali-developable photosensitive resin composition according to the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound can be used together with the alkali-developable compound which may have ethylenically unsaturated bonds. The alkali-developable compound which may have ethylenically unsaturated bonds preferably has an acid value of 5 to 120 mgKOH / g in its solid content, and the amount of monofunctional or polyfunctional epoxy compound used is preferably selected to satisfy the above acid value.

[0151] Examples of monofunctional epoxy compounds 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, and propargyl glycidyl ether. Examples include lysidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, and compounds No. A2 and No. A3 mentioned above.

[0152] As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, as this can yield a (colored) alkali-developable photosensitive resin composition with even better properties. As the bisphenol-type epoxy compound, epoxy compounds represented by general formula (VI) can be used, as well as bisphenol-type epoxy compounds such as hydrogenated bisphenol-type epoxy compounds.

[0153] In addition, as glycidyl ethers, 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, 1,1,1,1-tetra(glycidyloxymethyl)methane, etc. can be used.

[0154] Other novolac-type epoxy compounds such as phenol novolac-type epoxy compounds, biphenyl novolac-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol A novolac-type epoxy compounds, and dicyclopentadiene novolac-type epoxy compounds; alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane; phthalate dig Glycidyl esters such as lysidyl esters, diglycidyl tetrahydrophthalate, and glycidyl dimer acid; glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl p-aminophenol, and N,N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene-type epoxy compounds; triphenylmethane-type epoxy compounds; and dicyclopentadiene-type epoxy compounds may also be used.

[0155] In particular, when the polymerizable composition according to the present invention is an alkali-developable photosensitive resin composition, the content of the alkali-developable compound which may have the ethylenically unsaturated bond is preferably 1 to 20% by mass, and particularly preferably 3 to 12% by mass, in the alkali-developable photosensitive resin composition according to the present invention.

[0156] A solvent may be added to the polymerizable composition according to the present invention. The solvent may typically be one that can dissolve or disperse the above components (polymerization initiator (A) and ethylenically unsaturated compound (B), etc.) as needed, such as ketones including methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; or methyl acetate, ethyl acetate. Ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol-1 Ether ester solvents such as monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, and ethoxyethyl ether 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, D-limonene, and pinene; and paraffin such as mineral spirits, Swazole #310 (Cosmo Matsuyama Petroleum Co., Ltd.) and Solvesso #100 (Exxon Chemicals). Examples of solvents include: phosphate-based solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide (DMAc); N-methylpyrrolidone; dimethyl sulfoxide; and water. These solvents can be used individually or as a mixture of two or more solvents.

[0157] Among these, ketones, ether ester solvents, and especially propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone are preferred because they exhibit good compatibility between the resist and polymerization initiator (A) in polymerizable compositions.

[0158] Furthermore, the polymerizable composition according to the present invention may optionally contain conventional additives such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; defoamers; leveling agents; surface modifiers; antioxidants; ultraviolet absorbers; dispersion aids; anti-aggregation agents; catalysts; effect enhancers; crosslinking agents; and thickeners.

[0159] The polymerizable composition according to the present invention may contain a dispersant for dispersing a colorant (C) and / or an inorganic compound. The dispersant is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and commercially available dispersants, such as the BYK series from Bic Chemie, can be used. In particular, polymeric dispersants made of polyester, polyether, or polyurethane having a basic functional group are preferably used, the basic functional group having a nitrogen atom, the functional group having a nitrogen atom being an amine and / or a quaternary salt thereof, and having an amine value of 1 to 100 mgKOH / g.

[0160] Latent additives are represented by the following general formulas (A) to (C).

[0161] [ka] In general formula (A), ring A 2 R is a six-membered ring alicyclic, aromatic, or heterocyclic ring, 81 , R 82 , R 83 , R 84 and R 85is a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or -O-R 86 represents, R 81 R 82 R 83 R 84 and R 85 at least one of which is not a hydrogen atom, R 86 represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or a trialkylsilyl group.

[0162]

Chemical formula

[0163]

Chemical formula

[0164] [ka] In the general formula (C), k = 2 to 6, and X 9 When k=2, it is the group represented by the above general formula (2), when k=3, it is the group represented by the following general formula (3), when k=4, it is the group represented by the following general formula (4), when k=5, it is the following general formula (5), and when k=6, it is the following general formula (6). 111 , R 112 , R 113 and R 114R represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have substituents, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. 111 , R 112 , R 113 and R 114 At least one of them is not a hydrogen atom, and ring A 1 and R 86 This is the same as the general formula (A) above.

[0165] [ka] In general formula (3), Y 11 This represents a trivalent aliphatic hydrocarbon group with 3 to 35 carbon atoms, an alicyclic hydrocarbon group with 3 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms. 11 , Z 12 and Z 13 These are, independently, direct bonds, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO-, -NR 121 -,-PR 121 - Represents an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have substituents, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have substituents, or a heterocyclic group having 2 to 35 carbon atoms which may have substituents, R 121 This represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have substituents, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have substituents, or a heterocyclic group having 2 to 35 carbon atoms which may have substituents, and the methylene group in the aliphatic hydrocarbon group may be substituted with a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O-, or -SO2-.

[0166] [ka] In general formula (4), Y 12represents a carbon atom, or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and the methylene group in the aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, Z 11 ~Z 14 These are, independently, Z in general formula (3). 11 ~Z 13 These are groups within the same range as the groups represented by .

[0167] [ka] In general formula (5), Y 13 Z represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms, and the methylene group in the aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-. 11 ~Z 15 These are, independently, Z in general formula (3). 11 ~Z 13 These are groups within the same range as the groups represented by .

[0168] [ka] In general formula (6), Y 14 Z represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and the methylene group in the aliphatic hydrocarbon group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-. 11 ~Z 16 These are, independently, Z in general formula (3). 11 ~Z 13 These are groups within the same range as the groups represented by .

[0169] In the above polymerizable composition, the properties of the cured product can be improved by using organic polymers (excluding ethylenically unsaturated compound (B)). Examples of organic polymers include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin, etc. Among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred. When using organic polymers, the amount used is preferably 10 to 500 parts by mass per 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

[0170] Sulfur atom-containing compounds are generally used as chain transfer agents or sensitizers. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropantris (3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptoethanol) Mercapto compounds such as lucaptopropionate, disulfide compounds obtained by oxidation of mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, and other iodized alkyl compounds, trimethylolpropanetris(3-mercaptoisobutyrate), butanediolbis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, Tandiol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, and the following compound No.Examples include C1, aliphatic polyfunctional thiol compounds such as tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, and Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko Corporation.

[0171] [ka]

[0172] As surfactants, fluorinated surfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates; anionic surfactants such as alkali salts of higher fatty acids, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halates and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; and silicone-based surfactants can be used, and these may be used in combination.

[0173] As a silane coupling agent, for example, silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, silane coupling agents having an isocyanate group, acryloyl group, methacryloyl group, or epoxy group, such as KBE-9007, KBM-5103, KBM-502, and KBE-403, are preferably used.

[0174] Examples of melamine compounds include (poly)methylolmelamine, (poly)methylol glycoluryl, (poly)methylolbenzoguanamine, and (poly)methylolurea, in which all or part (at least two) of the active methylol groups (CH2OH groups) in the nitrogen compound are alkyl etherified.

[0175] Here, the alkyl group constituting the alkyl ether can be a methyl group, an ethyl group, or a butyl group, and these may be the same or different from each other. Furthermore, the methylol group that has not been alkyl etherified may undergo self-condensation within a single molecule, or it may undergo condensation between two molecules, resulting in the formation of an oligomeric component.

[0176] Specifically, hexamethoxymethylmelamine, hexasubtoxymethylmelamine, tetramethoxymethylglycoluryl, tetrabutoxymethylglycoluryl, etc., can be used. Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexasubtoxymethylmelamine are preferred.

[0177] As a leveling agent, any existing leveling agent that provides a leveling effect can be used, but among them, silicone-based leveling agents and fluorine-based leveling agents are particularly preferred.

[0178] Commercially available silicone leveling agents can be used as silicone leveling agents, such as BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, and BYK-34. 1. BYK-344, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720 (all manufactured by Big Chemie Japan); AC Commercially available products such as FS 180, AC FS 360, AC S 20 (all manufactured by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (all manufactured by Kyoeisha Chemical); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (all manufactured by Shin-Etsu Chemical Co., Ltd.); LP-7001, LP-7002, 8032 ADDITIVE, 57 ADDITIVE, L-7604, FZ-2110, FZ-2105, 67 ADDITIVE, 8618 ADDITIVE, 3 ADDITIVE, 56 ADDITIVE (all manufactured by Toray Dow Corning) can be used.

[0179] As a fluorine-based leveling agent, commercially available fluorine-based leveling agents can be used, for example: Optool DSX, Optool DAC-HP (both manufactured by Daikin Industries); Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-611, Surflon S-651, Surflon S-386 (all manufactured by AGC Seimi Chemical); BYK-340 (manufactured by Bic Chemie Japan); AC 110a, AC 100a (both manufactured by Algin Chemie); Megafac F-114, Megafac F-410, Megafac F-444, Megafac EXP TP-2066, Megafuck F-430, Megafuck F-472SF, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck R-94, Megafuck RS-72-K, Megafuck RS-75, Megafuck F-556, Megafuck EXP TF-1367, Megafuck EXP TF-1437, Megafuck F-558, Megafuck EXP TF-1537 (all manufactured by DIC); FC-4430, FC-4432 (all manufactured by Sumitomo 3M); Futegent 100, Futegent 100C, Futegent 110, Futegent 150, Futegent 150CH, Futegent AK, Futegent 501, Futegent 250, Futegent Commercially available products such as 251, Futergent 222F, Futergent 208G, Futergent 300, Futergent 310, Futergent 400SW (all manufactured by Neos); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, PF-3320 (all manufactured by Kitamura Chemical Industry) can be used.

[0180] In the polymerizable composition described above, the amounts of any component other than the polymerization initiator (A), ethylenically unsaturated compound (B), colorant (C), alkali-developable compound (D), solvent, inorganic compound, and organic polymer are appropriately selected according to their intended use and are not particularly limited, but preferably the total amount is 50 parts by mass or less per 100 parts by mass of the ethylenically unsaturated compound (B).

[0181] The cured product of the present invention is obtained by curing the above polymerizable composition or alkali-developable photosensitive resin composition.

[0182] The polymerizable composition, alkali-developable photosensitive resin composition, or cured product according to the present invention is a photocurable paint or varnish; photocurable adhesive; printed circuit board; color filter in liquid crystal display elements for color displays in display devices (color televisions, PC monitors, personal digital assistants, digital cameras, etc.); color filter for CCD image sensors; electrode material for plasma display panels; powder coating; printing ink; printing plate; adhesive; dental composition; gel coat; photoresist for electronics; electroplating resist; etching resist; dry film; solder resist; resist for forming structures for various display devices; composition for encapsulating electrical and electronic components; solder resist; magnetic It can be used in a variety of applications, including: recording materials; micro-mechanical parts; waveguides; optical switches; plating masks; etching masks; color test systems; glass fiber cable coatings; screen printing stencils; materials for manufacturing three-dimensional objects by stereolithography; holographic recording materials; image recording materials; micro-electronic circuits; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules; photoresist materials for printed circuit boards; photoresist materials for UV and visible laser direct imaging systems; and photoresist materials or protective films used for dielectric layer formation in sequential lamination of printed circuit boards, with no particular limitations on its applications.

[0183] The polymerizable composition or alkali-developable photosensitive resin composition according to the present invention is useful as a polymerizable composition for color filters because it can form a high-brightness cured product.

[0184] The polymerizable composition or alkali-developable photosensitive resin composition according to the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertically aligned liquid crystal display elements. It is particularly useful as a polymerizable composition for simultaneously forming protrusions and spacers for vertically aligned liquid crystal display elements.

[0185] Next, the method for producing a cured product of the above polymerizable composition or alkali-developable photosensitive resin composition will be described in detail below.

[0186] The above polymerizable composition or alkali-developable photosensitive resin composition can be applied onto a support substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, dipping, etc. Further, after once applying it onto a support substrate such as a film, it can also be transferred onto another support substrate, and there is no limitation on the application method.

[0187] The method for producing a cured product of the above polymerizable composition includes a step of curing the polymerizable composition by light irradiation or a step of curing it by heating.

[0188] As the light source used in the step of curing by light irradiation, electromagnetic wave energy having a wavelength of 2000 Å to 7000 Å obtained from an ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, mercury vapor arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc., or high energy rays such as electron beams, X-rays, radiation, etc. can be used. Preferably, examples include ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm.

[0189] Furthermore, by using laser light as the exposure light source, laser direct lithography, which forms images directly from digital information such as computers without using masks, is useful because it improves not only productivity but also resolution and positional accuracy. While laser light with a wavelength of 340-430 nm is preferably used, lasers emitting light in the visible to infrared region, such as excimer lasers, nitrogen lasers, argon ion lasers, helium-cadmium lasers, helium-neon lasers, krypton ion lasers, various semiconductor lasers, and YAG lasers, can also be used. When using these lasers, a sensitizing dye that absorbs the relevant region from visible to infrared is added.

[0190] The process of curing by heating will now be described. The heating temperature is set appropriately according to the thickness of the coating film or cured product of the composition to be treated, the polymerization initiation temperature of the thermal polymerization initiator, etc., but for example it can be 50°C to 250°C, and more preferably 100°C to 200°C, and especially preferably 100°C to 150°C. In the method for producing the cured product of the present invention, the heating temperature refers to, for example, the surface temperature of the polymerizable composition or cured product. The heating time can be 10 minutes to 2 hours. The heating time refers to the time during which the composition or cured product maintains the temperature after it has reached the predetermined temperature.

[0191] The above-mentioned spacer for liquid crystal display panels is preferably formed by (1) forming a coating film of the polymerizable composition according to the present invention on a substrate, (2) irradiating the coating film with radiation through a mask having a predetermined pattern shape, (3) baking after exposure, (4) developing the coating after exposure, and (5) heating the coating after development.

[0192] The polymerizable composition according to the present invention, to which an ink-repellent agent has been added, is useful as a partition-forming resin composition for inkjet systems. The composition is used for color filters, and is particularly preferably used for partitions in inkjet color filters with a profile angle of 50° or more. As the ink-repellent agent, a composition consisting of a fluorine-based surfactant and a fluorine-based surfactant is preferably used.

[0193] An optical element is manufactured by a method in which partitions formed from a polymerizable composition according to the present invention divide a transfer target, and droplets are applied to the recesses on the divided transfer target by an inkjet method to form an image region. In this case, it is preferable that the droplets contain a coloring agent and that the image region is colored, and an optical element manufactured by the above optical element manufacturing method is preferably used, having at least a group of pixels consisting of a plurality of colored regions and partitions separating each colored region of the pixel group on a substrate. [Examples]

[0194] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0195] <Example 1: Synthesis of Compound 1> (Production of intermediate 1-A) Carbazole (10.7 g, 63.7 mmol), DMF (45.0 g), bromocyclopentane (38.0 g, 255 mmol), and potassium hydroxide (14.3 g, 255 mmol) were charged into a reaction vessel and reacted at 50°C for 6 hours. After the reaction, deionized water and ethyl acetate were added, and the oil-water separation was performed. The organic layer was washed three times with water, and intermediate 1-A was obtained by silica gel column purification.

[0196] [ka]

[0197] (Production of intermediate 1-B) Charge an aluminum chloride (9.5 g, 71.8 mmol) and 100 g of dichloroethane into a reaction vessel. While cooling with ice, charge intermediate 1-A (15.4 g, 62.3 mmol) and cyclohexylpropionyl chloride (12.5 g, 71.8 mmol) in this order. After reacting at room temperature for 1 hour, pour the reaction solution into ice water. After separating the oil and water layers, wash the organic layer three times with water and perform silica gel column purification to obtain intermediate 1-B.

[0198]

Chemical formula

[0199] (Production of intermediate 1-C) Charge an aluminum chloride (12.8 g, 95.7 mmol) and 100 g of dichloroethane into a reaction vessel. While cooling with ice, charge intermediate 1-B (18.2 g, 43.5 mmol) and methyl chloroglyoxylate (5.9 g, 47.9 mmol) in this order. After reacting at room temperature for 1 hour, pour the reaction solution into ice water. After separating the oil and water layers, wash the organic layer three times with water and perform silica gel column purification to obtain intermediate 1-C.

[0200]

Chemical formula

[0201] [[ID=2,6]](Production of intermediate 1-D) Charge intermediate 1-C (8.0 g, 17.4 mmol) and DMF (30.0 g) into a reaction vessel. Then, while stirring at 5 °C, charge 1.8 g of 35% hydrochloric acid and isobutyl nitrite (3.6 g, 34.8 mmol) in this order, and react at room temperature for 12 hours. Charge ethyl acetate, and after separating the oil and water layers, wash the organic layer three times with water and perform silica gel column purification to obtain intermediate 1-D.

[0202]

Chemical formula

[0203] (Production of compound 1) Intermediate 1-D (9.24 g, 17.9 mmol) and 30.0 g of ethyl acetate were charged into a reaction vessel. Acetyl chloride (1.54 g, 19.7 mmol) and triethylamine (1.99 g, 19.7 mmol) were added dropwise under ice cooling. After stirring at room temperature for 1 hour, deionized water was added and oil-water separation was performed. The organic layer was washed three times with water, and after desolvation, it was purified by silica gel column (ethyl acetate / hexane = 3 / 10) to obtain compound 1 (2.1 g, yield 21%). The obtained compound is dissolved in deuterated chloroform. 1 1H-NMR measurements were performed. The results are shown in Table 1.

[0204] [ka]

[0205] <Example 2: Synthesis of Compound 2> Compound 2 was obtained in the same manner as in Example 1, except that the bromocyclopentane used in the preparation of intermediate 1-A was replaced with 1-bromo-2-ethylhexane. The obtained compound is dissolved in deuterated chloroform. 1 1H-NMR measurements were performed. The results are shown in Table 1.

[0206] [ka]

[0207] <Example 3: Synthesis of Compound 3> Compound 3 was obtained in the same manner as in Example 1, except that the bromocyclopentane used in the preparation of intermediate 1-A was replaced with 1-bromo-2-methylpropane. The obtained compound is dissolved in deuterated chloroform. 1 1H-NMR measurements were performed. The results are shown in Table 1.

[0208] [ka]

[0209] <Example 4: Synthesis of Compound 4> Compound 4 was obtained in the same manner as in Example 1, except that bromocyclopentane used in the production of intermediate 1-A was replaced with 1-bromo-2-ethylhexane, and cyclohexylpropionyl chloride used in the production of compound 1-B was replaced with phenylacetyl chloride. The obtained compound is dissolved in deuterated chloroform. 1 1H-NMR measurements were performed. The results are shown in Table 1.

[0210] [ka]

[0211] [Table 1]

[0212] <Manufacturing Example 1: Blue Pigment Dispersion No. 1> A blue pigment dispersion was prepared by dispersing DISPERBYK-161 (12.5 parts by mass; manufactured by BIC Chemie Japan) as a dispersant and Pigment Blue 15:6 (15 parts by mass) as a colorant in PGMEA (72.5 parts by mass) using a bead mill.

[0213] <Evaluation method: Solubility> Compounds 1-4 prepared in Examples 1-4 and comparative compound A'-1 described below were each dissolved in an organic solvent (propylene glycol monomethyl ether acetate (PGMEA)) at room temperature, and their solubility was evaluated according to the following criteria. The results are shown in Table 2. A: 2wt% or more B: Less than 2 wt%

[0214] [Table 2]

[0215] [ka]

[0216] <Evaluation method: Sensitivity> Polymerizable compositions were prepared according to the formulations listed in Table 3. The polymerizable compositions were spin-coated onto a glass substrate (so that the chromaticity coordinates after post-baking were (x, y) = (0.135, 0.098)), pre-baked at 90°C for 120 seconds using a hot plate, and then cooled at 23°C for 60 seconds. Subsequently, the substrates were exposed using an ultra-high pressure mercury lamp through a photomask (mask aperture 30 μm) (exposure gap 100 μm, exposure dose 40 mJ / cm²). 2 The images were developed using a 0.04% by mass aqueous KOH solution as the developer, then thoroughly washed with water, and post-baked in a clean oven at 230°C for 20 minutes to fix the pattern. The obtained patterns were observed with an electron microscope, and the line width of the area corresponding to the mask aperture was measured. Sensitivity was evaluated according to the following criteria. The results are shown in Table 3. A larger line width indicates better sensitivity. Line width of 30 μm or more is classified as A Line width less than 30 μm is classified as B

[0217] <Evaluation method: Brightness> A polymerizable composition was spin-coated onto a glass substrate (so that the chromaticity coordinates after post-baking were (x, y) = (0.135, 0.098)). Pre-baking was performed using a hot plate at 90°C for 120 seconds, followed by cooling at 23°C for 60 seconds. Subsequently, a pressure of 150 mJ / cm² was applied using an ultra-high pressure mercury lamp. 2 After exposure, evaluation samples were prepared by post-baking at 230°C for 20 minutes using a clean oven. The Y value was determined from the transmittance of the obtained samples in the 380-780nm range according to JIS Z8701, and the brightness was evaluated according to the following criteria. The results are shown in Table 3. A higher Y value indicates higher brightness and higher transmittance in the visible light region, making it more useful. Y value of 11.0 or higher is A If the Y value is less than 11.0, then B

[0218] The symbols in the table are as follows: A-1: Compound 1 A-2: Compound 2 A-3: Compound 3 A-4: Compound 4 A'-1: Comparative compound A'-1 B-1: Kayarad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku Co., Ltd.) C-1: Blue Pigment Dispersion No. 1 D-1: SPC-3000 (Alkali-developable compound; polymer containing acrylic and carboxyl groups; manufactured by Showa Denko Corporation, solids content 42.7%, PGMEA solution) E-1: KBE-403 (Coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) F-1: PGMEA (solvent)

[0219] [Table 3]

[0220] As shown in Table 2, the compound of the present invention exhibits excellent solubility in solvents. Furthermore, as shown in Table 3, it was confirmed that polymerizable compositions using a polymerization initiator containing the compound of the present invention exhibit excellent sensitivity, yielding cured products with high brightness and high transmittance in the visible light region. [Industrial applicability]

[0221] The compound of the present invention is useful as a polymerization initiator because it is highly sensitive and has excellent solubility in solvents. Furthermore, polymerizable compositions using a polymerization initiator containing the compound of the present invention yield cured products with high transmittance in the visible light region, making them particularly useful as polymerizable compositions for color filters.

Claims

1. A compound having a group represented by the following general formula (I) and a group represented by the following general formula (II) within the same molecule, and having a structure represented by the following general formula (III). 【Chemistry 1】 In the formula, R1 represents butyl, hexyl, heptyl, octyl, nonyl, decyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, isononyl, a cycloalkylalkyl group having 4 to 10 carbon atoms, or a phenyl group. R2 represents an alkyl group having 1 to 10 carbon atoms. n represents 0 or 1, * represents a coupling, If a compound contains multiple groups represented by general formula (I), then multiple R groups exist. １ , R ２ And n may be the same or different. 【Chemistry 2】 In the formula, R ４ This represents an alkoxy group with 1 to 10 carbon atoms. * represents a coupling, If a compound contains multiple groups represented by general formula (II), then multiple R groups exist. ４ They may be the same or different. 【Transformation 3】 R 11 represents the group represented by the above general formula (I), R 12 represents the group represented by the above general formula (II), R 13 represents a branched alkyl group or cycloalkyl group having 3 to 20 carbon atoms. a represents an integer from 1 to 3, and if a is an integer greater than or equal to 2, the multiple R11s may be the same or different. b represents an integer from 1 to 3, and if b is an integer greater than or equal to 2, the multiple R12s may be the same or different. c represents 1, A1 is a structure represented by the following general formula (IVα). 【Chemistry 4】 The above general formula (IVα) represents the structure when the groups R11, R12, and R13 in the above general formula (III) are replaced with hydrogen atoms. In the formula, X1 represents NR13, and X2 represents a single bond. The substituent positions of R11 and R12 are in the para position relative to the binding site of X1.

2. A polymerization initiator containing the compound described in claim 1.

3. A polymerizable composition containing the polymerization initiator (A) and the ethylenically unsaturated compound (B) according to claim 2.

4. The polymerizable composition according to claim 3, further containing a coloring agent (C).

5. A cured product of the polymerizable composition according to claim 3 or 4.

6. A color filter containing the cured product described in claim 5.

7. A method for producing a cured product comprising the steps of curing the polymerizable composition according to claim 3 or 4 by light irradiation or by heating.

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