Polymerizable composition, cured product, display device, and method for producing the cured product

Abstract

To provide a polymerizable composition having storage stability in addition to low temperature curability, and capable of patterning with high definition.SOLUTION: A polymerizable composition comprises a tertiary amine compound or its salt (A), an annular ether compound (B), an alkali developing resin (C), a polymerization initiator (D) and a compound (E) having an active hydrogen capable of reacting with the annular ether compound. The tertiary amine compound is preferably a compound represented by the following general formula (I). (R101,R102 and R103 each independently represent a heterocyclic group of 2 to 10 carbon atoms, a group of from 3 to 20 carbon atoms containing a heterocyclic ring, a hydrocarbon group of 1 to 20 carbon atoms, etc., and R104 is a hydrogen atom or a hydrocarbon group of 1 to 20 carbon atoms).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymerizable composition containing a cyclic ether compound, an alkali-developable resin, and a polymerization initiator, a cured product obtained from the polymerizable composition, a method for producing the cured product, and a display device using the cured product. [Background technology]

[0002] 2. Description of the Related Art Polymerizable compositions containing a cyclic ether compound, an alkali-developable resin, and a polymerization initiator have been used in a variety of applications, such as solder resists, color filters, black matrices, and black column spacers.

[0003] For example, Patent Document 1 describes a photosensitive resin composition used for producing a resin film-coated substrate by applying the photosensitive resin composition onto a substrate having a heat resistance of 140° C. or less, exposing the composition through a photomask, removing the unexposed areas by development, and then heating the composition at 140° C. or less to form a predetermined resin film pattern, (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds; (C) an epoxy compound, (D) a curing agent and / or a curing accelerator for an epoxy compound; (E) a photopolymerization initiator, (F) a solvent, The photosensitive resin composition is characterized in that the total amount of components C and D is 6 to 24 mass % of the solid content excluding component F. Patent Document 1 describes that the composition described therein has low-temperature curing properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-70720 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, a polymerizable composition that contains a cyclic ether compound, an alkali developable resin, and a polymerization initiator, has low-temperature curing properties and storage stability, and is capable of forming high-definition patterning has not been obtained.

[0006] An object of the present invention is to solve the problems associated with the above-mentioned conventional techniques, and to provide a polymerizable composition that has storage stability in addition to low-temperature curing properties and is capable of high-definition patterning, a cured product thereof, a method for producing the cured product, and a display device using the cured product. [Means for solving the problem]

[0007] As a result of extensive investigations, the present invention has achieved the above object by providing the following [1] to

[11] .

[0008] [1] A tertiary amine compound or a salt thereof (A), Cyclic ether compound (B), Alkaline developing resin (C), A polymerization initiator (D) and A polymerizable composition comprising a compound (E) having an active hydrogen capable of reacting with the cyclic ether compound.

[0009] [2] The polymerizable composition according to [1], wherein the tertiary amine compound is a compound represented by the following general formula (I): [ka] (In the formula, R 101 , R 102 and R 103 each independently represents a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic ring-containing group having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms in which one or more methylene groups are substituted with a divalent group selected from the following <Group A>, <Group A> is -O-, -S-, -NR 104-, -CO-, -O-CO-, -CO-O- and -SO2-; R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 104 When multiple are present, they may be independently the same or different.)

[0010] [3] The polymerizable composition according to [1] or [2], wherein the cyclic ether compound (B) is an epoxy compound.

[0011] [4] The alkaline developable resin (C) is The polymerizable composition according to any one of [1] to [3], which is an unsaturated compound having a structure obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (II), and a polybasic acid anhydride:

[0012] [ka] (In the formula, M represents a direct bond, -O-, -S-, -SO2-, -SS-, -SO-, -CO-, -OCO-, 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 an unsaturated bond, -O- or -S-, or represents a group selected from the group represented by the following formulae (a), (b), (c) and (d): R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 (Hereinafter referred to as “R 1 ~R 8 ) each independently represent a hydrogen atom, a halogen atom, 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 an unsaturated bond, -O- or -S-; n is a number from 0 to 10, If n ≥ 1, multiple R 1 ~R8 and M may be the same or different.) [ka] (In the formula, R 9 represents a hydrocarbon group having 1 to 20 carbon atoms, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 (Hereinafter referred to as “R 10 ~R 38 ) each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the group having 3 to 20 carbon atoms are substituted with an unsaturated bond, -O- or -S-; R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 22 and R 15 , R 15 and R 16 , R 30 and R23 , R 23 and R 24 , R 24 and R 25 , R 38 and R 31 , R 31 and R 32 , R 32 and R 33 , R 34 and R 35 , R 35 and R 36 and R 36 and R 37 may combine to form a ring, In the groups represented by formulae (a), (b), (c) and (d), * represents a bond.

[0013] [5] The polymerizable composition according to any one of [1] to [4], wherein the polymerization initiator (D) is a polymerization initiator having a group represented by the following general formula (III): [ka] (In the formula, R 41 and R 42 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle and having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the group having 3 to 20 carbon atoms are substituted with the following <Group B>, <Group B> is -O-, -CO-, -COO-, -OCO-, -NR 43 -, -NR 43 CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- and CSO-, R 43 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, m1 represents 0 or 1; In the formula, * represents a bond.

[0014] [6] The polymerizable composition according to any one of [1] to [5], wherein the compound (E) having an active hydrogen capable of reacting with the cyclic ether compound is a thiol compound.

[0015] [7] The polymerizable composition according to any one of [1] to [6], further comprising a colorant (F).

[0016] [8] A polymerizable composition comprising the polymerizable composition according to any one of [1] to [7], further comprising an ethylenically unsaturated compound (G) having a molecular weight of 1,000 or less.

[0017] [9] A cured product of the polymerizable composition according to any one of [1] to [8].

[0018]

[10] A display device containing the cured product described in [9].

[0019]

[11] A method for producing a cured product using the polymerizable composition described in [9]. Effect of the Invention

[0020] The polymerizable composition of the present invention has excellent storage stability and enables high-precision patterning, while having excellent low-temperature curing properties that have been difficult to obtain in the past, contributing to energy saving in the manufacturing process. In addition, since it can be applied to members with poor heat resistance, it is useful as a patterning material for OLEDs and quantum dot devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The polymerizable composition of the present invention will be described in detail below based on preferred embodiments. The polymerizable composition of the present invention contains a tertiary amine compound or a salt thereof (A), a cyclic ether compound (B), an alkali-developable resin (C), a polymerization initiator (D), and a compound having an active hydrogen capable of reacting with the cyclic ether compound (E).

[0022] The present inventors have intensively studied a configuration that provides low-temperature curing in a polymerizable composition having a cyclic ether compound, an alkali-developable resin, and a polymerization initiator. As a result, it has been surprisingly found that by using a specific amine compound and a compound having active hydrogen capable of reacting with the cyclic ether compound in combination, high-definition patterning is possible, and remarkable low-temperature curing properties that have been difficult to obtain in the past can be obtained while maintaining storage stability. The present invention enables energy saving in the manufacturing process and application of non-heat-resistant members that have not been possible in the past, for example, in black column spacer applications, black matrix applications, and color resist applications, since the curing temperature, which has conventionally been required at 200 to 250°C, can be reduced to about 100°C. Each component will be described in turn below.

[0023] <Tertiary amine compound or its salt (A)> In the present invention, a tertiary amine compound refers to a compound in which one nitrogen atom is bonded to three different carbon atoms. As the tertiary amine compound or its salt (A) (hereinafter also referred to as "(A) component"), an aliphatic tertiary amine compound or its salt and an aromatic tertiary amine compound or its salt are known, but from the viewpoint of high low-temperature curing property and storage stability, an aromatic tertiary amine compound or its salt is preferable. For the same reason, as the (A) component, a heterocyclic aromatic tertiary amine compound or its salt is more preferable, an azole heterocyclic aromatic compound or its salt is even more preferable, and an imidazole compound or its salt is particularly preferable. A suitable example of a tertiary amine compound that is an imidazole compound is a compound in which a hydrocarbon group or the like is bonded to one of the two nitrogen atoms on the imidazole ring and is not bonded to the other nitrogen atom. The hydrocarbon group or the like is a group that is bonded to the nitrogen atom of the imidazole ring through a carbon atom, and examples thereof include a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in a hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <Group A>. Examples of the salts of tertiary amine compounds include organic acid salts and inorganic acid salts of tertiary amine compounds. Examples of organic acid salts include carboxylates such as stearic acid and behenic acid, and sulfonates, and examples of inorganic acid salts include sulfates, hydrochlorides, nitrates, phosphates, and the like.

[0024] From the viewpoints of excellent low-temperature curing properties and high storage stability, the most preferred tertiary amine compound is a compound represented by the following general formula (I).

[0025] [ka]

[0026] (In the formula, R 101 , R 102 and R 103each independently represents a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in a hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the following <Group A>, <Group A> is -O-, -S-, -NR 104 -, -CO-, -O-CO-, -CO-O- and -SO2-; R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 104 When multiple are present, they may be independently the same or different.)

[0027] R 101 , R 102 , R 103 and R 104 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (1) include aliphatic hydrocarbon groups such as a linear or branched chain alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 4 to 20 carbon atoms, and aromatic hydrocarbon groups such as an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms.

[0028] Examples of the linear or branched chain alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl.

[0029] Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 3-cyclohexenyl.

[0030] Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl, and tetradecahydroanthracenyl.

[0031] Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl, and decahydronaphthylpropyl.

[0032] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 2-fluorophenyl, and 3-fluorophenyl.

[0033] Examples of the arylalkyl group having 7 to 20 carbon atoms include the above-mentioned alkyl groups in which one or more hydrogen atoms have been substituted with the above-mentioned aryl groups. Specific examples include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, naphthylpropyl, and groups in which hydrogen atoms in these rings have been substituted with the above-mentioned aliphatic hydrocarbon groups.

[0034] R 101 , R 102 and R 103 The heterocyclic group represented by the following formula means a group in which one hydrogen atom has been removed from a heterocyclic compound.

[0035] The heterocyclic group is not particularly limited, and examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, cinnolyl, phthalazyl, pryl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzoyl, benzo ... Examples of such aryl groups include thiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, indolyl, benzoxazolyl, benzotriazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, and 2,4-dioxyoxazolidin-3-yl, as well as isocyanuric and 1,3-dioxolanyl.

[0036] R 101 , R 102 and R 103 The group having 3 to 20 carbon atoms and containing a heterocycle, represented by the following formula (1), means a group in which a heterocycle group and a group other than a heterocycle group are bonded. The bonding site may be located on the heterocycle or on the group other than the heterocycle. The group other than the heterocyclic group is not particularly limited, but may be, for example, a hydrocarbon group having 1 to 6 carbon atoms, and any number of bonds, 1 or more, is possible as long as the number of carbon atoms in the group containing the heterocycle is 20 or less. Examples of the hydrocarbon group having 1 to 6 carbon atoms include the above-mentioned R 101 Examples of the hydrocarbon group having 1 to 20 carbon atoms, represented by the above formulae, include divalent groups having a predetermined number of carbon atoms obtained by removing one hydrogen atom from the groups exemplified above.

[0037] Examples of the heterocyclic ring-containing group having 3 to 20 carbon atoms include groups having the following structures.

[0038] [ka]

[0039] (In the above formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents an alkylene group having 1 to 6 carbon atoms. In addition, * in the formula means a bond. A bond spanning multiple rings indicates that the bond may be on any of these rings.)

[0040] The alkyl group having 1 to 6 carbon atoms represented by R in the above formula is the above-mentioned R 101 Among the examples of the alkyl group having 1 to 20 carbon atoms, which are represented by the above formulae, those having 1 to 6 carbon atoms can be mentioned. The alkylene group having 20 carbon atoms and 1 to 6 represented by Z in the above formula includes divalent groups corresponding to the alkyl group having 1 to 6 carbon atoms.

[0041] In this specification, examples of specific groups such as hydrocarbon groups and groups containing a heterocycle, as long as they have the appropriate number of carbon atoms, are all examples of the specific groups in which a methylene group in the specific group is substituted with a divalent group selected from <Group A>. For example, R 101 As the group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) are substituted with a divalent group selected from <Group A>, R101 Examples of the hydrocarbon group having 1 to 20 carbon atoms and represented by the formula (I) include groups in which one or more methylene groups in the various groups listed above are substituted with a divalent group selected from <Group A>. This also applies to the case in which a methylene group in the above-mentioned specific group is substituted with a group selected from <Group B> described below, the case in which a methylene group in the above-mentioned specific group is substituted with a group selected from <Group III>, the case in which a methylene group in the above-mentioned specific group is substituted with an unsaturated bond, -O- or -S-, and the case in which a methylene group in the above-mentioned specific group is substituted with -O- or -CO-.

[0042] In the present specification, when two or more methylene groups in a hydrocarbon group such as an alkyl group or a group containing a heterocycle are substituted with a divalent group selected from <Group A>, the oxygen atoms are not adjacent to each other, and preferably the divalent groups selected from <Group A> are not adjacent to each other. The same applies to the case where the methylene groups are substituted with a group selected from <Group B>, a group selected from <Group III>, an unsaturated bond, -O- or -S-, or -O- or -CO-.

[0043] R 101 , R 102 and R 103 In the heterocyclic group represented by the following formula (I), a heterocyclic ring-containing group having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, and a group in which a methylene group in the hydrocarbon group is substituted with a group selected from <Group A>, a hydrogen atom in the group may be substituted or may be unsubstituted. If substituted, the substituent is preferably selected from the following Substituent Group 1. Substituent group 1: an alkoxysilyl group, a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -C(R')=N-OH, -COOH or -SO3H. R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when there are a plurality of R', they may be the same or different.

[0044] In addition, the alkyl group having 1 to 8 carbon atoms used for R' in the above-mentioned Substituent Group 1 includes R 101As examples of the alkyl group, those having a predetermined number of carbon atoms among the alkyl groups having 1 to 20 carbon atoms given above can be used.

[0045] In this specification, examples of a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0046] In this specification, the number of carbon atoms of the group substituted by the substituent is within the scope of the annotation of the general formula. For example, R 101 When a hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms, represented by the formula (I), is substituted with a group containing a carbon atom as a substituent, the number of carbon atoms in the substituted hydrocarbon group, including the number of carbon atoms of the substituent, is the same as R in the notes of formula (I). 101 The number of carbon atoms in the hydrocarbon group represented by the formula (I) is 1 to 20.

[0047] In the polymerizable composition of the present invention, the tertiary amine compound represented by general formula (I) is preferably the following compound.

[0048] In terms of the concentration of active sites, R 101 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0049] From the viewpoints of excellent storage stability and excellent low-temperature curing properties, R 102is preferably a hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a group selected from <Group A>, and is preferably a hydrocarbon group having 2 to 20 carbon atoms or a group in which a methylene group other than the bonding site in the hydrocarbon group has been substituted with a group selected from <Group A>. In particular, a group in which a methylene group in an alkyl group having 2 to 20 carbon atoms has been substituted with -COO- is preferred because it provides excellent storage stability and, in particular, low-temperature curing properties. From this perspective, R 102 is even more preferably a group represented by the following formula (α):

[0050] [ka] (In the formula, L 1 is an alkylene group having 1 to 4 carbon atoms, and X 1 is -CO-O- or -O-CO-, and L 2 is an alkyl group having 3 to 18 carbon atoms.

[0051] In particular, from the standpoint of storage stability and low-temperature curing 1 The alkylene group represented by the formula (I) preferably has 2 to 3 carbon atoms, and most preferably has a 1,2-ethanediyl group. 2 is preferably an alkyl group having 3 to 17 carbon atoms, more preferably a branched alkyl group having 3 to 12 carbon atoms, particularly preferably a branched alkyl group having 5 to 10 carbon atoms, and most preferably a branched alkyl group having 7 to 9 carbon atoms.

[0052] Furthermore, in terms of the concentration and solubility of the active site, R 103 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably an ethyl group.

[0053] Specific examples of the tertiary amine compound represented by general formula (I) include the compounds represented by No. 1 to No. 14 below.

[0054] [ka]

[0055] [ka]

[0056] The content of the tertiary amine compound or a salt thereof (A) is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and particularly preferably 5 to 20 parts by mass, relative to 100 parts by mass of the cyclic ether compound (B). A polymerizable composition in which the content of the tertiary amine compound or a salt thereof (A) is within the above range is preferred because it has an excellent balance between storage stability and low-temperature curing property and is easy to form high-definition patterning.

[0057] The content of the tertiary amine compound or a salt thereof (A) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the alkali-developable resin (C). A polymerizable composition in which the content of the tertiary amine compound or a salt thereof (A) is within the above range is preferred, since it has an excellent balance between storage stability and low-temperature curing property and is easy to form high-definition patterning.

[0058] The content of the tertiary amine compound or a salt thereof (A) is preferably 0.02 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.2 to 1.5 parts by mass, based on 100 parts by mass of the solid content of the composition (excluding the colorant). A polymerizable composition in which the content of the tertiary amine compound or a salt thereof (A) is within the above range is preferred because it has an excellent balance between storage stability and low-temperature curing properties and is easy to form high-definition patterning.

[0059] <Cyclic Ether Compound (B)> The cyclic ether compound (B) refers to a compound having a cyclic ether group. The cyclic ether compound is contained in the composition as a component other than the above-mentioned tertiary amine compound or a salt thereof (A), and even if the compound has a cyclic ether group, the compound corresponding to the tertiary amine compound or a salt thereof (A) is not considered to be a cyclic ether compound. The cyclic ether group may be any group having at least one ether bond in the ring structure, and examples thereof include an epoxy group, an oxetanyl group, etc. In addition to the cyclic ether group, compounds having an ethylenically unsaturated group, a carboxy group, an acid anhydride structure, or a hydroxyl group such as a phenol group are also considered to be cyclic ether compounds. Examples of the ethylenically unsaturated group include an acryloyl group, a methacryloyl group, and a vinyl group.

[0060] On the other hand, compounds having alkoxysilyl groups together with cyclic ether groups are generally classified as silane coupling agents, and are not considered to be the above-mentioned cyclic ether compounds. For example, compounds having alkoxysilyl groups together with epoxy groups, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, are generally classified as silane coupling agents, and are not considered to be the epoxy compounds. Specific examples of the cyclic ether compound (B) are given below.

[0061] (1) Epoxy compounds The epoxy compound includes all compounds having an epoxy group as a cyclic ether group among cyclic ether compounds. For example, a compound containing an epoxy group and another cyclic ether group such as an oxetanyl group in one molecule is included in the epoxy compound. Examples of such epoxy compounds include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds.

[0062] (1-1) Aromatic epoxy compounds The aromatic epoxy compound has an aromatic ring and an epoxy group, but does not have a cycloalkene oxide structure. As such an aromatic epoxy compound, a compound having at least one aromatic hydrocarbon ring can also be used. Examples of the aromatic epoxy compound include polyglycidyl ethers of polyhydric phenols having at least one aromatic ring, such as bisphenol A and bisphenol F, or their alkylene oxide adducts; epoxy novolac resins (phenol novolac type epoxy compounds); polyglycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as phenyl dimethanol, phenyl diethanol, and phenyl dibutanol; polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid; diepoxidized products of divinylbenzene; and glycidyl amine compounds such as N,N-diglycidylaniline and its derivatives. In addition, compounds obtained by reacting an aromatic epoxy compound having two or more glycidyl ether groups with a main chain skeleton containing a rubber component and a group capable of reacting with an epoxy group to form a covalent bond can also be mentioned.

[0063] As the aromatic epoxy compound, commercially available products can be used, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Corporation); Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Tohto Kasei Co., Ltd.) ); YX8800 (Mitsubishi Chemical); Marproof G-0105SA, Marproof G-0130SP (NOF Corp.); Epicron N-665, Epicron HP-7200 (DIC Corp.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN- 501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901, EP-3950S, EP-3950L, EP-3980S (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.), and the like.

[0064] (1-2) Aliphatic epoxy compounds The aliphatic epoxy compound has an epoxy group and does not contain a cycloalkene oxide structure or an aromatic ring. Specific examples of such aliphatic epoxy compounds include glycidyl ethers of aliphatic alcohols, and polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts. More specifically, examples of the glycidyl ethers include glycidyl ethers of polyhydric alcohols such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of neopentyl glycol; and polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin, monoglycidyl ethers of aliphatic higher alcohols, and epoxidized polybutadienes. Other examples include compounds having a tricyclodecane structure and a glycidyl ether group, such as dimethylol tricyclodecane diglycidyl ether and tricyclodecane diglycidyl ether, etc. Also included are compounds obtained by reacting an aliphatic glycidyl ether type epoxy compound having two or more glycidyl ether groups with a main chain skeleton that contains a rubber component and includes a group capable of reacting with an epoxy group to form a covalent bond. As the aliphatic epoxy compound, a hydrogenated product of an aromatic epoxy compound such as hydrogenated bisphenol A diglycidyl ether can also be used. As the aliphatic epoxy compound, a compound having a structure in which an oxiranyl group is directly bonded to a cycloalkyl ring derived from an epoxycycloalkyl ring via a single bond as a constituent unit and a structure in which epoxy groups of the epoxycycloalkyl ring are polymerized together as a main chain structure, such as a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, can also be used.

[0065] As the aliphatic epoxy compound, commercially available products can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, and Denacol EX-83. 2, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycirol ED-503, Adeka Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T (manufactured by ADEKA Corporation), and the like.

[0066] As the aliphatic epoxy compound, any of an aliphatic ring-containing epoxy compound having an aliphatic ring such as an aliphatic hydrocarbon ring or an aliphatic heterocycle, and a chain aliphatic epoxy compound having no aliphatic ring can be used.

[0067] (1-3) Alicyclic epoxy compounds Specific examples of the alicyclic epoxy compound include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring and a hydroxyl group directly bonded to the alicyclic ring, and compounds containing a cycloalkene oxide structure, such as cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent.

[0068] Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexyl, and the like. Examples of the epoxy groups include hexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, and ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

[0069] Examples of commercially available products that can be suitably used as the alicyclic epoxy compound include those described in Japanese Patent No. 6103653 and the like.

[0070] (1-4) In the present invention, the epoxy equivalent of the epoxy compound is preferably 70 to 300 g / eq., more preferably 200 g / eq. or less, and particularly preferably 100 g / eq. or less. This is because when the epoxy equivalent is within the above range, a highly precise pattern can be obtained.

[0071] (2) Oxetane compounds Specific examples of the oxetane compound include the following compounds: 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether, isobornyl oxetane, oxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether ter, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3 -ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methyleneyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, tricyclodecane diyl dimethylene (3-ethyl-3-oxetanyl methyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanyl methyl) ether, 1,4-bis(3-ethyl-3-oxetanyl methoxy) butane, 1,6-bis(3-ethyl-3-oxetanyl methoxy) hexane, pentaerythritol tris(3-ethyl-3-oxetanyl methyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanyl methyl) ether, polyethylene glycol bis(3-ethyl Dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditri Examples of such bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether include methylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether, EO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, and EO modified bisphenol F(3-ethyl-3-oxetanylmethyl)ether.

[0072] The oxetanyl equivalent of the oxetane compound may be any one that provides the desired pattern definition, storage stability, and low-temperature curing properties, but in terms of a balance with availability, etc., it is preferably 80 g / eq. or more and 500 g / eq. or less, and more preferably 100 g / eq. or more and 300 g / eq. or less.

[0073] (3)Other In one embodiment of the composition of the present invention, the molecular weight of the cyclic ether compound is not particularly limited as long as the desired curability and the like can be obtained, and may be, for example, from 50 to 20,000. From the viewpoints of the balance between the storage stability and low-temperature curability of the composition as well as the ease of application and adhesion of the composition, the molecular weight is more preferably from 100 to 2,000, and even more preferably from 200 to 1,500.

[0074] When the compound is a polymer, the molecular weight is the weight-average molecular weight (Mw). The weight-average molecular weight can be determined by gel permeation chromatography (GPC) using standard polystyrene as the conversion value.

[0075] The weight average molecular weight can be measured, for example, using a GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as an elution solvent, polystyrene standards for calibration curves of Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, and 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and measuring columns of KF-804, KF-803, and KF-802 (manufactured by Showa Denko K.K.). The measurement temperature can be 40° C., and the flow rate can be 1.0 mL / min.

[0076] The number of cyclic ether groups in the cyclic ether compound can be appropriately set according to the desired curability, etc. The number of cyclic ether groups may be 1 or more per molecule of the cyclic ether compound, but can be 2 to 10, preferably 2 to 8, and most preferably 3 or more. This is because a composition using such a cyclic ether compound can easily produce a cured product with a high-definition pattern and has good reactivity during curing.

[0077] In particular, in one embodiment of the polymerizable composition of the present invention, it is preferable to contain an epoxy compound as the cyclic ether component, because the composition can be more easily patterned with high definition and can easily achieve low temperature curing properties.

[0078] Furthermore, as an embodiment of the composition of the present invention, it is preferable that the cyclic ether component contains a glycidyl type epoxy compound having a glycidyl group as an epoxy compound. This is because the composition is easy to obtain low temperature curing properties and has excellent pattern definition. In particular, the epoxy compound may contain a glycidyl ether group, a glycidyl amino group, or a diglycidyl amino group as a glycidyl group.

[0079] In one embodiment of the composition of the present invention, as described above, the cyclic ether compound preferably contains a glycidyl-type epoxy compound. In order to enhance the effect of containing the glycidyl-type epoxy compound, the proportion of the glycidyl-type epoxy compound in 100 parts by mass of the cyclic ether compound is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 80 parts by mass or more.

[0080] According to the present invention, the content of the cyclic ether compound (B) is preferably from 2 to 30 parts by mass, and more preferably from 5 to 20 parts by mass, relative to 100 parts by mass of the alkali-developable resin (C), because the composition has an excellent balance between storage stability and low-temperature curing property, making it easier to obtain a high-definition pattern.

[0081] From the viewpoint of a balance between the storage stability and low-temperature curing property of the composition, and the ease of obtaining a high-resolution pattern, the content of the cyclic ether component is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass or less, and even more preferably 3 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the solid content of the composition (excluding the colorant). Moreover, the solid content in the present invention refers to the content excluding the solvent described later.

[0082] <Alkaline developable resin (C)> The alkali developable resin (C) according to the present invention is a compound having a carboxy group and a polymerizable group. Examples of the polymerizable group include radical polymerizable groups such as acrylic, methacrylic, and vinyl groups, isocyanate groups, and hydroxyl groups. The radical polymerizable groups are preferred due to their high sensitivity, and acrylic groups are particularly preferred.

[0083] In addition, compounds corresponding to the tertiary amine compound or its salt (A) are not considered to be alkaline developable resins (C), and compounds corresponding to the cyclic ether compound (B) are not considered to be alkaline developable resins (C). In the present invention, any compound that has been conventionally used can be used as the alkaline developable resin (C) as long as it satisfies the above conditions.

[0084] The preferred functional group equivalent of the carboxy group in the alkali developable resin (C) (the mass of the polymer compound containing 1 equivalent of a hydrophilic group) is 50 to 10,000. The weight average molecular weight of the alkali developable resin (C) is preferably 1,000 to 500,000, and it is preferable to use an alkali developable resin having a weight average molecular weight of 3,000 or more, and more preferably an alkali developable compound having a weight average molecular weight of 4,000 to 15,000. Such a weight average molecular weight is particularly preferable when the polymerizable composition of the present invention is used as a BCS, particularly as a black partition wall of an organic EL device, because it can verticalize the pattern shape, improve the development adhesion, and improve the heat resistance. In particular, as the unsaturated compound having such a molecular weight, it is preferable that the unsaturated compound has a structure obtained by esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the above formula (II) and a polybasic acid anhydride.

[0085] The weight average molecular weight can be measured by the following method. Using GPC (Hitachi, model number: ELITE LaChrom L-2000, columns: KF-805, 804, 803 connected), and using chloroform as the developing solvent, a calibration curve is created using standard polystyrene of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, the weight average molecular weight is calculated from the GPC retention time.

[0086] The alkali developable resin (C) has an acid value of preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. When the acid value is 10 mg / KOH or more, sufficient alkali developability is easily obtained, and when it is 200 mg / KOH or less, the polymer compound is easily produced. Here, the acid value is based on JIS K0050 and JIS K0211.

[0087] Specific examples of the alkali-developable resin (C) that can be used include copolymers of acrylic acid esters; phenol and / or cresol novolak epoxy resins, polyphenylmethane-type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins, and resins (unsaturated compounds) having a structure obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound such as the epoxy compound represented by the above formula (II) and a polybasic acid anhydride. Among these, it is preferable to use an alkali-developable compound which is a reaction product obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the above formula (II) and a polybasic acid anhydride, since it is possible to obtain a cured product having a high-definition pattern with excellent insulating properties. Furthermore, an alkali developable resin in which 0.2 to 1.0 equivalent of an unsaturated monobasic acid is added to an epoxy compound is particularly preferred because it provides a polymerizable composition with high sensitivity.

[0088] An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the above formula (II) usually has the following structure [(e)]. Also, a reaction product obtained by an esterification reaction of such an epoxy addition compound with a polybasic acid anhydride usually has the following structure [(f)].

[0089] [ka] (In the formula, Y 1 represents the residue of an unsaturated monobasic acid, and Y 2 represents a residue of a polybasic acid anhydride, and * represents a bond.)

[0090] The hydrocarbon group having 1 to 20 carbon atoms represented by M in the above formula (II) is not particularly limited, but is preferably a chain alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Among these, a chain alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms is more preferred because they provide good sensitivity when used as the alkali-developable resin (C).

[0091] Examples of the chain alkylene group having 1 to 20 carbon atoms represented by M in the above formula (II) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and icosylene groups.

[0092] Examples of the alkenylene group having 2 to 20 carbon atoms represented by M in the above formula (II) include 1,2-ethenediyl (also called ethenylene or vinylene), 2-butene-1,4-diyl, and 1,2-dimethyl-1,2-ethenediyl.

[0093] Examples of the cycloalkylene group having 3 to 20 carbon atoms represented by M in the above formula (II) include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene groups.

[0094] Examples of the arylene group having 6 to 20 carbon atoms represented by M in the above formula (II) include phenylene, tolylene, xylylene, naphthylene, biphenylene, fluorene, and indane.

[0095] R in the above formula (II) 1 ~R 8 , R 9 , R 10 ~R 38The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is not particularly limited, but preferably represents a chain alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. Specific examples of these groups include R 101 Examples of the groups mentioned above include those given as examples.

[0096] R in the above formula (II) 1 ~R 8 , R 9 , R 10 ~R 38 Since a hydrocarbon group having 1 to 20 carbon atoms represented by the following formula (I) has good sensitivity when used as the alkali-developable resin (C), chain alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkylalkyl groups having 4 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and arylalkyl groups having 7 to 10 carbon atoms are more preferred because they have excellent alkali developability.

[0097] R in the above formulas (a) to (d) 10 ~R 38 Examples of the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle and having 3 to 20 carbon atoms are R 101 and the groups containing a heterocycle and having 3 to 20 carbon atoms, each of which is represented by the same formula (I) and (II).

[0098] R 1 ~R 8 and R 10 ~R 38 Examples of the unsaturated bond which may substitute a methylene group in the group represented by the formula: include -C=C-, -C≡C- and the like.

[0099] R in the above formulas (a) to (d) 10 and R 11 , R 11 and R 12 , R 12and R 13 , R 13 and R 14 , R 22 and R 15 , R 15 and R 16 , R 30 and R 23 , R 23 and R 24 , R 24 and R 25 , R 38 and R 31 , R 31 and R 32 , R 32 and R 33 , R 34 and R 35 , R 35 and R 36 and R 36 and R 37 Examples of the ring formed by bonding include 5- to 7-membered rings such as cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone rings, and lactam rings, and condensed rings such as naphthalene and anthracene.

[0100] R 1 ~R 8 The hydrocarbon group having 1 to 20 carbon atoms represented by the following formula (I) and the group in which a methylene group in the hydrocarbon group is replaced with an unsaturated bond, -O- or -S- may have a hydrogen atom substituted or may be unsubstituted. When substituted, the substituent is preferably selected from the following Substituent Group 2. Substituent group 2: a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxy group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, a heterocyclic group having 2 to 10 carbon atoms, and a heterocyclic group containing 3 to 20 carbon atoms.

[0101] In this specification, examples of the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle having 3 to 20 carbon atoms as the substituent include R 101Examples of the heterocyclic group having 2 to 10 carbon atoms and represented by the following formula and the group containing a heterocycle and having 3 to 20 carbon atoms include the groups mentioned above.

[0102] R 9 The hydrocarbon group having 1 to 20 carbon atoms represented by the following formula may be unsubstituted or may have a hydrogen atom substituted therein. When the hydrocarbon group is substituted, the substituent is preferably selected from the above-mentioned substituent group 2.

[0103] R 10 ~R 38 The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, and the heterocyclic-containing group having 3 to 20 carbon atoms, as well as the groups in which the methylene group is substituted with an unsaturated bond, -O-, or -S-, may or may not have a hydrogen atom substituted. When substituted, the substituent is preferably selected from the above-mentioned Substituent Group 2.

[0104] In view of the ease of obtaining a cured product having a high-definition pattern with excellent insulating properties from the polymerizable composition, it is preferable that M is represented by formula (b) or (d) among formula (II), and it is particularly preferable that M is represented by formula (b). In addition, because the alkali-developable resin (C) is readily available and the resulting cured product has excellent heat resistance, R 1 ~R 8 , R 9 , R 10 ~R 38 is preferably a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, or a halogen atom, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom.

[0105] The above-mentioned unsaturated monobasic acid refers to an acid having an unsaturated bond in its structure and having one hydrogen atom per molecule that can be ionized to become a hydrogen ion. Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, and dicyclopentadiene maleate.

[0106] In addition, examples of the polybasic acid anhydride to be reacted with after the reaction with the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic 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-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylhimic anhydride.

[0107] The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably as follows, in terms of good alkali developability. That is, the epoxy addition compound is preferably added such that the ratio of the carboxy group of the unsaturated monobasic acid is 0.1 to 1.0 per epoxy group of the epoxy compound, and the alkali-developable resin (C) is preferably added such that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 per hydroxyl group of the epoxy adduct. The reaction of the epoxy compound represented by the above formula (II), the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to a conventional method.

[0108] In order to improve the developability of the polymerizable composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound can be further reacted together with the above-mentioned alkali developable resin (C). The above-mentioned alkali developable resin (C) preferably has an acid value of the solid content in the range of 5 to 120 mgKOH / g in order to obtain good alkali developability, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected so as to satisfy the above-mentioned acid value.

[0109] Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, and the following epoxy compounds No. E1 and No. E2.

[0110] [ka]

[0111] [ka]

[0112] 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, since this makes it possible to obtain a cured product having good heat resistance. As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the above formula (II), for example, bisphenol type epoxy compounds such as hydrogenated bisphenol type epoxy compounds can also be used. Examples of the glycidyl ethers that can be used include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, and 1,1,1,1-tetra(glycidyloxymethyl)methane. Other novolac type epoxy compounds (phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds, etc.); alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc. glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer acid ester; glycidyl amines 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; dicyclopentadiene-type epoxy compounds, etc. can also be used.

[0113] As the alkali developable resin (C), commercially available products can also be suitably used. Examples of commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, and SPRR-21X (all manufactured by Showa Denko K.K.), JET2000, AGOR1060, AGOR3060, ORGA1060, and ORGA2060 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), and CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.).

[0114] In the polymerizable composition of the present invention, the content of the alkali developable resin (C) is preferably 20 to 90 parts by mass relative to 100 parts by mass of the total amount of the tertiary amine compound or its salt (A), the cyclic ether compound (B), the alkali developable resin (C), the polymerization initiator (D), and the compound having active hydrogen capable of reacting with the cyclic ether compound (E), from the viewpoints of making it easier to obtain a cured product having a high-definition pattern and of obtaining stable solubility in an alkali developer, more preferably 30 to 80 parts by mass, and particularly preferably 35 to 70 parts by mass. The alkali developable resin (C) is preferably the component with the largest mass in the solid content of the polymerizable composition excluding the colorant.

[0115] From the same viewpoint as above, in the polymerizable composition of the present invention, the content of the alkali developable resin (C) is preferably 20 to 75 parts by mass, more preferably 30 to 70 parts by mass, and particularly preferably 35 to 65 parts by mass, per 100 parts by mass of the solids content (excluding the colorant) of the composition.

[0116] <Polymerization initiator (D)> As the polymerization initiator (D) used in the polymerizable composition of the present invention, a conventionally known radical polymerization initiator can be used. Note that those corresponding to the tertiary amine compound or its salt (A), the cyclic ether compound (B), or the alkali developable resin (C) are not considered to be the polymerization initiator (D).

[0117] The radical polymerization initiator includes a photoradical polymerization initiator and a thermal radical polymerization initiator. The photoradical polymerization initiator is more preferred because of its high reactivity.

[0118] The photoradical polymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and any conventionally known compound can be used. Preferred examples of the photoradical polymerization initiator include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime ester-based compounds.

[0119] Examples of 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-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxy ... Examples of the benzoin are cyclohexyl phenyl 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.

[0120] The benzyl compounds include benzyl and the like.

[0121] Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0122] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0123] The oxime ester compound means a compound having a group represented by the above formula (III), and can be preferably used in the polymerizable composition of the present invention because it has good sensitivity among the above photoradical polymerization initiators and can easily obtain a good pattern shape.

[0124] R in the above formula (III) 41 , R 42 and R 43 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) are 101 As examples of the hydrocarbon group having 1 to 20 carbon atoms, such as those shown above, can be used.

[0125] R in the above formula (III) 41 and R 42 Examples of the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle having 3 to 20 carbon atoms, represented by the formula (I), are R 101 The heterocyclic groups having 2 to 10 carbon atoms and the heterocyclic-containing groups having 3 to 20 carbon atoms are the same as those described above.

[0126] R 41 and R 42 In the hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, and the group containing a heterocycle and having 3 to 20 carbon atoms, represented by the formula (I), and the methylene group in the hydrocarbon group or the group containing a heterocycle and having 3 to 20 carbon atoms, which is substituted with a group selected from <Group B>, the hydrogen atom in the group may be substituted or may be unsubstituted. When substituted, the substituent is preferably selected from the above-mentioned Substituent Group 2, and is particularly preferably a halogen atom. R 43 The hydrocarbon group having 1 to 20 carbon atoms represented by the following formula may be unsubstituted or may have a hydrogen atom substituted therein. When the hydrocarbon group is substituted, the substituent is preferably selected from the above-mentioned substituent group 2, and is particularly preferably a halogen atom.

[0127] Among the compounds having a group represented by the above formula (III), the compound represented by the following formula (IV) has particularly high sensitivity and makes it easier to obtain a good pattern shape, and is therefore preferably used in the polymerizable composition of the present invention.

[0128] [ka]

[0129] (In the formula, R 41 , R 42 and m1 are each R in formula (III). 41 , R 42 and m1, R 51 and R 52 each independently represents a hydrogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle and having 3 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or the group containing a heterocycle and having 3 to 20 carbon atoms is substituted with -O- or -CO-; X 2 is an oxygen atom, a sulfur atom, a selenium atom, and a CR 53 R 54 , C.O., N.R. 55 Or PR 56 represents R 53 , R 54 , R 55 and R 56 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle and having 3 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or the group containing a heterocycle and having 3 to 20 carbon atoms is substituted with -O- or -CO-; R 53 , R 54 , R 55 and R 56 may each independently be combined with an adjacent benzene ring to form a ring, g represents a number from 0 to 5, h represents a number from 0 to 4. If g is 2 or more, multiple R 51 may be the same or different. When h is 2 or more, a plurality of R 52 may be the same or different from each other. R 51 , R 52 , R 53 , R 54 , R 55 and R56 The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, the group containing a heterocycle having 3 to 20 carbon atoms, or the hydrocarbon group or the group containing a heterocycle having 3 to 20 carbon atoms in which a methylene group is substituted with -O- or -CO-, may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxy group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, a heterocyclic group having 2 to 10 carbon atoms, or a group containing a heterocycle having 3 to 20 carbon atoms.

[0130] R in the above formula (IV) 51 , R 52 , R 53 , R 54 , R 55 and R 56 (Hereinafter referred to as “R 51 ~R 56 The hydrocarbon group having 1 to 20 carbon atoms represented by R 101 As examples of the hydrocarbon group having 1 to 20 carbon atoms, such as those shown above, can be used.

[0131] R in the above formula (IV) 51 ~R 56 Examples of the heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocycle having 3 to 20 carbon atoms, which are represented by the formula (I), include R 101 The heterocyclic groups having 2 to 10 carbon atoms and the heterocyclic-containing groups having 3 to 20 carbon atoms are the same as those described above. Also, R 51 ~R 56 Examples of the heterocyclic group having 2 to 10 carbon atoms and the heterocyclic group having 3 to 20 carbon atoms as the substituent substituting a hydrogen atom in the group represented by the formula (I) include R 101 Examples of the heterocyclic group include the heterocyclic group having 2 to 10 carbon atoms and the heterocyclic ring-containing group having 3 to 20 carbon atoms described above.

[0132] R 51 ~R 56The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, and the group containing a heterocycle having 3 to 20 carbon atoms, as well as the groups in which a methylene group is replaced with -O- or -CO-, may further have a substituent or may be unsubstituted. When the group has a substituent, the substituent is preferably selected from the above-mentioned Substituent Group 2, and more preferably a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a heterocyclic group having 2 to 10 carbon atoms, or a group containing a heterocycle having 3 to 20 carbon atoms.

[0133] Preferred examples of the polymerization initiator (D) include compounds No. D1 to No. D15 shown below, and examples of the compound represented by the above formula (IV) include compounds No. D1 and No. D3 to No. D15 shown below. However, the polymerization initiator (D) used in the present invention is not limited in any way by the following compounds.

[0134] [ka]

[0135] [ka]

[0136] As the polymerization initiator, in particular, those having a carbazole structure are preferred because of their high sensitivity, and further, those having both a carbazole structure and a nitro group are more preferred.

[0137] From the above viewpoints, among the compounds represented by formula (IV), X 2 NR 55 The one represented by NR is preferred because of its high sensitivity. 55 Preferably, the compound is represented by NR 55 If you use R 55 The number of carbon atoms of R is preferably 10 or less, particularly 5 or less, in terms of availability of the polymerization initiator and sensitivity. 55is preferably a phenyl group, an alkyl group or an alkenyl group, which may be substituted with a substituent.

[0138] Among the compounds represented by formula (IV), those in which h is 0 are preferred from the viewpoint of ease of production. Also, g is 1 or more, and R 51 In particular, a compound in which g is 1 or more and R 51 Among these, compounds in which one or more are nitro groups are preferred, and compounds having a nitro group at the 3-position of carbazole are particularly preferred.

[0139] In addition, among the compounds represented by formula (IV), R 41 From the viewpoint of sensitivity and ease of production, R is preferably a chain or cyclic alkyl group, an aryl group, or an arylalkyl group, or a group in which the methylene group is substituted with -O-, preferably a group in which the methylene group in the aryl group is substituted with -O-, and more preferably a group in which the methylene group in the alkyl group in a phenyl group substituted with an alkyl group is substituted with -O-. 41 The number of carbon atoms in the alkyl group is preferably 20 or less, more preferably 8 to 20, and particularly preferably 9 to 15.

[0140] Among the compounds represented by formula (IV), R 42 From the viewpoint of ease of production, R preferably has 10 or less carbon atoms, particularly preferably 7 or less, and particularly preferably 3 or less. 42 is preferably a substituted or unsubstituted chain alkyl or phenyl group in terms of sensitivity and ease of production, and is more preferably a chain alkyl group.

[0141] Other examples of the radical polymerization initiator include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyr-1-yl)]titanium.

[0142] Commercially available radical initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARCLES NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (all manufactured by Tronly); and the like.

[0143] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and any conventionally known compound can be used. For example, preferred examples include azo compounds, peroxides, and persulfates.

[0144] Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).

[0145] Examples of peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate.

[0146] Examples of the persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, and the like.

[0147] The polymerization initiator (D) may be used alone or in combination of two or more of the above-mentioned examples.

[0148] A polymerizable composition having a content of the polymerization initiator (D) of 1 to 80 parts by mass relative to 100 parts by mass of the alkali developable resin (C) is preferred because it has excellent sensitivity and can give a cured product having a high-definition pattern even when the light-shielding property is high, more preferably 1 to 50 parts by mass, and particularly preferably 3 to 30 parts by mass.

[0149] From the same viewpoint as above, the content of the polymerization initiator (D) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 15 parts by mass, per 100 parts by mass of the solid content (excluding the colorant) of the composition.

[0150] <Compound (E) having active hydrogen capable of reacting with a cyclic ether compound> The compound (E) having active hydrogen capable of reacting with a cyclic ether compound is a compound capable of reacting with a cyclic ether group such as an epoxy group or an oxetanyl group, and generally acts as a curing agent for an epoxy compound. Examples of the compound having an active hydrogen group include compounds having an amino group, a phenol group, a carboxy group, a thiol group, a sulfonic acid group, etc. In the present invention, it is preferable to contain a compound having two or more of these active hydrogen groups in one molecule.

[0151] In addition, any of the tertiary amine compounds or their salts (A), cyclic ether compounds (B), alkali developable resins (C) and polymerization initiators (D) is not considered to be a compound having an active hydrogen capable of reacting with a cyclic ether compound (E).

[0152] Specific examples include amines such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diaminodiphenyl sulfone; acid anhydrides such as phthalic anhydride, tetrahydromethylphthalic anhydride, trimellitic anhydride, methylnadic anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride; carboxylic acids such as adipic acid; phenol novolac; and phenol aralkyl. Phenols such as bisphenol A, bisphenol F, etc., and other alcohols such as 3-aminophenol, resorcinol, catechol, hydroquinone, 3-cyanophenol, 2,3-diaminophenol, 4,4'-dihydroxy-3,3'-diaminobiphenyl, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl di(trifluoromethyl)methane, 3,4-diaminobenzoic acid, 3-phenolsulfonic acid, and propylene glycol.

[0153] In particular, in the present invention, it is preferable to use a compound having a thiol group (hereinafter referred to as a "thiol compound") as the compound (E) having active hydrogen capable of reacting with a cyclic ether compound, in that this enhances low-temperature curing properties and makes it easier to obtain a polymerizable composition that can give a high-resolution pattern. As the thiol compound, it is preferable to use a compound represented by the following formula (A) as an example of a compound having 2 or more and 10 or less thiol groups. This is because the composition has excellent low-temperature curing properties. In addition, it is preferable in terms of availability and the balance between the storage stability and curing properties of the composition.

[0154] [ka] (In the formula, X1 represents an unsubstituted or substituted hydrocarbon group having 1 to 40 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, or a heterocyclic ring-containing group having 3 to 20 carbon atoms, each of which has the same valence as n1, or represents a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group having 3 to 20 carbon atoms are replaced by a divalent group selected from the following Group III, n1 represents an integer of 2 or more and 10 or less. Group III: -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'''-, -SS- or -SO2-. R''' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when there are multiple R''', they may be the same or different.

[0155] The above X1 is used as a linking group that bonds n1 -SH groups. The hydrocarbon group having 1 to 40 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, and the group containing a heterocycle and having 3 to 20 carbon atoms, each having a valence equal to n1, represented by the above X1, are groups having a structure in which (n1-1) hydrogen atoms have been removed from a monovalent hydrocarbon group having 1 to 40 carbon atoms, a monovalent heterocyclic group having 2 to 10 carbon atoms, and a monovalent group containing a heterocycle and having 3 to 20 carbon atoms, respectively.

[0156] Examples of the monovalent hydrocarbon group having 1 to 40 carbon atoms include monovalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms and monovalent aromatic hydrocarbon groups having 6 to 40 carbon atoms. Examples of monovalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms include R 101 Examples of the monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms include the above-mentioned linear or branched 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. 101Examples of the heterocyclic group include the above-mentioned aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms. Examples of the monovalent heterocyclic group having 2 to 20 carbon atoms include R 101 Examples of the heterocyclic group having 2 to 10 carbon atoms include the heterocyclic groups listed above. Examples of the monovalent heterocyclic group having 3 to 20 carbon atoms include R 101 Examples of the heterocyclic ring include the above-mentioned groups having 3 to 20 carbon atoms. When the above-mentioned hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, and group containing a heterocyclic ring have a substituent, examples of the substituent include those in the above-mentioned Substituent Group 2.

[0157] In terms of the balance between the storage stability and low-temperature curing properties of the composition, the aliphatic hydrocarbon group having 1 to 40 carbon atoms and the same valence as n1 preferably has 1 to 30 carbon atoms, and may have 1 to 20 carbon atoms. The alkyl group having 1 to 8 carbon atoms used for R''' in the above group III is R 101 As examples of the alkyl group, those having a predetermined number of carbon atoms among the alkyl groups having 1 to 20 carbon atoms given above can be used. When two or more methylene groups in the above-mentioned hydrocarbon group or the above-mentioned group containing a heterocycle are replaced with a divalent group selected from Group III, the divalent groups are not adjacent to each other. The divalent groups may be the same or different.

[0158] Preferred examples of groups represented by X1 from the viewpoint of the balance between the low-temperature curing property of the composition and ease of availability will be further described below. As the above-mentioned X1, the aliphatic hydrocarbon group or the group in which a methylene group is replaced by a group selected from group III is preferably the following. When n1 is 2, alkylene groups and groups in which the methylene groups are replaced with groups selected from Group III are preferred. When n1 is 3, alkylidyne groups and groups in which one or more methylene groups are replaced with groups selected from Group III are preferred. When n1 is 4 or more, for example, polyol residues and groups in which the methylene groups are replaced with groups selected from Group III are preferred. As the aromatic hydrocarbon group or the aromatic hydrocarbon group in which a methylene group has been replaced by a group selected from group III as X1, the following are preferred. When n1 is 2, preferred are groups containing arylene groups such as phenylene and naphthylene, residues of bifunctional phenols such as catechol, bisphenol, and alkylene oxide adducts thereof; 2,4,8,10-tetraoxaspiro[5,5]undecane, and the like. When n=3, containing groups such as phenyl-1,3,5-trimethylene are preferred.

[0159] The heterocyclic group represented by X1 is preferably, for example, a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring, an isocyanuric ring, a triazine ring, or a glycoluril ring having n1 bonds.

[0160] The heterocyclic ring-containing group having 3 to 20 carbon atoms represented by X1 is preferably, for example, a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring, an isocyanuric ring, a triazine ring, a group in which one or more hydrocarbon groups are bonded to a glycoluril group, or a group in which n1 hydrocarbon groups are bonded. The number of carbon atoms of the hydrocarbon group may be 1 to 6.

[0161] In the present invention, from the viewpoint of a balance between the low temperature curing property and easy availability of the composition, X1 is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group containing a heterocycle, in which one or more methylene groups have been replaced with groups selected from Group III, and particularly preferably one or more methylene groups have been replaced with -O-CO- or -CO-O-, and particularly preferably n1 methylene groups have been replaced with -O-CO- or -CO-O-.

[0162] In view of the low-temperature curing property and easy availability of the thiol compound, for example, preferred thiol compounds include groups represented by any of the following (A1) to (A6). [ka] (In the formula, L 11 , L 12 , L 21 , L 22 , L 23 , L 31 , L 32 , L 33 , L 34 , L 41 , L 42 , L 43 , L 44 , L 45 , L 46 , L 51 , L 52 , L 53 , L 61 , L 62 , L 63 and L 64 (Hereinafter referred to as “L 11 ~L 64 Each of R 1 to R 2 independently represents a linear or branched alkylene group having 1 to 10 carbon atoms. 64 , R 65 and R 66 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. a21 represents an integer of 1 to 20.

[0163] The above L 11 ~L 64 Examples of the alkylene group having 1 to 10 carbon atoms represented by the following formula include divalent groups having a structure in which one hydrogen atom has been removed from an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include the above-mentioned R 101 Among the alkyl groups having 1 to 20 carbon atoms in the above, those having a predetermined number of carbon atoms can be used. Also, R 64 , R 65 and R 66 The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in R 101and the like. L 11 ~L 64 and an alkylene group having 1 to 10 carbon atoms represented by the formula: 64 , R 65 and R 66 The aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by the following formula (I) is unsubstituted or one or more hydrogen atoms in the group are substituted. In the case where the group is substituted, the substituent may be the same as the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group represented by the above formula (I). The content can be:

[0164] From the viewpoint of the balance between the storage stability and low-temperature curing property of the composition, 11 ~L 64 is preferably an alkylene group having 1 to 5 carbon atoms, and particularly preferably a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms, and particularly preferably a branched alkylene group having 3 to 5 carbon atoms, because the composition has an excellent balance between storage stability and low-temperature curing properties.

[0165] The above L 11 ~L 64 Specific examples of the linear alkylene group having 1 to 3 carbon atoms represented by the following formula include methylene, ethylene (ethane-1,2-diyl), and propylene (propane-1,3-diyl). The above L 11 ~L 64 Specific examples of the branched alkylene group having 3 to 5 carbon atoms represented by the formula (1) include propane-1,1-diyl, propane-1,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, pentane-1,1-diyl, pentane-1,2-diyl, pentane-1,3-diyl, and pentane-1,4-diyl.

[0166] L in (A1) 11 and L 12may be the same or different groups, but from the viewpoint of ease of synthesis, it is preferable that they are the same group. This is because the composition has a better balance between low-temperature solidification property and ease of availability. This is because L in (A2) 21 ~L 23 , (A3) L 31 ~L 34 , (A4) L 41 ~L 46 , (A5) L 51 ~L 53 , (A6) L 61 ~L 64 The same applies to.

[0167] In the present invention, the above R 64 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms, because the composition has an excellent balance between storage stability and low-temperature curing property.

[0168] From the viewpoint of the balance between the storage stability and curability of the composition, the thiol compound preferably has a molecular weight of 100 or more and 1,000 or less, more preferably 300 or more and 900 or less, and particularly preferably 350 or more and 800 or less, because the composition has an excellent balance between the storage stability and the low-temperature curability.

[0169] The type of thiol group in the thiol compound can be a primary thiol group, a secondary thiol group, a tertiary thiol group, etc. From the viewpoint of more effectively exerting the effect of excellent low-temperature curing property of the present invention, the type of the thiol group is preferably a secondary thiol group. For example, when the thiol compound contains a secondary thiol, the amount of the secondary thiol in the thiol compound is preferably 30% by mass or more, more preferably 40% by mass or more.

[0170] In order to further enhance the effects of excellent storage stability and low-temperature curing property, the number of thiol groups contained in one molecule of the thiol compound is preferably 2 or more, and more preferably 3 or more. In order to further enhance the storage stability, the number of thiol groups is preferably 10 or less, more preferably 8 or less, even more preferably 7 or less, preferably 6 or less, preferably 5 or less, and preferably 4 or less.

[0171] As the thiol compound, commercially available products may be used. Examples of commercially available thiol compounds include dodecanethiol (monofunctional thiol compound), KarenzMT (registered trademark) BD (trade name, bifunctional thiol compound, 1,4-bis(3-mercaptobutyryloxy)butane, Showa Denko K.K.), KarenzMT (registered trademark) NR (trade name, trifunctional thiol compound, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, Showa Denko K.K.), KarenzMT (registered trademark) PE (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis(3-mercaptobutyrate ), Showa Denko K.K.), EGMP-4 (trade name, bifunctional thiol compound, tetraethylene glycol bis(3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TMMP (trade name, trifunctional thiol compound, trimethylolpropane tris(3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TEMPIC (trade name, trifunctional thiol compound, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, SC Organic Chemical Co., Ltd.), PEMP (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis(3-mercaptopropionate), SC Organic Chemical Co., Ltd. ), DPMP (trade name, hexafunctional thiol compound, dipentaerythritol hexakis, (3-mercaptopropionate), SC Organic Chemicals Co., Ltd.), and the like.

[0172] The thiol compound preferably has an ester bond in the molecule, since this provides an excellent balance between storage stability and low-temperature curing property and makes it easier to obtain a high-definition pattern.

[0173] The content of the compound (E) is more preferably 0.5 parts by mass or more and 30 parts by mass or less, further preferably 1 part by mass or more and 20 parts by mass or less, and particularly preferably 3 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the solid content of the composition (excluding the colorant), because the composition has an excellent balance between storage stability and low-temperature curing property.

[0174] The content of the compound (E) is preferably 5 parts by mass or more and 400 parts by mass or less, more preferably 5 parts by mass or more and 300 parts by mass or less, further preferably 30 parts by mass or more and 200 parts by mass or less, and particularly preferably 50 parts by mass or more and 150 parts by mass or less, relative to 100 parts by mass of the cyclic ether compound (B). This is because the composition has an excellent balance between storage stability and low-temperature curing property, and a high-definition pattern can be easily obtained.

[0175] The content of the compound (E) is more preferably from 2 to 60 parts by mass, further preferably from 3 to 50 parts by mass, and particularly preferably from 7 to 35 parts by mass, relative to 100 parts by mass of the alkali-developable resin (C), because the composition has an excellent balance between storage stability and low-temperature curing property, and can easily produce a high-definition pattern.

[0176] <Colorant (F)> As the colorant (F) used in the polymerizable composition of the present invention, a pigment or a dye can be used. As the pigment and the dye, an inorganic colorant or an organic colorant can be used, respectively. These can be used alone or in a mixture of two or more. Here, the pigment means a colorant insoluble in a solvent described later, and includes inorganic or organic colorants that are insoluble in a solvent, or inorganic or organic dyes that have been made into lakes. Those that correspond to the tertiary amine compound or its salt (A), the cyclic ether compound (B), the alkali developable resin (C), the polymerization initiator (D), or the compound (E) having an active hydrogen that can react with the cyclic ether compound are not considered to be colorants (F).

[0177] Examples of the pigment include carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin; the above carbon black previously dispersed in a resin in a solvent and coated with 20 to 200 mg / g of resin; the above carbon black subjected to an acidic or alkaline surface treatment; carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less; carbon black having a total oxygen content calculated from CO and CO2 in the volatile matter at 950°C of 100% or less of surface area; 2 Examples of organic or inorganic pigments include carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, synthetic iron black, pigment black 7, titanium black, lactam black, and perylene black, as well as black pigments, such as chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, amber, and lake pigments.

[0178] The black pigments can be divided into organic black pigments and inorganic black pigments. The organic black pigments are organic black pigments, such as lactam black and perylene black, and the inorganic black pigments are inorganic black pigments, such as the various carbon blacks mentioned above.

[0179] As the pigment, commercially available products can be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 198, 199, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 250, 251, 252, 253 5, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 and 71; Pigment Yellow 1 , 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 1 14, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 15t, 152, 153, 154, 166, 168, 1 75, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62 and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50, etc.

[0180] Examples of the dye include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthranthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, azo dyes, and metal complex compounds of cyanine dyes.

[0181] Among the above colorants, the polymerizable composition in which the colorant (F) is a black pigment has excellent light-shielding properties and is therefore useful as a polymerizable composition for a black matrix (BM) or a black column spacer (BCS). When carbon black is used among the black pigments, it is preferred in that it has excellent low-temperature curing properties and light-shielding properties when combined with the tertiary amine compound or its salt (A) and the compound (E). In addition, among black pigments, organic black pigments are useful as polymerizable compositions for BM and BCS because the resistance value of the cured film increases. Among organic black pigments, lactam black is preferred because it has excellent light shielding properties in the visible light region of 400 nm to 700 nm, and is excellent in low-temperature curing properties, light shielding properties, and electrical properties (electrical resistance value) when combined with a tertiary amine compound or a salt thereof (A). Lactam black is a black organic pigment having a lactam structure or an isomeric ring structure thereof, or a combination thereof, and has a structure represented by, for example, formula (4) or formula (5) in JP-A-2016-133574. Specific examples of lactam black include IRGAPHOR (registered trademark) BLACK S0100CF and Black 582 from BASF. When the colorant of the present invention contains lactam black, the proportion of lactam black in the colorant is preferably 50% by mass or more, more preferably 75% by mass or more, and particularly preferably 90% by mass or more.

[0182] In the polymerizable composition of the present invention, the content of the colorant (F) is preferably 10 to 500 parts by mass relative to 100 parts by mass of the alkali-developable resin (C), since a cured product obtained from the polymerizable composition has excellent light-shielding properties and has a high-definition pattern, more preferably 50 to 300 parts by mass, and particularly preferably 80 to 200 parts by mass.

[0183] <Ethylenically unsaturated compounds (G)> In the present invention, an ethylenically unsaturated compound (G) may be further used. The ethylenically unsaturated compound (G) is a compound having an ethylenically unsaturated bond and not corresponding to any of the above-mentioned components (A) to (F). In the present invention, it is preferable to use an ethylenically unsaturated compound (G) having a molecular weight of 1000 or less, since the sensitivity is further increased. Examples of the ethylenically unsaturated compound (G) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)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, and the like. vinyl acrylate, allyl (meth)acrylate, benzyl (meth)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 hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester (meth)acrylate oligomers, and other unsaturated monobasic acids and esters of polyhydric alcohols or polyhydric phenols;Metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; amides of unsaturated monobasic acids and polyamines such as (meth)acrylamide, methylene bis-(meth)acrylamide, diethylenetriamine tris(meth)acrylamide, xylylene bis(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; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine. Examples of the vinyl ethers include unsaturated amine compounds; 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 a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, and the like; The above ethylenically unsaturated compounds (G) can be used alone or in combination of two or more.

[0184] The ethylenically unsaturated compound may be a commercially available product. Examples of the commercially available product include Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (all manufactured by Nippon Kayaku Co., Ltd.); Aronix M-215, M-350 (all manufactured by Toagosei Co., Ltd.); NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0185] Ethylenically unsaturated compounds having a molecular weight of 1,000 or less are excellent in sensitivity, and the resulting cured products have excellent chemical resistance. For the same reasons, those having a molecular weight of 200 or more and 800 or less are particularly preferred.

[0186] A polymerizable composition containing a polyethylenically unsaturated compound having two or more ethylenically unsaturated bonds in the molecule is preferred because it has excellent sensitivity and the obtained cured product has excellent chemical resistance, and a polyethylenically unsaturated compound having 2 to 6 ethylenically unsaturated bonds in the molecule is preferred because in addition to the above properties, a cured product having a high-resolution pattern can be obtained.

[0187] As the ethylenically unsaturated compound, a urethane acrylate having a structure obtained by reacting an alcohol having an ethylenically unsaturated bond with a polyfunctional isocyanate compound having two or more isocyanate groups can also be preferably used. The polymerizable composition containing the urethane acrylate is preferred because it has excellent sensitivity and the obtained cured product has excellent chemical resistance.

[0188] A polymerizable composition having an ethylenically unsaturated compound (G) content of 5 to 150 parts by mass relative to 100 parts by mass of the alkali developable resin (C) is preferred because it gives a cured product having high sensitivity and excellent chemical resistance, more preferably 7 to 100 parts by mass, and particularly preferably 10 to 70 parts by mass.

[0189] A solvent may be further added to the polymerizable composition of the present invention. The solvent is a compound that is liquid at 25°C under 1 atmospheric pressure and does not fall under the above (A) to (E). As the solvent, a solvent that can dissolve or disperse each of the above components ((A) to (E), and further (F), (G), etc., as necessary) can usually be used as needed.For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGM EA), ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; paraffinic solvents such as mineral spirits, Swazol #310 (all manufactured by Cosmo Matsuyama Oil); and Solvesso #100 (all manufactured by Exxon Chemical); 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 solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and water, and these solvents can be used alone or as a mixed solvent of two or more. Among these, ketones and ether ester solvents, especially PGMEA and cyclohexanone, are preferred because they have good compatibility with the resist and the polymerization initiator in the polymerizable composition.

[0190] In the polymerizable composition of the present invention, the content of the above-mentioned solvent is not particularly limited, but is preferably 30 to 95 mass % relative to 100 mass % of the total amount of the polymerizable composition, and more preferably 50 to 95 mass %. When the content of the solvent is within the above range, the polymerizable composition has excellent handleability (viscosity and wettability of the polymerizable composition), reduced unevenness during drying, and liquid stability (no precipitation or sedimentation of the components contained in the composition), and this is preferable because it allows appropriate control of the thickness of the cured product when it is obtained.

[0191] To the polymerizable composition of the present invention, conventional additives such as dispersants, organic polymers, inorganic compounds, coupling agents, chain transfer agents, sensitizers, surfactants, leveling agents, melamine compounds, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; fillers; defoamers; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-aggregation agents; catalysts; curing accelerators; crosslinking agents; and thickeners may be further added, as necessary.

[0192] The dispersant may be any dispersant capable of dispersing and stabilizing the colorant (F), and commercially available dispersants, such as the BYK series manufactured by BYK Chemie, may be used. Polymer dispersants made of polyester, polyether, or polyurethane having a basic functional group, having a nitrogen atom as the basic functional group, 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 are preferably used.

[0193] Examples of the organic polymer 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, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and the like. By using the organic polymer together with the alkali developable resin (C), the properties of the cured product can be improved.

[0194] Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder, mica, talc, kaolin, ferrocyanides, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper; and among these, titanium oxide, silica, layered clay minerals, and silver are preferred.

[0195] Examples of the coupling agent include alkyl-functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane; alkenyl-functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane; 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyltriethoxysilane; (Meth)acrylic acid ester functional alkoxysilanes such as propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 2-methacryloxypropyltrimethoxysilane; epoxy functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane; N-β(amino) Amino-functional alkoxysilanes such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane; isocyanate-functional alkoxysilanes such as 3-isocyanatepropyltriethoxysilane; ureido-functional alkoxysilanes such as 3-ureidopropyltrialkoxysilane; isocyanurate-functional alkoxysilanes such as tris-(trimethoxysilylpropyl)isocyanurate; Examples of the usable silane include titanium alkoxides such as alkoxysilane, titanium tetraisopropoxide, and titanium tetra normal butoxide; titanium chelates such as titanium dioctyloxybis(octylene glycolate) and titanium diisopropoxybis(ethyl acetoacetate); zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxy monoacetylacetonate; zirconium acylates such as zirconium tributoxy monostearate; and isocyanate silanes such as methyl triisocyanate silane. The addition of a coupling agent is preferable because it improves the adhesion between the cured product and the substrate.

[0196] As the coupling agent, commercially available products can be used, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9 103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE-103, HMDS-3, KBM-3063, KBM-3103C, KPN-3504 and KF-99 (all manufactured by Shin-Etsu Silicones).

[0197] Examples of the surfactant that can be used include anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halogen acid salts 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 surfactants.

[0198] The leveling agent can be broadly classified into silicone-based leveling agents, acrylic-based leveling agents, fluorine-based leveling agents, vinyl-based leveling agents, etc. For example, the fluorine-based leveling agent can be a leveling agent having a fluoroaliphatic hydrocarbon skeleton or a leveling agent having a polyfluoroalkylene ether skeleton, which is a repeating unit via an ether bond. It is preferable to contain a leveling agent in that a uniform cured product can be obtained.

[0199] When the polymerizable composition contains a leveling agent, the amount of the leveling agent is preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 15 parts by mass, per 100 parts by mass of the solid content (excluding colorants) in the composition, in order to enhance the above-mentioned effects of containing the leveling agent.

[0200] In the polymerizable composition of the present invention, the content of the optional components other than the above-mentioned (A) to (G) and the solvent is appropriately selected depending on the purpose of use, and is not particularly limited as long as it does not impair the effects of the present invention. However, the total content is preferably 20 parts by mass or less per 100 parts by mass of the total of the above-mentioned components (A) to (G).

[0201] The polymerizable composition of the present invention and its cured product can be used in a wide variety of applications, including curable paints, varnishes, curable adhesives, printed circuit boards, display devices (color filters in liquid crystal display panels for color displays in color televisions, PC monitors, personal digital assistants, digital cameras, etc., color filters for various display applications, color filters in CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, and black partition walls in organic EL), powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electric and electronic components, solder resists, magnetic recording Materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials and protective films used in forming dielectric layers in the sequential lamination of printed circuit boards, and various other applications, with no particular limitations on the applications, but among the above applications, they can be particularly suitably used in display devices.

[0202] In particular, when the polymerizable composition of the present invention contains a colorant (F), particularly a black pigment, it has photosensitivity and alkali developability, and is a composition that is particularly suitable for forming a BCS. In liquid crystal display devices and organic EL display devices, spacers are used to maintain the distance between the upper and lower substrates of the cell. The spacers are formed by applying a polymerizable composition to a substrate, exposing the composition through a specified mask and display device, and then developing the composition. In recent years, BCS, which integrates column spacers and black matrices into one module and has light-shielding properties, has been used.

[0203] The method for producing a cured product using the polymerizable composition of the present invention will be described in detail below. The polymerizable composition of the present invention can be applied onto a supporting substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, etc., by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing methods, immersion, etc. In addition, after being applied onto a supporting substrate such as a film, it can also be transferred onto another supporting substrate, and there is no limitation on the application method.

[0204] The light source of the energy rays used when curing the polymerizable composition of the present invention can be electromagnetic wave energy having a wavelength of 2,000 angstroms to 7,000 angstroms obtained from ultra-high pressure mercury lamps, LEDs, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., as well as high energy rays such as electron beams, X-rays, and radiation. Of these, ultra-high pressure mercury lamps and LEDs emitting light with a wavelength of 300 to 450 nm are preferred because they are highly productive and can produce high quality cured products.

[0205] Furthermore, a laser direct writing method in which an image is formed directly from digital information from a computer or the like without using a mask by using a laser beam as an exposure light source is useful because it can improve not only productivity but also resolution and positional accuracy, and light with a wavelength of 340 to 430 nm is preferably used as the laser beam, but lasers that emit 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 light in the relevant visible to infrared region is added.

[0206] The cured product of the present invention is preferably formed by the steps of (1) forming a coating film of the polymerizable composition of 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 film after exposure, and (5) heating the coating film after development. As the mask, a multi-tone mask such as a halftone mask or a grayscale mask can also be used.

[0207] The display device of the present invention has the same configuration as a conventionally known display device, except that it is provided with the cured product of the present invention. In particular, when the cured product is BCS, it is preferable that the BCS is provided between cells. EXAMPLES

[0208] EXAMPLES 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.

[0209] [Production Example 1] Preparation of alkaline developing compound PGMEA solution C-1 184 g of 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane, 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide, and 105 g of PGMEA were charged and stirred for 16 hours at 120° C. The reaction solution was cooled to room temperature, and 160 g of PGMEA, 59 g of biphthalic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added, followed by stirring at 120° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120° C. for 4 hours, at 100° C. for 3 hours, at 80° C. for 4 hours, at 60° C. for 6 hours, and at 40° C. for 11 hours, after which 128 g of PGMEA was added to obtain an alkaline developable compound C-1 as a PGMEA solution (Mw=5000, Mn=2100, acid value (solid content) 92.7 mg KOH / g). The content of the alkaline developable compound in the alkaline developable compound PGMEA solution C-1 was 45 mass%.

[0210] [Production Example 2] Production of alkaline developing compound PGMEA solution C-2 75.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 23.8 g of acrylic acid, 0.273 g of 2,6-di-t-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA were charged, and the mixture was stirred for 1 hour at 90° C., 1 hour at 100° C., 1 hour at 110° C., and 14 hours at 120° C. The mixture was cooled to room temperature, and 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, followed by stirring at 100° C. for 5 hours. Further, 30.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA were added, and the mixture was stirred at 90°C for 90 minutes and at 120°C for 4 hours, after which 122.2 g of PGMEA was added to obtain the target alkaline developable compound C-2 as a PGMEA solution (Mw=4190, Mn=2170, acid value (solid content) 52 mg KOH / g). The content of the alkaline developable compound in the alkaline developable compound PGMEA solution C-2 was 45 mass%.

[0211] [Production Example 3] Production of Carbon Black No. 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a deionized aqueous solution of sodium peroxodisulfate (concentration 2.0N) were mixed and stirred for 10 hours at 60° C. After filtration, the resulting slurry was neutralized with sodium hydroxide and treated by diafiltration. The resulting solid was dried overnight at 75° C. to obtain Carbon Black No. 1 as a black powder.

[0212] [Production Example 4] Production of Carbon Black Dispersion No. 1 20 g of Carbon Black No. 1, 3 g of Alkaline Developable Compound PGMEA Solution C-1, 3 g of DISPERBYK-161 (dispersant, manufactured by BYK-Chemie), and 100 g of PGMEA were weighed out, combined, and processed in a bead mill to obtain Carbon Black Dispersion No. 1 (solid content 20 mass %).

[0213] [Production Example 5] Preparation of Lactam Black Dispersion No. 1 An organic black pigment (lactam black, Black 582; manufactured by BASF), a dispersant (BYK-167), and a polymer for dispersion (the above-mentioned alkaline developable compound PGMEA solution C-1) were mixed in amounts of 16 parts by mass, 4.0 parts by mass, and 1.0 parts by mass, respectively, and then propylene glycol monomethyl ether acetate (PGMEA) was weighed out into this mixture so that the solids concentration was 25% by mass, to prepare a mixture. The mixture was premixed with a stirrer, and then zirconia beads with a diameter of 0.3 mm were added in the same weight as the dispersion (solvent: excluding PGMEA), and the dispersion was treated with a paint shaker at a temperature of 25 to 60°C for 6 hours, after which the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20 mass%, and the mixture was homogenized with a stirrer to obtain lactam black dispersion No. 1.

[0214] [Examples 1 to 19 and Comparative Examples 1 to 6] Preparation of polymerizable compositions Each component was mixed according to the composition shown in Tables 1 to 5 to obtain polymerizable compositions (Examples 1 to 19 and Comparative Examples 1 to 6). Note that the composition values ​​in the tables indicate parts by mass. The symbols of each component in the table represent the following components.

[0215] A-1: Compound represented by the following formula (a1) (1 mass% PGMEA solution) A-2 San-Apro Co., Ltd., U-CATSA102 (diazabicycloundecene octylate salt, 1% by mass solution in PGMEA) A-3 Shikoku Chemical Industry Co., Ltd., 2MUSIZ (a compound represented by the following formula (a3)), 1 mass% PGMEA solution A'-1 2-Ethyl-4-methylimidazole, 1% by mass solution in PGMEA B-1 A compound represented by the following formula (b1): B-2 A compound represented by the following formula (b2): B-3 A compound represented by the following formula (b3): B-4 A compound represented by the following formula (b4)

[0216] [ka] C-1 Alkaline developing compound PGMEA solution C-1 C-2 Alkaline developing compound PGMEA solution C-2 D-1 Polymerization initiator (Compound No. D9 above) D-2 BASF, OXE-01 D-3 BASF, OXE-02 E-1 Showa Denko Co., Ltd., PE-1 (compound of the following formula (e1)) E-2 Compound of the following formula (e2)

[0217] [ka]

[0218] F-1 Carbon black dispersion No.1 F-2 Lactam Black Dispersion No.1 G-1 Choko Chemical Co., Ltd., EM2692 (caprolactone-modified dipentaerythritol) G-2 Nippon Kayaku Co., Ltd., DPHA (Dipentaerythritol Hexaacrylate) G-3 Shin Nakamura Chemical Co., Ltd., A-TMPT (trimethylolpropane triacrylate) G-4 Toagosei, M-315 (isocyanuric acid EO modified di- and triacrylate) G-5 Toagosei, M-405 (Dipentaerythritol penta- and hexaacrylate, penta 10-20%) H-1 BYK-323 I-1 Propylene glycol monomethyl ether acetate (PGMEA)

[0219] [Evaluation of polymerizable composition] The storage stability, plate-making properties (line width), and low-temperature curing properties of the polymerizable compositions of Examples 1 to 19 and Comparative Examples 1 to 6 were evaluated according to the following procedures. The results are shown in [Tables 1] to [Tables 5].

[0220] <Storage stability> After blending each composition, it was stored at 5-10°C, and the change in development time was evaluated. After 2 weeks of storage, the development time (time for the coating film to dissolve) per 1 μm of film thickness was evaluated in an aqueous solution of 0.4% by mass potassium hydroxide. The development time was rated C for more than 200% of that immediately after production, B for more than 150% and 200%, A for more than 110% and 150%, and S for 110% or less. If the stability is poor, the reaction of the components in the system progresses and the components become polymerized, making it difficult to dissolve, and the development time becomes longer. In general photolithography, C and B cannot be manufactured stably. Those rated S and A are preferably used because they have excellent storage stability, and S and A are preferable, with S being particularly preferable.

[0221] <Plate making (line width)> The polymerizable compositions obtained in Examples 1 to 19 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 6 were applied onto a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 100°C for 100 seconds to obtain a coating film having a thickness of 4 μm. The obtained coating film was irradiated with a dose of 50 mJ / cm using a Proximity Liner (product name: TME-150R, manufactured by Topcon Corporation) as a light source through a 20 μm mask. 2 The exposure was performed at . The exposed coating was developed by immersing in an aqueous solution of 0.4% by mass potassium hydroxide at 25°C for 60 seconds, and thoroughly rinsed with water. After rinsing and drying, it was further baked at 120°C for 30 minutes. It can be judged that the closer the line width of the pattern is to the mask width of 20μm, the more highly precise the patterning is possible. The pattern line width was evaluated as A when it was 19μm or more and less than 21μm, B when it was 18μm or more and less than 19μm or 21μm or more and less than 22μm, and C when it was less than 18μm or 22μm or more.

[0222] <Low temperature curability> The polymerizable compositions obtained in Examples 1 to 19 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 6 were applied onto a glass substrate (100 mm × 100 mm) using a spin coater and prebaked at 100°C for 100 seconds to obtain a coating film having a thickness of 4 μm. The obtained coating film was irradiated with a dose of 50 mJ / cm using a mirror projection aligner (product name: TME-150RAK, manufactured by Topcon Corporation) as a light source through a 20 μm mask. 2 The exposure was performed at . The exposed coating was developed by immersing in a 4% by weight aqueous solution of potassium hydroxide at 25°C for 60 seconds and thoroughly rinsed with water. After rinsing and drying, post-baking (120°C for a specified time) was performed, and the resulting cured product was then immersed in PGMEA at room temperature for 10 minutes to check for any changes such as peeling or a thinner film thickness. The hardened product that showed no change after 30 minutes of post-baking was classified as A, the hardened product that showed a change after 30 minutes of post-baking and no change after 60 minutes of post-baking was classified as B, and the hardened product that showed a change even after 60 minutes of post-baking was classified as C.

[0223] [Table 1]

[0224] [Table 2]

[0225] [Table 3]

[0226] [Table 4]

[0227] [Table 5]

[0228] As can be seen from the results of Tables 1 to 5, the polymerizable compositions of the examples containing a tertiary amine compound or its salt (A), a cyclic ether compound (B), an alkali-developable resin (C), a polymerization initiator (D), and a compound having active hydrogen capable of reacting with the cyclic ether compound (E) have low-temperature curing properties and storage stability, and are capable of high-definition patterning (excellent plate-making properties). In contrast, Comparative Examples 1, 3, 5, and 6, which do not contain the (A), (B), (D), or (E) components, were poor in low-temperature curing properties (Comparative Examples 1, 3, and 6 did not cure at 120°C). Comparative Examples 5 and 6 also had poor plate-making properties. Furthermore, Comparative Example 2, which used a secondary amine instead of a tertiary amine, was poor in storage stability and plate-making properties, and Comparative Example 4, which did not contain the (C) component, had poor patterns and plate-making properties could not be evaluated.

Claims

1. A tertiary amine compound represented by the following general formula (I) or a salt thereof (A): A cyclic ether compound (B), Alkaline developable resin (C), A polymerization initiator (D) and A polymerizable composition comprising a compound (E) having an active hydrogen capable of reacting with the cyclic ether compound. 【Chemistry 1】 (In the formula, R 101 and R 103 each independently represent a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic ring-containing group having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms in which one or more methylene groups are substituted with a divalent group selected from the following <Group A>; <Group A> is —O—, —S—, —NR 104 —, —CO—, —O—CO—, —CO—O— and —SO 2 —; R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 104 s are present, they may be independently the same or different; R 102 is a group represented by the following formula (α): 【Chemistry 2】 (In the formula, L 1 is an alkylene group having 1 to 4 carbon atoms, X 1 is --CO--O-- or --O--CO--, and L 2 is an alkyl group having 3 to 18 carbon atoms.)

2. A tertiary amine compound or a salt thereof (A), which is a compound represented by the following general formula (I): A cyclic ether compound (B), Alkaline developable resin (C), A polymerization initiator (D) and The composition contains a compound (E) having an active hydrogen capable of reacting with the cyclic ether compound, The alkali developable resin (C) is A polymerizable composition comprising an epoxy addition compound having a structure obtained by an esterification reaction between a polybasic acid anhydride and an epoxy compound represented by the following general formula (II) and an unsaturated monobasic acid added thereto: 【Chemistry 3】 (In the formula, R 101 , R 102 and R 103 each independently represent a heterocyclic group having 2 to 10 carbon atoms, a heterocyclic ring-containing group having 3 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms in which one or more methylene groups have been substituted with a divalent group selected from the following <Group A>; <Group A> is —O—, —S—, —NR 104 —, —CO—, —O—CO—, —CO—O— and —SO 2 —; R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R 104 s, they may be independently the same or different. 【Chemistry 4】 (In the formula, M represents a direct bond, -O-, -S-, -SO 2 -, -SS-, -SO-, -CO-, -OCO-, 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 an unsaturated bond, -O- or -S-, or represents a group selected from the group represented by the following formulas (a), (b), (c) and (d): R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, 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 an unsaturated bond, -O- or -S-; n is a number from 0 to 10, When n≧1, each of the multiple occurrences of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and M may be the same or different. 【Chemistry 5】 (In the formula, R 9 represents a hydrocarbon group having 1 to 20 carbon atoms, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the group having 3 to 20 carbon atoms are substituted with an unsaturated bond, -O- or -S-; R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 22 and R 15 , R 15 and R 16 , R 30 and R 23 , R 23 and R 24 , R 24 and R 25 , R 38 and R 31 , R 31 and R 32 , R 32 and R 33 , R 34 and R 35 , R 35 and R 36 , and R 36 and R 37 may be bonded to form a ring; In the groups represented by formulas (a), (b), (c) and (d), * represents a bond.

3. 3. The polymerizable composition according to claim 1, wherein the cyclic ether compound (B) is an epoxy compound.

4. The alkali developable resin (C) is The polymerizable composition according to claim 1, which is an unsaturated compound having a structure obtained by an esterification reaction between an epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following general formula (II) and a polybasic acid anhydride: 【Chemistry 6】 (In the formula, M is a direct bond, —O—, —S—, —SO ２ -, -SS-, -SO-, -CO-, -OCO-, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are replaced with an unsaturated bond, -O- or -S-, or a group selected from the group represented by the following formulas (a), (b), (c) and (d): R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ each independently represents a hydrogen atom, a halogen atom, 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 an unsaturated bond, -O- or -S-; n is a number from 0 to 10, When n ≥ 1, multiple R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ and M may be the same or different. 【Chemistry 7】 (In the formula, R ９ represents a hydrocarbon group having 1 to 20 carbon atoms, R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , R １８ , R １９ , R ２０ , R ２１ , R ２２ , R ２３ , R ２４ , R ２５ , R ２６ , R ２７ , R ２８ , R ２９ , R ３０ , R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ and R ３８ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the group having 3 to 20 carbon atoms are substituted with an unsaturated bond, -O- or -S-; R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R ２２ and R １５ , R １５ and R １６ , R ３０ and R ２３ , R ２３ and R ２４ , R ２４ and R ２５ , R ３８ and R ３１ , R ３１ and R ３２ , R ３２ and R ３３ , R ３４ and R ３５ , R ３５ and R ３６ and R ３６ and R ３７ may combine to form a ring, In the groups represented by formulas (a), (b), (c) and (d), * represents a bond.

5. The polymerizable composition according to any one of claims 1 to 4, wherein the polymerization initiator (D) is a polymerization initiator having a group represented by the following general formula (III): 【Chemistry 8】 (In the formula, R ４１ and R ４２ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a group containing a heterocycle and having 3 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the group having 3 to 20 carbon atoms are substituted with the following <Group B>, <Group B> is -O-, -CO-, -COO-, -OCO-, -NR ４３ --, --NR ４３ CO-, -S-, -CS-, -SO ２ -, -SCO-, -COS-, -OCS- and CSO-; R ４３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, m1 represents 0 or 1; In the formula, * represents a bond.

6. 6. The polymerizable composition according to claim 1, wherein the compound (E) having an active hydrogen capable of reacting with the cyclic ether compound is a thiol compound.

7. The polymerizable composition according to any one of claims 1 to 6, further comprising a colorant (F).

8. The polymerizable composition according to any one of claims 1 to 7, further comprising (G) an ethylenically unsaturated compound having a molecular weight of 1,000 or less.

9. A cured product of the polymerizable composition according to any one of claims 1 to 8.

10. A display device comprising the cured product according to claim 9.

11. A method for producing a cured product using the polymerizable composition according to any one of claims 1 to 8.

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