Composition, black matrix, cured product, method for producing cured product, and display device

Abstract

The composition contains a compound (A) having a carboxyl group, an epoxy compound (B), a thiol compound (C), a tertiary amine compound (D) having a fused ring and not having an NH group, a colorant (E) and a polymerization initiator (F). The epoxy equivalent weight of the epoxy compound (B) is preferably 80 g / eq. Or more and less than 300 g / eq. The thiol compound (C) is preferably a secondary thiol compound. The colorant (E) is preferably a sulfonic acid-treated carbon black.

Description

Technical Field

[0001] The present invention relates to a composition containing a compound having a carboxyl group, an epoxy compound, a thiol compound, a tertiary amine compound, a colorant and a polymerization initiator. Background Art

[0002] Conventionally, a composition containing an epoxy compound, a compound having a carboxyl group, and a polymerization initiator has been used for various applications such as a solder resist, a color filter, a black matrix, and a black columnar spacer.

[0003] For example, Patent Document 1 describes a photosensitive resin composition used for manufacturing a substrate with a resin film, wherein the photosensitive resin composition is applied to a substrate having a heat-resistant temperature of 140° C. or less, exposed through a photomask, unexposed portions are removed by development, and then heated at 140° C. or less to form a predetermined resin film pattern, thereby manufacturing the substrate with a resin film. The photosensitive resin composition comprises:

[0004] (A) an alkali-soluble resin containing an unsaturated group,

[0005] (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds,

[0006] (C) Epoxy compounds,

[0007] (D) a curing agent and / or a curing accelerator of an epoxy compound,

[0008] (E) a photopolymerization initiator,

[0009] (F) Solvent: The total amount of the components C and D in the solid content other than the component F is 6 to 24% by mass.

[0010] Patent Document 1 describes that the composition disclosed in the document has low-temperature curing properties.

[0011] In addition, the applicant has proposed a polymerizable composition comprising 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 active hydrogen that can react with the above-mentioned cyclic ether compound (E) (Patent Document 2).

[0012] The polymerizable composition of Patent Document 2 is excellent in storage stability, enables high-precision patterning, and has excellent low-temperature curing properties that have been difficult to obtain conventionally, thus contributing to energy saving in the production process.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Application Publication No. 2019-70720

[0016] Patent Document 2: Japanese Patent Application Publication No. 2022-061912 Summary of the invention

[0017] However, the photosensitive resin composition described in Patent Document 1 has problems with low-temperature curability, storage stability, and patterning properties.

[0018] Furthermore, the present inventors have conducted studies and have found that the low-temperature curability and storage stability, particularly the storage stability at room temperature, of the composition described in Patent Document 2 have room for improvement.

[0019] The present invention aims to solve the problems of the above-mentioned prior art and to provide a polymerizable composition having storage stability in addition to low-temperature curability and capable of high-definition patterning, a cured product thereof, a method for producing the cured product, and a display device using the cured product.

[0020] As a result of intensive research, the present invention has solved the above-mentioned problems by providing the following [1] to

[12] .

[0021] [1] A composition comprising:

[0022] A compound having a carboxyl group (A),

[0023] Epoxy compounds (B),

[0024] Thiol compounds (C),

[0025] A tertiary amine compound (D) having a condensed ring and having no NH group,

[0026] Colorant (E) and

[0027] A polymerization initiator (F).

[0028] [2] The composition according to [1], wherein

[0029] The compound (A) having a carboxyl group includes an unsaturated compound having a structure obtained by an esterification reaction between an epoxy addition compound and a polybasic acid anhydride,

[0030] The epoxy addition compound has a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following formula (I).

[0031] [Chemical formula 1]

[0032]

[0033] (wherein, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO 2 -, -SS-, -SO-, -CO-, -OCO-, or a substituent selected from the group represented by the following formulae (a), (b), (c) and (d),

[0034] The hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with halogen atoms.

[0035] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom,

[0036] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 The methylene group in the hydrocarbon group having 1 to 20 carbon atoms represented by is sometimes substituted with an unsaturated bond, -O- or -S-.

[0037] n represents a number from 0 to 10,

[0038] In the case of n ≥ 1, multiple R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and M are sometimes the same and sometimes different.)

[0039] [Chemical formula 2]

[0040]

[0041] (Where R 9 represents a hydrocarbon group having 1 to 20 carbon atoms,

[0042] 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 hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom,

[0043] 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 The methylene group in the hydrocarbon group having 1 to 20 carbon atoms represented by is sometimes substituted with an unsaturated bond, -O- or -S-.

[0044] R 10 With R 11 , R 11 With R 12 , R 12 With R 13 , R 13 With R 14 , R 22With R 15 , R 15 With R 16 , R 30 With R 23 , R 23 With R 24 , R 24 With R 25 , R 38 With R 31 , R 31 With R 32 , R 32 With R 33 , R 34 With R 35 , R 35 With R 36 and R 36 With R 37 Sometimes they bond to form rings,

[0045] In the groups represented by formulae (a), (b), (c) and (d), * represents a bonding site.)

[0046] [3] The composition according to [1] or [2], wherein

[0047] The epoxy compound (B) has an epoxy equivalent of 80 g / eq. or more and less than 300 g / eq.

[0048] [4] The composition according to any one of [1] to [3], wherein

[0049] The above-mentioned thiol compound (C) is a secondary thiol (may also be called a secondary thiol) compound.

[0050] [5] The composition according to any one of [1] to [4], wherein

[0051] The tertiary amine compound (D) is 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0052] [6] The composition according to any one of [1] to [5], wherein

[0053] The colorant (E) is sulfonic acid treated carbon black.

[0054] [7] The composition according to any one of [1] to [6], wherein

[0055] The above-mentioned polymerization initiator (F) is an oxime ester compound.

[0056] [8] The composition according to any one of [1] to [7], wherein

[0057] It further contains an ethylenically unsaturated compound (G).

[0058] [9] A black matrix comprising the composition according to any one of [1] to [8].

[0059]

[10] A method for producing a cured product, comprising the step of irradiating the composition according to any one of [1] to [8] with light.

[0060]

[11] A cured product, which is a cured product of the composition according to any one of [1] to [8].

[0061]

[12] A display device comprising the cured product described in

[11] . DETAILED DESCRIPTION

[0062] Hereinafter, the composition of the present invention will be described in detail based on preferred embodiments.

[0063] The composition of the present invention contains a compound having a carboxyl group (A), an epoxy compound (B), a thiol compound (C), a tertiary amine compound having a condensed ring and having no NH group (D), a colorant (E), and a polymerization initiator (F).

[0064] The inventors have conducted in-depth research on the composition containing a compound having a carboxyl group, an epoxy compound, a thiol compound, an amine compound, a colorant and a polymerization initiator, which can obtain low-temperature curing and storage stability. As a result, it is surprisingly recognized that by using a specific amine compound in combination with an epoxy compound and a thiol compound, high-precision patterning can be achieved, and significant low-temperature curing and storage stability that were previously difficult to obtain can be obtained. Since the present invention can suppress the curing temperature that previously required 200 to 250°C to about 100°C in, for example, black columnar spacers or black matrix applications, and color resist applications, it is possible to achieve energy saving in the manufacturing process and the applicability of non-heat-resistant components that were previously impossible.

[0065] Each component will be described below in order.

[0066] <Compound (A) Having a Carboxyl Group>

[0067] The compound (A) having a carboxyl group of the present invention (hereinafter also referred to as "compound (A)") refers to a compound having a carboxyl group in the molecule. In the present invention, from the perspective of forming a composition with further excellent patterning properties, the compound (A) preferably has an ethylenically unsaturated bond group such as an acrylic group, a methacrylic group, and a vinyl group.

[0068] It should be noted that compounds belonging to the tertiary amine compound (D) having a condensed ring and having no NH group described later are not considered to belong to the compound (A). In the present invention, as the compound (A), any conventionally used compound can be used as long as it satisfies the above conditions.

[0069] The preferred functional group equivalent of the carboxyl group in the compound (A) (mass of the polymer compound containing 1 equivalent of the carboxyl group) is 50 to 10,000 g / eq.

[0070] The preferred weight average molecular weight of compound (A) is 1,000 to 500,000, preferably a compound having a weight average molecular weight of 3,000 or more, and more preferably a compound having a carboxyl group having a weight average molecular weight of 4,000 to 15,000. Such a weight average molecular weight is particularly preferred when the composition of the present invention is used as a black columnar spacer (hereinafter also referred to as BCS), especially a black partition wall of an organic EL, because of the verticalization of the pattern shape, the improvement of the development adhesion, the improvement of the heat resistance, etc.

[0071] In addition, when a compound is a polymer, the molecular weight means a weight average molecular weight (Mw). In addition, the weight average molecular weight can be calculated|required as a standard polystyrene conversion value by gel permeation chromatography (GPC).

[0072] The weight average molecular weight can be obtained by, for example, using GPC (LC-2000plus series) manufactured by JASCO Corporation, setting the elution solvent to tetrahydrofuran, setting the calibration curve to polystyrene standards of Mw1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and setting the measurement column to KF-804, KF-803 or KF-802 (manufactured by Showa Denko K.K.). In addition, the measurement temperature can be set to 40°C, and the flow rate can be set to 1.0 mL / min.

[0073] The acid value of the compound (A) is preferably 10 to 200 mg·KOH / g, and more preferably 30 to 150 mg·KOH / g. When the acid value is 10 mg·KOH / g or more, sufficient alkali developability is easily obtained, and when the acid value is 200 mg·KOH / g or less, the production of the polymer compound becomes easy. Here, the acid value can be calculated based on JIS K 0070.

[0074] As compound (A), specifically, a copolymer of acrylate having a carboxyl group, an epoxy acrylate resin having a carboxyl group, etc. can be used. In addition, as compound (A), an unsaturated compound having a structure obtained by an esterification reaction of an epoxy addition compound and a polyacid anhydride (hereinafter, also described as compound (A1)) can also be used.

[0075] Among the compounds (A1), it is preferred to use a compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the formula (I) as the epoxy addition compound, because the low-temperature curing property is more excellent.

[0076] The epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by formula (I) generally has the following structure [(e)]. In addition, the reaction product obtained by the esterification reaction of the epoxy addition compound and a polybasic acid anhydride generally has the following structure [(f)].

[0077] [Chemical formula 3]

[0078]

[0079] (Where Y 1 represents the residue of an unsaturated monobasic acid, Y 2 Indicates the residue of a polyacid anhydride, and * indicates the bonding site. )

[0080] The hydrocarbon group having 1 to 20 carbon atoms represented by M in the above formula (I) is not particularly limited, but preferably represents 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 them, 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 from the viewpoint of good sensitivity when used as compound (A).

[0081] Examples of the chain alkylene group having 1 to 20 carbon atoms represented by M in the above formula (I) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and eicosylene.

[0082] Examples of the alkenylene group having 2 to 20 carbon atoms represented by M in the above formula (I) include 1,2-ethylenediyl (also referred to as vinylene or 1,2-vinylene), 2-butene-1,4-diyl, and 1,2-dimethyl-1,2-ethylenediyl.

[0083] Examples of the cycloalkylene group having 3 to 20 carbon atoms represented by M in the above formula (I) include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene.

[0084] Examples of the arylene group having 6 to 20 carbon atoms represented by M in the above formula (I) include phenylene, tolylene, xylylene, naphthylene, biphenylene, fluorene and indan.

[0085] In the above formula (I), R 1 ~R 8 , R 9 , R 10 ~R 38 (hereinafter referred to as “R 1 The hydrocarbon group having 1 to 20 carbon atoms represented by "(etc.") 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.

[0086] The chain alkyl group having 1 to 20 carbon atoms may be straight chain or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl.

[0087] 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.

[0088] Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalenyl, bicyclo[1.1.1]pentyl and tetradecahydroanthracenyl.

[0089] 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.

[0090] 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.

[0091] Examples of the arylalkyl group having 7 to 20 carbon atoms include groups in which one or more hydrogen atoms in the above-mentioned alkyl groups are replaced with the above-mentioned aryl groups. Specifically, examples include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and naphthylpropyl groups, or groups in which hydrogen atoms in the rings of these groups are replaced with the above-mentioned aliphatic hydrocarbon groups.

[0092] In the present specification, regarding a hydrocarbon group or a group containing a heterocyclic ring described later, a methylene group in the group may be substituted by an unsaturated bond, -O- or -S- (hereinafter also referred to as "unsaturated bond, etc."). 1 The group in which one or more methylene groups in a hydrocarbon group having 1 to 20 carbon atoms represented by the formula (e.g., 1 The hydrocarbon group having 1 to 20 carbon atoms represented by the above-mentioned groups wherein one or more methylene groups in the above-mentioned groups are substituted with an unsaturated bond, etc. The same applies to the case where the methylene group in the specified group is substituted with a group selected from the group B described later.

[0093] In addition, in this 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 an unsaturated bond, etc., it is set that the oxygen atoms are not adjacent, and it is preferably set that the divalent groups selected from an unsaturated bond, -O- and -S- are not adjacent to each other. It should be noted that the same is true when the above-mentioned methylene group is substituted with a group selected from <Group B> described later.

[0094] R 1The hydrocarbon group having 1 to 20 carbon atoms represented by the above, wherein the methylene group in the group is sometimes substituted with an unsaturated bond, etc., may have a hydrogen atom substituted or unsubstituted. When the hydrogen atom in the hydrocarbon group is substituted, the substituent is preferably selected from the following substituent group 1.

[0095] Substituent Group 1: halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups, heterocyclic groups having 2 to 10 carbon atoms, and groups having 3 to 20 carbon atoms containing heterocyclic groups.

[0096] The heterocyclic group in the substituent group 1 refers to a group obtained by removing one hydrogen atom from a heterocyclic compound. The heterocyclic group is not particularly limited, but examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazinyl, piperazinyl, piperidinyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, purinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzo[1,2-d]pyrazol ... furanyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, indolyl, benzoxazolyl, benzotriazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-oxoimidazolidin-3-yl and 2,4-dioxooxazolidin-3-yl, isocyanurate, 1,3-dioxolanyl, and the like.

[0097] The group having 3 to 20 carbon atoms and containing a heterocyclic ring in Substituent Group 1 refers to a group in which a heterocyclic group is bonded to a group other than a heterocyclic group. The bonding site may be on the heterocyclic ring or on a group other than the heterocyclic ring.

[0098] The groups other than the above heterocyclic groups are not particularly limited, but examples thereof include hydrocarbon groups having 1 to 6 carbon atoms. If the number of carbon atoms in the group containing the heterocyclic ring is 20 or less, any number of bonds may be formed, one or more. Examples of the hydrocarbon groups having 1 to 6 carbon atoms include the above R 1 Among the groups exemplified as the hydrocarbon groups having 1 to 20 carbon atoms represented by the above, the hydrocarbon groups satisfying the prescribed number of carbon atoms are mentioned.

[0099] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0100] In this specification, the number of carbon atoms in a group obtained by substitution with a substituent is set as specified in the annotations of the general formula. 1When a hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms represented by , etc. is substituted by a carbon atom-containing group as a substituent, the number of carbon atoms of the substituted hydrocarbon group including the number of carbon atoms of the substituent is set to R in the explanation of formula (I). 1 The hydrocarbon group represented by is 1 to 20 carbon atoms.

[0101] For R in the above formula (I), 1 ~R 8 , R 9 , R 10 ~R 38 The hydrocarbon group having 1 to 20 carbon atoms represented is preferably 10 or less in terms of good sensitivity when used as compound (A) and excellent alkali developability. That is, the hydrocarbon group is preferably a chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms.

[0102] As sometimes replace R 1 ~R 8 and R 10 ~R 38 Examples of the unsaturated bond of the methylene group in the group represented by include -C=C- and -C≡C-.

[0103] As R in the above formulas (a) to (d), 10 With R 11 , R 11 With R 12 , R 12 With R 13 , R 13 With R 14 , R 22 With R 15 , R 15 With R 16 , R 30 With R 23 , R 23 With R 24 , R 24 With R 25 , R 38 With R 31 , R 31 With R 32 , R 32 With R 33 , R 34 With R 35 , R 35 With R 36 and R 36 With R 37Examples of the ring formed by bonding include cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, 5- to 7-membered rings such as lactone rings and lactam rings, and condensed rings such as naphthalene and anthracene.

[0104] In particular, from the viewpoint of obtaining a composition having excellent low-temperature curability and storage stability, in formula (I), M is preferably a substituent represented by formula (b) or (d).

[0105] In addition, from the viewpoint of the availability of compound (A) and the excellent heat resistance of the obtained cured product, R 1 ~R 8 , R 10 ~R 38 It 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.

[0106] The 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.

[0107] 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.

[0108] Examples of the polybasic acid anhydride that is activated after the unsaturated monobasic acid is activated include biphenyltetracarboxylic anhydride, tetrahydrophthalic anhydride, succinic anhydride, diphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol ditrimellitic anhydride, glycerol trimellitic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylnadic anhydride.

[0109] The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably set as follows from the viewpoint of good alkali developability.

[0110] That is, the epoxy addition compound is preferably added in a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid to one epoxy group of the epoxy compound, and more preferably added in a ratio of 0.2 to 1.0. In addition, the compound (A) is preferably added in a ratio of 0.1 to 1.0 acid anhydride structures of the polybasic acid anhydride to one hydroxyl group of the epoxy addition product, and more preferably added in a ratio of 0.2 to 1.0.

[0111] The reaction of the epoxy compound represented by the above formula (I), the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to a conventional method.

[0112] As compound (A1), a compound obtained by further reacting an epoxy addition compound with a polybasic acid anhydride with a monofunctional or polyfunctional epoxy compound (hereinafter, compound (A1-2) can be used. In order to distinguish from compound (A1-2), the compound at the stage of esterification reaction between the epoxy addition compound and the polybasic acid anhydride is also referred to as compound (A1-1). By using compound (A1-2), it becomes possible to adjust the acid value of the composition of the present invention, and by adjusting the acid value, it is possible to fine-tune the alkali developability (development speed, pattern shape, etc.).

[0113] Regarding the epoxy addition compound, the acid value of the solid content of the compound (A) is preferably in the range of 5 to 120 mg·KOH / g from the viewpoint of good alkali developability, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected so that the compound (A1-2) satisfies the above acid value.

[0114] In addition, the solid content referred to in this specification means a component obtained by removing a solvent described later from a composition.

[0115] 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, tert-butyl glycidyl ether, amyl 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, Oily ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl 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, butyric acid glycidyl ester, vinyl cyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the following epoxy compounds No.E1, No.E2, etc.

[0116] [Chemical formula 4]

[0117] Epoxy Compound No.E1

[0118]

[0119] [Chemical formula 5]

[0120] Epoxy Compound No.E2

[0121]

[0122] As the polyfunctional epoxy compound, it is preferred to use one or more compounds selected from the group consisting of bisphenol epoxy compounds and glycidyl ethers, because a cured product having good heat resistance can be obtained.

[0123] As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the above formula (I), for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can be used.

[0124] In addition, as the above-mentioned glycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tris(glycidyloxymethyl)propane, 1,1,1-tris(glycidyloxymethyl)ethane, 1,1,1-tris(glycidyloxymethyl)methane, 1,1,1,1-tetra(glycidyloxymethyl)methane, and the like can be used.

[0125] In addition, novolac epoxy compounds (phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds and other novolac epoxy compounds); alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane ; Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer acid ester; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, and N,N-diglycidyl aniline; 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.

[0126] As the compound (A), a commercially available item can also be used appropriately.

[0127] Examples of the 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 Co., Ltd.), and CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.).

[0128] In the composition of the present invention, the content of compound (A) is preferably 20 to 90 parts by mass relative to 100 parts by mass of the total amount of compound (A), epoxy compound (B), thiol compound (C), tertiary amine compound (D) having a condensed ring and no NH group, colorant (E) and polymerization initiator (F), from the perspective of being more easily obtaining a cured product with a high-definition pattern and being able to obtain stable solubility in an alkaline developer, more preferably 25 to 75 parts by mass, and particularly preferably 25 to 50 parts by mass. Compound (A) is preferably the component with the largest mass in the solid content other than the colorant in the composition.

[0129] From the same viewpoint as above, in the composition of the present invention, the content of compound (A) is preferably 20 to 85 parts by mass, more preferably 30 to 75 parts by mass, and particularly preferably 40 to 65 parts by mass, relative to 100 parts by mass of the solid content of the composition (excluding the colorant).

[0130] <Epoxy Compound (B)>

[0131] The epoxy compound (B) of the present invention (hereinafter also referred to as "compound B") refers to a compound having no carboxyl group in the molecule and having one or more epoxy groups. For example, a compound having no carboxyl group in one molecule and having an epoxy group is included in compound (B).

[0132] Examples of such a compound (B) include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds.

[0133] (B-1) Aromatic Epoxy Compound

[0134] The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group, and having no cycloolefin oxide structure.

[0135] As such an aromatic epoxy compound, a compound having at least one aromatic hydrocarbon ring may also be used. Examples of the aromatic epoxy compound include polyglycidyl ethers of polyphenols 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 dibutyl alcohol; polyglycidyl esters of polyacid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid; diepoxides of divinylbenzene; glycidylamine compounds such as N,N-diglycidylaniline or its derivatives, etc. In addition, there can be mentioned 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 containing a group capable of reacting with an epoxy group to form a covalent bond.

[0136] 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 Co., Ltd.); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (manufactured by Osaka Gas Chemicals (Co., Ltd.); HP4032, HP4032D, HP4700 (DIC (Co., Ltd.)); ESN-475V (Toto Kasei Co., Ltd.); YX8800 (Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (NOF Co., Ltd.); EPICLON N-665、EPICLON HP-7200 (manufactured by DIC Co., Ltd.); 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 P-4100, ADEKA RESIN EP-4901, EP-3950S, EP-3950L, EP-3980S (manufactured by ADEKA Co., Ltd.); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.), etc.

[0137] (B-2) Aliphatic Epoxy Compound

[0138] The aliphatic epoxy compound is a compound having an epoxy group and not containing an oxycycloolefin structure and an aromatic ring.

[0139] Specific examples of such aliphatic epoxy compounds include glycidyl ethers of aliphatic alcohols and polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. More specifically, glycidyl ethers of polyols 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 glycerol, 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; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to an aliphatic polyol such as propylene glycol, trimethylolpropane, and glycerol; monoglycidyl ethers of aliphatic higher alcohols; and epoxidized polybutadiene. In addition, compounds having a tricyclodecane structure and a glycidyl ether group, such as dimethylol tricyclodecane diglycidyl ether and tricyclodecane diglycidyl ether, can be cited. In addition, compounds obtained by reacting an aliphatic glycidyl ether type epoxy compound having two or more glycidyl ether groups with a main chain skeleton containing a rubber component and containing a group that can react with an epoxy group to form a covalent bond can be cited.

[0140] Furthermore, as the aliphatic epoxy compound, a hydrogenated product of an aromatic epoxy compound such as hydrogenated bisphenol A diglycidyl ether may be used.

[0141] As the aliphatic epoxy compound, a compound having a structure in which an oxirane group is directly single-bonded to a cycloalkyl ring derived from an oxirane cycloalkyl ring as a constituent unit and a structure in which epoxy groups having an oxirane cycloalkyl ring are polymerized with each other, such as a 1,2-epoxy-4-(2-oxirane)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, as a main chain structure may be used.

[0142] As the aliphatic epoxy compound, commercially available aliphatic epoxy compounds 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, DENACOL EX-831, DENACOL EX-832, DENACOL EX-833, DENACOL EX-834, DENACOL EX-835, DENACOL EX-836, DENACOL EX-837, DENACOL EX-838, DENACOL EX-839, DENACOL EX-840, DENACOL EX-841, DENACOL EX-842, DENACOL EX-843, DENACOL EX-844, DENACOL EX-845, DENACOL EX-846, DENACOL EX-847, DENACOL EX-848, DENACOL EX-849, DENACOL EX-850, DENACOL EX-851, DENACOL EX-852 EX-832, DENACOL EX-841, DENACOL EX-861, DENACOL EX-911, DENACOL EX-941, DENACOL EX-920, DENACOL EX-931 (manufactured by Nagase ChemteX Co., Ltd.); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (made by Kyeisha Chemical Co., Ltd.), ADEKA Glycirol ED-503, ADEKA Glycirol ED-503G, ADEKA Glycirol ED-506, ADEKA Glycirol ED-523T (manufactured by AIDICO Co., Ltd.), etc.

[0143] 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 hetero ring and a chain aliphatic epoxy compound having no aliphatic ring can be used.

[0144] (B-3) Alicyclic Epoxy Compound

[0145] Specific examples of alicyclic epoxy compounds include polyglycidyl ethers of polyols having at least one alicyclic ring and a hydroxyl group directly bonded to the alicyclic ring, and compounds containing an oxidized cycloolefin structure such as cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.

[0146] Examples of the alicyclic epoxy compound 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)cyclohexane-1,3-dioxadioxane, alkane, bis(3,4-epoxycyclohexylmethyl)adipate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-epoxypinene, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, etc.

[0147] Examples of commercially available products that can be preferably used as the alicyclic epoxy compound include alicyclic epoxy compounds described in Japanese Patent No. 6103653 and the like.

[0148] In the present invention, the epoxy equivalent of compound (B) is preferably 80 g / eq. or more and less than 300 g / eq., preferably 200 g / eq. or less, and particularly preferably 150 g / eq. or less. This is because when the epoxy equivalent is within the above range, low temperature curing property becomes good.

[0149] From the perspective of the balance between storage stability and low temperature curing properties of the composition, it is preferred to use a compound (B) having an epoxy equivalent of 80 g / eq. or more and 150 g / eq. or less and a compound (B) having an epoxy equivalent of more than 150 g / eq. and less than 300 g / eq. in combination. In this case, the amount of the compound (B) having an epoxy equivalent of 80 g / eq. or more and 150 g / eq. or less is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and particularly preferably 17 to 33% by mass relative to the total content of the compound (B).

[0150] The molecular weight of compound (B) is not particularly limited as long as the desired curing properties can be obtained, and can be set, for example, to 50 or more and 20,000 or less. From the viewpoint of the balance between the storage stability and low-temperature curing properties of the composition, and the ease of coating and bonding of the composition, it is more preferably 100 or more and 2,000 or less, and further preferably 200 or more and 1,500 or less. The molecular weight in the case of a polymer is the polymerization average molecular weight, and can be measured by the same method as described in the compound (A) section.

[0151] The number of epoxy groups contained in the compound (B) can be appropriately set according to the desired curing properties, etc. The number of epoxy groups contained in the compound (B) can be set to 1 or more per molecule of the compound (B), but can be set to 2 or more and 12 or less, preferably 2 or more and 10 or less, and most preferably 3 or more. This is because a composition using such a compound (B) can easily obtain a cured product with a high-definition pattern, and the reactivity during curing is good.

[0152] Furthermore, as one embodiment of the composition of the present invention, as compound (B), it is preferred to include an epoxy compound having a glycidyl group (hereinafter also referred to as a "glycidyl-type epoxy compound"). Because the above-mentioned composition becomes a composition that is easy to obtain low-temperature curing properties and has better pattern fineness. In particular, in compound (B), as a glycidyl group, it is also possible to contain a glycidyl ether group, a glycidyl amino group, or a diglycidyl amino group. From the perspective of further improving the low-temperature curing properties, compound (B) preferably contains a glycidyl ether group or a diglycidyl amino group, and more preferably contains a diglycidyl amino group.

[0153] As one embodiment of the composition of the present invention, as described above, it is preferred that compound (B) contains a glycidyl epoxy compound. From the perspective of improving the effect of containing the glycidyl epoxy compound, the proportion of the glycidyl epoxy compound in 100 parts by mass of the epoxy compound is preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more, and particularly preferably 80 parts by mass or more.

[0154] According to the present invention, the content of compound (B) is preferably 2 parts by mass or more and 45 parts by mass or less, more preferably 8 parts by mass or more and 35 parts by mass or less, and further preferably 15 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of compound (A). This is because the above composition has an excellent balance between storage stability and low-temperature curing properties, and it is further easy to obtain a high-definition pattern.

[0155] From the perspective of balancing the storage stability and low-temperature curing properties of the composition and the availability of high-definition patterns, the content of the compound (B) is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, and even more preferably 10 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the solid content of the composition (excluding the colorant).

[0156] From the perspective of balancing the storage stability and low-temperature curing properties of the composition and the availability of high-definition patterns, compound (B) preferably contains an aromatic epoxy compound. In compound (B), the amount of the aromatic epoxy compound is preferably 30% by mass or more, more preferably 40% by mass or more, and may also be 60% by mass or more.

[0157] <Thiol compound (C)>

[0158] The thiol compound (C) of the present invention (hereinafter also referred to as "compound (C)") refers to a compound having no carboxyl group and epoxy group in the molecule and having one or more thiol groups.

[0159] In the present invention, as examples of compound (C), compounds represented by the following formulae (C1) to (C6) are preferably used. This is because the above composition has a better low-temperature curing property. In addition, it is preferred from the perspective of easy availability, storage stability of the composition, and balance of curing properties.

[0160] [Chemical formula 6]

[0161]

[0162] (Where 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 also referred to as "L 11 ~L 64”) each 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] As the above L 11 ~L 64 The alkylene group having 1 to 10 carbon atoms represented by the above-mentioned group includes a divalent group having a structure obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms.

[0164] As the alkyl group having 1 to 10 carbon atoms, for example, the above R 1 The alkyl group having the specified number of carbon atoms among the alkyl group having 1 to 20 carbon atoms in the above.

[0165] In addition, as R 64 , R 65 and R 66 The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in the 1 The same is true for the aliphatic hydrocarbon group having 1 to 20 carbon atoms (specifically, 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, or a cycloalkylalkyl group having 4 to 20 carbon atoms).

[0166] L 11 ~L 64 An alkylene group having 1 to 10 carbon atoms represented by 64 , R 65 and R 66 The aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by the formula (a) may be substituted with one or more hydrogen atoms in the group or with two or more hydrogen atoms in the group. The substituents in the case of substitution may be the same as those in the group replacing X. 1 The same applies to the substituents for one or more hydrogen atoms of the aliphatic hydrocarbon group represented.

[0167] From the perspective of balancing the storage stability and low temperature curing properties of the composition, the above L 11 ~L 64 An alkylene group having 1 to 5 carbon atoms is preferred, and a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms is preferred, and a branched alkylene group having 3 to 5 carbon atoms is particularly preferred. This is because the composition has a better balance between storage stability and low-temperature curing properties.

[0168] As the above L 11 ~L 64Specific examples of the linear alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group (ethane-1,2-diyl group), and a propylene group (propane-1,3-diyl group).

[0169] As the above L 11 ~L 64 Specific examples of the branched alkylene group having 3 to 5 carbon atoms 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.

[0170] L in (C1) 11 and L 12 They may be the same group or different groups, but are preferably the same group from the viewpoint of ease of synthesis. This is because the above composition is a composition with a better balance between low temperature curing property and easy availability. This is for L of (C2) 21 ~L 23 , L of (C3) 31 ~L 34 , L of (C4) 41 ~L 46 、L of (C5) 51 ~L 53 、L of (C6) 61 ~L 64 Same here.

[0171] In the present invention, the above R 64 An alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is particularly preferred. This is because the composition has a better balance between storage stability and low-temperature curability.

[0172] The molecular weight of compound (C) is preferably 100 to 1,000, more preferably 300 to 900, and particularly preferably 350 to 800, from the viewpoint of the balance between storage stability and curability of the composition. This is because the composition has a better balance between storage stability and low-temperature curability.

[0173] In the present invention, as compound (C), primary thiol compounds, secondary thiol compounds, tertiary thiol compounds, etc. can be used. From the viewpoint of more significantly exerting the excellent effect of low temperature curing property of the present invention, the above-mentioned compound (C) is preferably a secondary thiol compound. For example, when compound (C) contains a secondary thiol compound, the content of the secondary thiol compound contained in compound (C) is preferably 30% by mass or more, more preferably 40% by mass or more.

[0174] Compound (C) may be monofunctional or polyfunctional. As compound (C), polyfunctional is preferred from the aspect of improving storage stability and excellent low temperature curing properties. The number of thiol groups contained in the molecule of the polyfunctional thiol compound is preferably 2 to 10, more preferably 3 to 10, more preferably 4 to 6, and particularly preferably 4. When the number of thiol groups contained in the molecule of compound (C) is within the above range, the composition becomes a composition with excellent low temperature curing properties.

[0175] As the compound (C), commercial products may be used. Examples of commercial products of the compound (C) include dodecanethiol (monofunctional thiol compound), Karenz MT (registered trademark) BD (trade name, bifunctional thiol compound, 1,4-bis(3-mercaptobutyryloxy)butane, Showa Denko KK), Karenz MT (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 KK), Karenz MT (registered trademark) PE (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko KK), EGMP-4 (trade name, bifunctional thiol compound, tetraethylene glycol bis (3-mercaptopropionate), SC Organic Chemicals KK), TMMP (trade name, trifunctional thiol compound, trimethylolpropane tris (3-mercaptopropionate), SC Organic Chemicals KK), TEMPIC (trade name, trifunctional thiol compound, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, SC Organic Chemicals KK), PEMP (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptopropionate), SC Organic Chemicals KK), DPMP (trade name, hexafunctional thiol compound, dipentaerythritol hexa (3-mercaptopropionate), SC Organic Chemicals KK), etc.

[0176] The content of the compound (C) is more preferably 5 parts by mass or more and 40 parts by mass or less, further preferably 10 parts by mass or more and 30 parts by mass or less, and particularly preferably 15 parts by mass or more and 25 parts by mass or less, based on 100 parts by mass of the solid content of the composition (excluding the colorant). This is because the above composition is a composition with an excellent balance between storage stability and low-temperature curing properties.

[0177] The content of the compound (C) is preferably 5 parts by mass or more and 400 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, further preferably 50 parts by mass or more and 200 parts by mass or less, and particularly preferably 80 parts by mass or more and 160 parts by mass or less, based on 100 parts by mass of the epoxy compound (B). This is because the composition has an excellent balance between storage stability and low-temperature curing properties, and a high-definition pattern can be easily obtained.

[0178] The content of the compound (C) is more preferably 10 parts by mass or more and 65 parts by mass or less, further preferably 15 parts by mass or more and 55 parts by mass or less, and particularly preferably 25 parts by mass or more and 45 parts by mass or less relative to 100 parts by mass of the compound (A). This is because the composition has an excellent balance between storage stability and low-temperature curing properties, and a high-definition pattern can be easily obtained.

[0179] <Tertiary amine compound (D) having a condensed ring and no NH group>

[0180] The tertiary amine compound having a condensed ring and no NH group (hereinafter also referred to as "compound (D)") of the present invention refers to a compound having no carboxyl group, epoxy group, thiol group or NH group in the molecule and having one or more condensed rings.

[0181] The composition of the present invention contains the compound (D) to be a composition having excellent storage stability. Even if an amine compound other than the compound (D) is used instead of the compound (D), the composition having excellent storage stability and low-temperature curing properties cannot be achieved.

[0182] From the viewpoint of storage stability, the compound (D) of the present invention is preferably a polycyclic tertiary amine compound. A polycyclic tertiary amine compound refers to a compound having at least a nitrogen atom in a condensed ring. The polycyclic tertiary amine compound of the present invention includes a form in which only a nitrogen atom is contained in the ring as a heteroatom and a form in which, in addition to a nitrogen atom, an oxygen atom, a sulfur atom, etc. are contained in the ring as a heteroatom. In the present invention, from the viewpoint of storage stability, it is preferred to use a polycyclic tertiary amine compound in which only nitrogen is contained in the ring as a heteroatom.

[0183] Preferred forms of polycyclic tertiary amine compounds without NH groups include: (1) a form in which a nitrogen atom in a condensed ring is bonded to one of two carbon atoms (preferably carbon atoms in the ring) located on the left and right sides thereof by a single bond and to the other by a double bond; and (2) a form in which a hydrogen atom on a nitrogen atom in a condensed ring is substituted with a substituent; and (3) a form in which a nitrogen atom in a condensed ring is shared by two or more rings and is bonded to three carbon atoms (carbon atoms in the ring). In the present invention, from the viewpoint of storage stability, the form (1), the form (2) or the form (3) is preferred, and a specific amine compound containing the forms (1) and / or (3) is preferred. "In a ring" means constituting a ring.

[0184] From the viewpoint of storage stability, the polycyclic tertiary amine compound is preferably a bicyclic or tricyclic compound, more preferably a bicyclic compound. In particular, in the case of a condensed ring, a condensed ring formed by condensing two or three rings is preferred, and a condensed ring formed by condensing two rings is preferred.

[0185] The number of nitrogen atoms contained in the condensed ring of the polycyclic tertiary amine compound having no NH group is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 2, from the viewpoint of storage stability.

[0186] Examples of polycyclic tertiary amine compounds without an NH group include aliphatic polycyclic tertiary amine compounds and aromatic polycyclic tertiary amine compounds. Aliphatic polycyclic refers to a bicyclic or polycyclic ring system having two or more, preferably three or more atoms, and all of the rings are aliphatic rings. Aromatic polycyclic refers to a ring in which at least one of the rings constituting the condensed ring is an aromatic ring.

[0187] Examples of the aliphatic polycyclic tertiary amine compound having no NH group include aliphatic bicyclic tertiary amine compounds such as 1,8-diazabicyclo[5.4.0]undec-7-ene, diazabicyclononene, and 1,5-diazabicyclo[4.3.0]nonene-5-ene.

[0188] Examples of the aromatic polycyclic tertiary amine compound having no NH group include aromatic bicyclic tertiary amine compounds such as 3H-indole, indolizine, quinoline, isoquinoline, 4H-quinolizine, and quinoline.

[0189] As the compound (D), a compound represented by the following formula (D) is preferred because both low-temperature curability and storage stability can be achieved.

[0190] [Chemical formula 7]

[0191]

[0192] In formula (D), R 101 , R 102 , R 103and R 104 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

[0193] a represents an integer from 3 to 8,

[0194] b represents an integer of 3 to 7.

[0195] As R in formula (D) 101 ~R 104 The hydrocarbon group having 1 to 4 carbon atoms represented by can be exemplified as the above R 1 The hydrocarbon groups having 1 to 20 carbon atoms represented by the above are hydrocarbon groups having the specified number of carbon atoms. 101 ~R 104 In the case of a hydrocarbon group, a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group is preferred.

[0196] In the present invention, a is preferably 3 to 6, more preferably 3 to 5, and particularly preferably 5. 101 and R 102 The number of the hydrocarbon groups in (total (2×a) groups) is preferably 0 to 2, particularly preferably 0.

[0197] In the present invention, b is preferably 3 to 5, and particularly preferably 3. 103 and R 104 The number of the hydrocarbon groups in (total (2×b) groups) is preferably 0 to 2, and particularly preferably 0.

[0198] In the present invention, a composition in which the compound (D) is particularly 1,8-diazabicyclo[5.4.0]undec-7-ene is preferred from the viewpoint of being able to achieve both low-temperature curability and storage stability.

[0199] In the composition of the present invention, the content of the compound (D) is preferably 1 to 20 parts by mass relative to 100 parts by mass of the compound (A), from the viewpoint that the low temperature curability of the composition is further improved, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 8 parts by mass.

[0200] The composition of the present invention may contain other tertiary amine compounds other than compound (D) in addition to compound (D). When containing other tertiary amine compounds, the content of other tertiary amine compounds in the composition is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less in 100 parts by mass of the total of compound (D) and other tertiary amine compounds.

[0201] <Colorant (E)>

[0202] As the colorant (E) used in the composition of the present invention, pigments and dyes can be listed. As the pigment and dye, inorganic color materials or organic color materials can be used respectively. They can be used alone or in a mixture of two or more. Among them, the pigment refers to a colorant that is insoluble in the solvent described later, and also includes those that are insoluble in the solvent in the inorganic or organic color material, or those obtained by lake-forming the inorganic or organic dye. Compound (A), epoxy compound (B), thiol compound (C), and compounds having condensed rings and belonging to compound (D) and polymerization initiator (F) are set as not belonging to colorant (E).

[0203] Examples of the pigment include carbon black obtained by a furnace process, a tank process or a thermal cracking process, or carbon black such as acetylene black, ketjen black or lamp black, carbon black prepared by adjusting or coating the carbon black with an epoxy resin, carbon black prepared by pre-dispersing the carbon black in a resin in a solvent and coating the carbon black with 20 to 200 mg / g of the resin, carbon black prepared by subjecting the carbon black 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 prepared by volatile components such as CO and CO2 at 950°C, and carbon black prepared by volatile components such as CO2 and CO2 at 950°C. 2 The total oxygen content is calculated for every 100m 2 Black pigments represented by carbon black having a surface area of ​​9 mg or more, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, helical carbon fiber, carbon nanohorn, carbon aerogel, fullerene, aniline black, synthetic iron black, pigment black 7, titanium black, lactam black and perylene black, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese series, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cobalt sky blue, chrome green, emerald green, lead sulfate, chrome yellow, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, umber, lake pigments and the like.

[0204] The black pigments can be divided into organic black pigments and inorganic black pigments. Organic black pigments are organic black pigments, and examples thereof include lactam black and perylene black, while inorganic black pigments are inorganic black pigments, and examples thereof include the various carbon blacks mentioned above.

[0205] As the above-mentioned pigment, commercially available products can also 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, 18 4, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 254, 228, 240 and 254; pigment orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 and 71; Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 15t, 152, 1 53, 154, 166, 168, 175, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62 and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50, etc.

[0206] 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, isoindolinoline compounds, quinacridone compounds, anthraquinone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, and metal complex compounds of cyanine dyes.

[0207] In the present invention, a composition in which the colorant is a black pigment is preferred from the perspective of excellent light-shielding properties. Among black pigments, carbon black is more preferred from the perspective of more excellent light-shielding properties. In the present invention, from the perspective of obtaining a composition with excellent storage stability and a cured product with excellent electrical properties (high resistance, dielectric constant properties), it is preferred to use those obtained by surface-treating carbon black. As the type of surface treatment, sulfonic acid treatment can be cited. In this specification, carbon black treated with sulfonic acid is also referred to as sulfonic acid-treated carbon black.

[0208] The method of treating the carbon black with sulfonic acid is a method of placing sulfonic acid groups on the surface of the carbon black, and examples thereof include a method (1) of oxidizing the carbon black with peroxodisulfuric acid or a salt thereof, and a method (2) of treating the carbon black with a sulfonating agent.

[0209] The method (1) for oxidizing the above-mentioned carbon black using peroxodisulfuric acid or a salt thereof can be carried out by any known method, for example, by mixing carbon black, peroxodisulfuric acid or a salt thereof, and an aqueous medium (water or a mixture of water and a water-soluble solvent) using a surfactant or a dispersant as needed, and heating the mixture at a temperature below 100° C., preferably at 40 to 90° C., for less than 24 hours, preferably for 2 to 20 hours, and neutralizing to pH 7 as needed.

[0210] Examples of the salt of peroxodisulfuric acid include metal salts such as lithium, sodium, potassium, and aluminum, and ammonium salts.

[0211] The amount of peroxodisulfuric acid or a salt thereof used is preferably in the range of 0.5 to 5 parts by mass based on 1 part by mass of carbon black.

[0212] The method (2) of treating the above-mentioned carbon black with a sulfonating agent can be carried out by any known method, for example, by mixing or dissolving the carbon black and the sulfonating agent in a solvent and stirring at a temperature below 200°C, preferably at 0 to 100°C.

[0213] Examples of the sulfonating agent include concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, halogenated sulfuric acid, amidosulfuric acid, hydrogensulfite, sulfite, SO 3 -Dioxane complex, SO 3 -Keto complex, sulfamic acid, sulfonated pyridinium salt, etc.

[0214] As the above-mentioned solvent, water; acidic solvents such as sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid, acetic anhydride, etc.; alkaline solvents such as pyridine, triethylamine, trimethylamine, etc.; ethers such as tetrahydrofuran, dioxane, diethyl ether, etc.; polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, cyclopentane, nitromethane, acetone, acetonitrile, benzonitrile, etc.; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, xylene, nitrobenzene, etc.; alcohol solvents such as methanol, ethanol, isopropanol, etc.; chlorine solvents such as chloroform, trichlorofluoromethane, dichloromethane, chlorobenzene, etc., etc., and their mixed solvents can also be used.

[0215] The amount of the sulfonating agent used is preferably in the range of 0.5 to 20 parts by mass relative to 1 part by mass of carbon black. When a plurality of sulfonating agents are used, the total amount thereof is preferably in the above range.

[0216] Furthermore, in order to suppress the formation of sulfones known as a side reaction of the sulfonation reaction, 0.01 to 5 mass % of known sulfone inhibitors such as fatty acids, organic peracids, acid anhydrides, acetic acid, ketones, etc. may be added within a range that does not inhibit the reaction.

[0217] In addition, in the case of an organic black pigment, since the resistance value of the cured film increases, it is useful as a composition for BM and BCS. As an organic black pigment, for example, lactam black can be used. Lactam black has excellent light shielding properties in the visible light range of 400nm to 700nm. By combining with compound (D), it is expected that low-temperature curing properties will be improved, as well as the light shielding properties and electrical properties (resistance value) of the obtained cured product will be improved. Lactam black is a black organic pigment having a lactam structure or its isomer ring structure or a combination thereof, for example, having a structure represented by formula (4) or formula (5) of Japanese Patent Publication No. 2016-133574. As specific examples of lactam black, IRGAPHOR (registered trademark) BLACK S0100CF and BLACK 582 of BASF can be cited. In the case where 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.

[0218] In the composition of the present invention, a cured product obtained from a composition in which the content of the colorant is 10 to 300 parts by mass relative to 100 parts by mass of the compound (A) is preferred from the perspective of excellent light-shielding properties and the ability to obtain a cured product with a high-definition pattern. The content of the colorant is more preferably 30 to 200 parts by mass, particularly preferably 55 to 150 parts by mass, and most preferably 70 to 145 parts by mass.

[0219] <Polymerization Initiator (F)>

[0220] As the polymerization initiator (F) used in the composition of the present invention, a conventionally known free radical polymerization initiator can be used. It should be noted that compounds belonging to compound (A), compound (B), or compound (D) are not considered to belong to the polymerization initiator (F).

[0221] The radical polymerization initiator is a photoradical polymerization initiator or a thermal radical polymerization initiator. From the viewpoint of high reactivity, a photoradical polymerization initiator is more preferred.

[0222] As the photo-radical polymerization initiator, as long as it is a substance that generates free radicals by light irradiation, there is no particular limitation, and conventionally known compounds can be used. As the photo-radical polymerization initiator, for example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds and oxime ester compounds can be illustrated as preferred examples.

[0223] Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1-hydroxy 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-propane-1-one, etc.

[0224] Examples of the benzil compound include benzil and the like.

[0225] Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide.

[0226] Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0227] In the present invention, a composition in which the polymerization initiator (F) is an oxime ester compound is preferred from the viewpoint of excellent low-temperature curability and patterning properties. Examples of the oxime ester compound include compounds having a group represented by the following formula (III).

[0228] [Chemical formula 8]

[0229]

[0230] (Where 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 having 3 to 20 carbon atoms containing a heterocycle, 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>,

[0231] <Group B> -O-, -CO-, -COO-, -OCO-, -NR 43 -、-NR 43 CO-, -S-, -CS-, -SO2 -, -SCO-, -COS-, -OCS- and CSO-,

[0232] R 43 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0233] m represents 0 or 1,

[0234] The * in the formula represents the bonding site. )

[0235] As 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 1 Examples of the hydrocarbon groups having 1 to 20 carbon atoms represented by the above-mentioned hydrocarbon groups are given.

[0236] In the above formula (III), R 41 and R 42 Examples of the heterocyclic group having 2 to 10 carbon atoms and the group having 3 to 20 carbon atoms containing a heterocyclic ring are the same as the heterocyclic group having 2 to 10 carbon atoms and the group having 3 to 20 carbon atoms containing a heterocyclic ring listed as examples of the heterocyclic group in the above-mentioned substituent group 1.

[0237] R 41 and R 42 The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, the group having 3 to 20 carbon atoms containing a heterocyclic ring, and the methylene group in the hydrocarbon group or the group having 3 to 20 carbon atoms containing a heterocyclic ring represented by the above are substituted with a group selected from <Group B>, and the hydrogen atom in the group may be substituted or unsubstituted. In the case of being substituted, the substituent is preferably selected from the following substituent group 2, and a halogen atom is particularly preferred.

[0238] R 43 The hydrocarbon group having 1 to 20 carbon atoms represented may have hydrogen atoms substituted or unsubstituted. When substituted, the substituent is preferably selected from the following substituent group 2, and a halogen atom is particularly preferred.

[0239] Substituent Group 2: halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups, heterocyclic groups having 2 to 10 carbon atoms, and heterocyclic group-containing groups having 3 to 20 carbon atoms. The explanations of these are the same as those of Substituent Group 1.

[0240] Among the compounds having a group represented by the above formula (III), the compound represented by the following formula (IV) is preferably used in the composition of the present invention because it has particularly high sensitivity and a good pattern shape can be easily obtained.

[0241] [Chemical formula 9]

[0242]

[0243] (Where R 41 , R 42 and m1 are respectively the same as R in formula (III) 41 , R 42 and m are the same,

[0244] 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 having 3 to 20 carbon atoms containing a heterocyclic ring, or a group in which a methylene group in the hydrocarbon group or the group having 3 to 20 carbon atoms containing a heterocyclic ring is substituted with -O- or -CO-,

[0245] X 2 Indicates oxygen atoms, sulfur atoms, selenium atoms, CR 53 R 54 、CO、NR 55 or PR 56 ,

[0246] R 53 , R 54 , R 55 and R 56 (hereinafter, also with R 51 and R 52 Recorded as "R 51 ~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 having 3 to 20 carbon atoms containing a heterocyclic ring, or a group in which a methylene group in the hydrocarbon group or the group having 3 to 20 carbon atoms containing a heterocyclic ring is substituted with -O- or -CO-,

[0247] R 51 and R 52 Sometimes they independently form a ring with any adjacent benzene ring.

[0248] g represents a number from 0 to 5,

[0249] h represents a number from 0 to 4.

[0250] When g is 2 or more, multiple R 51They can be the same as each other or different.

[0251] When h is 2 or more, multiple R 52 They can be the same as each other or different.

[0252] R 51 , R 52 , R 53 , R 54 , R 55 and R 56 The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, the group having 3 to 20 carbon atoms containing a heterocyclic ring, or the group obtained by replacing the methylene group in the hydrocarbon group or the group having 3 to 20 carbon atoms containing a heterocyclic ring with -O- or -CO- may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl 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 having 3 to 20 carbon atoms containing a heterocyclic ring.)

[0253] In the above formula (IV), R 51 ~R 56 The hydrocarbon groups having 1 to 20 carbon atoms represented by 1 Examples of the hydrocarbon groups having 1 to 20 carbon atoms represented by the above-mentioned hydrocarbon groups are given.

[0254] As R in the above formula (IV) 51 ~R 56 The heterocyclic group having 2 to 10 carbon atoms and the group containing a heterocyclic ring having 3 to 20 carbon atoms represented by 1 The same applies to the heterocyclic group having 2 to 10 carbon atoms and the group having 3 to 20 carbon atoms containing a heterocyclic ring as described in the above.

[0255] In addition, as a replacement for R 51 ~R 56 Examples of the heterocyclic group having 2 to 10 carbon atoms and the group having 3 to 20 carbon atoms containing a heterocyclic ring as a substituent of a hydrogen atom in the group represented by include R 1 The heterocyclic group having 2 to 10 carbon atoms and the group having 3 to 20 carbon atoms containing a heterocyclic ring as described in the above and the like.

[0256] R 51 ~R 56The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms, the group having 3 to 20 carbon atoms containing a heterocyclic ring, and the group obtained by replacing the methylene group in these groups with -O- or -CO- may further have a substituent or may be unsubstituted. In the case of having 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 carboxyl group, a heterocyclic group having 2 to 10 carbon atoms, or a group having 3 to 20 carbon atoms containing a heterocyclic ring.

[0257] For R 51 and R 52 Each independently forms a ring with any adjacent benzene ring, and the following cases can be mentioned: 51 or R 52 Bonded to the adjacent benzene ring, through R 51 and R 52 The two carbon atoms of the two benzene rings bonded to each other and X 2 (oxygen atoms, sulfur atoms, selenium atoms, CR 53 R 54 The carbon atom of CO, the carbon atom of NR 55 The nitrogen atom, PR 56 The phosphorus atom of the formula (IV) forms a 5-membered ring, and the two benzene rings in the formula (IV) form a condensed ring with the 5-membered ring. Examples of such rings include carbazole rings.

[0258] Preferred polymerization initiators (F) include, for example, the following compounds No. F1 to No. F17, and preferred compounds represented by the above formula (IV) include, for example, the following compounds No. F1 and No. F3 to No. F15. However, the polymerization initiator (F) used in the present invention is not limited to the following compounds.

[0259] [Chemical formula 10]

[0260]

[0261] [Chemical formula 11]

[0262]

[0263] [Chemical formula 12]

[0264]

[0265] A composition using a compound having a carbazole skeleton as the polymerization initiator (F) is preferred from the viewpoint of excellent curability. In particular, a compound having a carbazole structure and a nitro group is preferably used as the polymerization initiator (F).

[0266] From the above aspects, in the compound represented by formula (IV), X 2 NR 55 The compounds shown are preferred because of their high sensitivity. 55 In the case of R 55 The carbon number of R is preferably 10 or less, particularly 5 or less, from the perspective of the availability and sensitivity of the polymerization initiator. 55 Preferred are phenyl, alkyl or alkenyl groups, which may be substituted by a substituent.

[0267] Among the compounds represented by formula (IV), compounds wherein h is 0 are preferred from the viewpoint of ease of production.

[0268] In the compound represented by formula (IV), g is 1 or more, R 51 Compounds in which one or more of the nitro groups or benzoyl groups having a substituent (e.g., a group having a 1,3-dioxolane ring or an alkyl group having 5 or less carbon atoms) are preferred because of their high sensitivity. In particular, compounds in which g is 1 or more and R 51 The compound having at least one nitro group is particularly preferably a compound having a nitro group at the 3-position of carbazole.

[0269] In the compound represented by formula (IV), R 41 A group in which a chain or cyclic alkyl group, an aryl group or an arylalkyl group or a methylene group thereof is substituted with -O- is preferred from the viewpoint of sensitivity and ease of production, a group in which a methylene group in an aryl group is substituted with -O- is preferred, and a group in which a methylene group in an alkyl-substituted phenyl group is substituted with -O- is more preferred. 41 The number of carbon atoms in the moiety is preferably 20 or less, more preferably 8-20, particularly preferably 9-15.

[0270] In the compound represented by formula (IV), R 42 Compounds having 10 or less carbon atoms, particularly 7 or less carbon atoms, and particularly 3 or less carbon atoms are preferred from the viewpoint of ease of production. 42 A substituted or unsubstituted chain alkyl group or a phenyl group is preferred from the viewpoint of sensitivity and ease of production, and a chain alkyl group is more preferred.

[0271] In the present invention, the polymerization initiator (F) is a compound having an indole skeleton, and in particular, a composition having a group represented by the above formula (III) and an indole skeleton is preferred from the perspective of excellent patterning properties. Examples of the compound having an indole skeleton include the above compound No. F16 and F17.

[0272] Examples of other radical polymerization initiators used as the polymerization initiator (F) include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrol-1-yl)]titanium.

[0273] Examples of commercially available free radical initiators include Adeka Optomer N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831, and NCI-930 (all manufactured by ADEKA Corporation); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, and IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly); and the like.

[0274] The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides, and persulfates are preferred.

[0275] Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis(methyl isobutyrate), 2,2′-azobis-2,4-dimethylvaleronitrile, and 1,1′-azobis(1-acetoxy-1-phenylethane).

[0276] Examples of the peroxide include benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butylcyclohexyl)peroxydicarbonate.

[0277] Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0278] The polymerization initiator listed above may be used alone or in combination of two or more.

[0279] A composition containing 1 to 80 parts by mass of the polymerization initiator (F) relative to 100 parts by mass of the compound (A) is preferred from the viewpoint of excellent sensitivity and the ability to obtain 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.

[0280] From the same viewpoint, the content of the polymerization initiator (F) 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 based on 100 parts by mass of the solid content of the composition (excluding the colorant).

[0281] <Ethylenically Unsaturated Compound (G)>

[0282] The composition of the present invention further contains an ethylenically unsaturated compound (G) (hereinafter, also described as "compound (G)"), which is preferred from the perspective of excellent low-temperature curing properties of the composition. An ethylenically unsaturated compound refers to a compound having one or more ethylenically unsaturated bond groups, having no carboxyl group, and not belonging to any of the components (A) to (F) mentioned above. In the present invention, if a compound (G) having a molecular weight of less than 1000 is used, the sensitivity becomes further higher, so it is preferred. Examples of the ethylenically unsaturated bond group include an acrylic group, a methacrylic group, a vinyl group, a maleimide group, and the like. Examples of the compound (G) include tert-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, and poly(meth)acrylate. Butoxyethoxyethyl, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)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, Esters of unsaturated monobasic acids and polyols or polyphenols such as trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, tricyclodecane dihydroxymethyl di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriamine tri(meth)acrylamide, phthalamide Amides of unsaturated monobasic acids and polyamines such as methylbis(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 nitrile; 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; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; 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; polystyrene , poly(meth)acrylate methyl, poly(meth)acrylate n-butyl, polysiloxane and other macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain; vinyl chloride, vinylidene chloride, tricyclododecane diacrylate, divinyl succinate, diallyl phthalate, triallyl phosphate, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl-containing vinyl monomers and vinyl carbamate compounds of polyisocyanate compounds. In the present invention, from the viewpoint of low temperature curing, it is preferred to use esters of unsaturated monobasic acids and polyols or polyphenols. ;

[0283] The above-mentioned compound (G) can be used alone or in combination of two or more.

[0284] As the compound (G), commercial products may be used. Examples of such commercial products include KAYARADDPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-215 and M-350 (all manufactured by Toa Gosei 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.).

[0285] The compound (G) having a molecular weight of 1,000 or less is excellent in sensitivity, and the resulting cured product is excellent in chemical resistance. From this point of view, the compound (G) having a molecular weight of 200 or more and 800 or less is particularly preferred.

[0286] In the present invention, the number of ethylenically unsaturated bond groups contained in the molecule of compound (G) is preferably 3 to 10, more preferably 4 to 8, and particularly preferably 4 to 6. This is because when the number of ethylenically unsaturated bond groups contained in the molecule of compound (G) is within the above range, the low temperature curability of the composition becomes excellent.

[0287] As compound (G), 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. A composition containing such urethane acrylate is preferred from the viewpoint of excellent sensitivity and excellent chemical resistance of the obtained cured product.

[0288] The content of the compound (G) is preferably 5 to 150 parts by mass based on 100 parts by mass of the compound (A), more preferably 7 to 100 parts by mass, and particularly preferably 9 to 50 parts by mass, from the viewpoint of high sensitivity and the ability to obtain a cured product having excellent chemical resistance.

[0289] A solvent may be further added to the composition of the present invention. The solvent is a compound that is liquid at 1 atmosphere and 25°C and does not belong to the above-mentioned (A) to (G). As the solvent, a solvent that can dissolve or disperse the above-mentioned components ((A) to (F) and further (G) as needed) can be generally used. 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 solvents such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and 2,2,4 - Ester solvents such as trimethyl-1,3-pentanediol monoisobutyrate (Texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol and amyl alcohol; ether ester solvents such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), 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, D-limonene and pinene; mineral spirits, SWAZOL #310 (above, manufactured by COSMO Matsuyama Oil); and SOLVESSO #100 (above, manufactured by Exxon Chemical); Paraffin solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane and 1,2-dichloroethane; halogenated aliphatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and water, etc. These solvents can be used as one or two or more mixed solvents. Among them, ketone and ether ester solvents, especially PGMEA and cyclohexanone, are preferred because they have good compatibility between the resist and the polymerization initiator in the composition.

[0290] In the composition of the present invention, the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, based on 100% by mass of the total amount of the composition.

[0291] When the content of the solvent is within the above range, it is preferred from the perspectives of obtaining a composition with excellent workability (viscosity and wettability of the composition), reduced unevenness during drying, and solution stability (without precipitation and sedimentation of components contained in the composition), and being able to appropriately control the thickness of the cured product when obtaining the cured product.

[0292] In the 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, p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol and phenothiazine can be further added as needed; thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; defoamers; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-agglomeration agents; catalysts; curing accelerators; crosslinking agents; thickeners, etc.

[0293] As the above-mentioned dispersant, any substance can be selected as long as it can disperse and stabilize the colorant (E). Commercially available dispersants, for example, BYK series manufactured by BYK-Chemie, etc. can be used. Preferably, a polymer dispersant containing polyester, polyether, or polyurethane having a basic functional group, a substance having a nitrogen atom as a basic functional group, an amine and / or a quaternary salt thereof as the functional group having a nitrogen atom, and an amine value of 1 to 100 mgKOH / g can be used.

[0294] 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, polyurethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, and the like.

[0295] By using the above-mentioned organic polymer together with the above-mentioned compound (A), the properties of the cured product can also be improved.

[0296] 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, silicon dioxide, and aluminum oxide; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper. Among them, titanium oxide, silicon dioxide, layered clay minerals, and silver are preferred.

[0297] As the coupling agent, for example, 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-methylacrylamide, and the like can be used. (Meth)acrylate functional alkoxysilanes such as acyloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 2-methacryloxypropyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane alkyl, epoxy-functional alkoxysilanes such as γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, amino-functional alkoxysilanes such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate-functional alkoxysilanes such as 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, etc. Urea-functional alkoxysilanes such as alkoxysilane, isocyanurate-functional alkoxysilanes such as tris-(trimethoxysilylpropyl)isocyanurate, titanium alkoxides such as titanium tetraisopropoxide and titanium tetra-n-butoxide, titanium chelates such as dioctyloxybis(octanediol)titanium and diisopropoxybis(ethyl acetoacetate)titanium, zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, acylated zirconiums such as zirconium tributoxymonostearate, isocyanate silanes such as methyl triisocyanate silane, and the like.

[0298] Adding a coupling agent is preferred because it improves the adhesion between the cured product and the substrate.

[0299] 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- 9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, K BE-04, KBM-13, KBE-13, KBE-22, KBE-103, HMDS-3, KBM-3063, KBM-3103C, KPN-3504 and KF-99 (above, Shin-Etsu Silicone), etc.

[0300] As the above-mentioned surfactant, there can be used anionic surfactants such as higher fatty acid alkali metal salts, alkyl sulfonates, and alkyl sulfates, cationic surfactants such as higher amine hydrohalides 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.

[0301] As the above-mentioned leveling agent, it can be roughly divided into silicone leveling agent, acrylic leveling agent, fluorine leveling agent, vinyl leveling agent, etc. For example, the fluorine leveling agent can include a leveling agent having a fluorinated aliphatic hydrocarbon skeleton, and a leveling agent having a repeating unit via an ether bond, that is, a polyfluoroalkylene ether skeleton. It is preferred to contain a leveling agent from the aspect of obtaining a uniform cured product.

[0302] As the leveling agent, a commercially available item can be used, and examples thereof include MEGAFACE RS-56, RS-72-A, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-78, and RS-90 (manufactured by DIC Corporation).

[0303] When the composition contains a leveling agent, the amount is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, based on 100 parts by mass of the solid content (excluding the colorant) in the composition from the viewpoint of enhancing the above-mentioned effect of the leveling agent.

[0304] In the composition of the present invention, the content of any component other than the above-mentioned (A) to (G) and the solvent is appropriately selected according to the intended use, and is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 20 parts by mass or less relative to 100 parts by mass of the total of the above-mentioned components (A) to (G).

[0305] The composition of the present invention and its cured product can be used for curable coatings, varnishes, curable adhesives, printed circuit boards, display devices (color filters in color display liquid crystal display panels such as color TVs, PC monitors, portable information terminals and digital cameras, color filters for various display purposes, color filters for CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, and black partitions of organic EL), powder coatings, printing inks, printing plates, adhesives, gel coatings, photoresists for electronic engineering, plating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic The present invention can be used in a variety of applications, including recording materials, micro-mechanical parts, waveguides, optical switches, masks for plating, etching masks, color test systems, glass fiber cable coatings, screen printing templates, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing 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 used in the formation of dielectric layers in the sequential lamination of printed circuit boards, and protective films. There is no particular limitation on the use of the present invention, but among the above-mentioned uses, it can be particularly suitably used in display devices.

[0306] In particular, when the composition of the present invention contains a colorant (E), particularly a black pigment, the composition has photosensitivity and alkali developability, and becomes particularly suitable for forming a BCS.

[0307] In liquid crystal display devices, organic EL display devices, etc., spacers are used to maintain the distance between the upper and lower substrates of the unit. The spacers are formed by applying the composition of the present invention on the substrate, exposing it through a predetermined mask and display device, and then developing it. In recent years, BCS with light-shielding properties by combining a columnar spacer and a black matrix into one module has been used.

[0308] The method for producing a cured product using the composition of the present invention will be described in detail below.

[0309] The composition of the present invention can be applied to a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by a spin coater, a roll coater, a rod coater, a die coater, a curtain coater, various printing, dipping, etc. In addition, it can also be temporarily applied to a supporting substrate such as a film and then transferred to another supporting substrate, and the application method is not limited.

[0310] In addition, as a light source of energy rays used when curing the composition of the present invention, electromagnetic wave energy having a wavelength of 2,000 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., or high energy rays such as electron beams, X-rays, and radiation can be used. From the perspective of high productivity and the ability to obtain a high-quality cured product, ultra-high pressure mercury lamps and LEDs that emit light with a wavelength of 300 to 450 nm are preferably used.

[0311] And then, by using laser to the exposure light source without using mask ground by the digital information of computer etc. directly forming the laser direct drawing method of image, can not only seek the raising of productivity, can also seek the raising of definition, positional accuracy etc., therefore be useful.As this laser, it is suitable to use the light of wavelength of 340~430nm.For example, it is also possible to use the light source of visible~infrared light of excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium-neon laser, krypton ion laser, various semiconductor lasers and YAG laser etc..When using these lasers, can add the sensitizing pigment of this region of visible~infrared absorption.

[0312] The cured product of the present invention is preferably formed by the following steps: (1) a step of forming a coating film of the composition of the present invention on a substrate, (2) a step of irradiating the coating film with radiation via a mask having a predetermined pattern shape, (3) a step of baking the exposed coating film, (4) a step of developing the baked coating film, and (5) a step of heating the developed coating film.

[0313] As the mask, a multi-tone mask such as a halftone mask or a grayscale mask may be used.

[0314] The display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product of the present invention. In particular, when the cured product is BCS, the BCS can be provided between cells.

[0315] Example

[0316] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[0317] [Manufacturing Example 1] Manufacture of Alkali-Developable Compound A-1

[0318] 184 g of 1,1-bis[4-(2,3-epoxypropoxy)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 added, and the mixture was stirred at 120° C. for 16 hours to obtain a reaction liquid. The obtained reaction liquid was cooled to room temperature (25°C), and 160 g of PGMEA, 59 g of diphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added to the cooled reaction liquid, and stirred at 120°C for 4 hours. 20 g of tetrahydrophthalic anhydride was further added, and stirring was carried out at 120°C for 4 hours, 100°C for 3 hours, 80°C for 4 hours, 60°C for 6 hours, and 40°C for 11 hours. Then, 128 g of PGMEA was added to obtain an alkali-developable compound A-1 (Mw=5,000, Mn=2,100, acid value (solid content) 92.7 mg·KOH / g) as a PGMEA solution. The content of the alkali-developable compound in the alkali-developable compound PGMEA solution A-1 was 45% by mass.

[0319] [Production Example 2] Production of Alkali-Developable Compound A-2

[0320] 75.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 23.8 g of acrylic acid, 0.273 g of 2,6-di-tert-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride and 65.9 g of PGMEA were added, and the mixture was stirred at 90° C. for 1 hour, 100° C. for 1 hour, 110° C. for 1 hour and 120° C. for 14 hours to obtain a reaction liquid. The obtained reaction solution was cooled to room temperature (25°C), and 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of propylene glycol monomethyl ether acetate (PGMEA) were added to the cooled reaction solution, and stirred at 100°C for 5 hours. 30.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 0.269 g of 2,6-di-tert-butyl-p-cresol and 1.50 g of PGMEA were further added, and stirred at 90°C for 90 minutes and 120°C for 4 hours, and then 122.2 g of PGMEA was added to obtain the target alkali-developable compound A-2 (Mw=4,190, Mn=2,170, acid value (solid content) 52 mg·KOH / g) as a PGMEA solution. The content of the alkali-developable compound in the alkali-developable compound PGMEA solution A-2 was 45% by mass.

[0321] [Manufacturing Example 3] Manufacture of Carbon Black No. 1

[0322] 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a deionized sodium peroxodisulfate solution (concentration 2.0 N) were mixed and stirred at 60° C. for 10 hours to obtain a reaction solution. The obtained reaction solution was filtered to obtain a slurry. The obtained slurry was neutralized with sodium hydroxide, treated by diafiltration, and the obtained solid was dried at 75° C. overnight to obtain carbon black No. 1 as a black powder.

[0323] [Manufacturing Example 4] Manufacture of Carbon Black Dispersion No. 1

[0324] 20 g of carbon black No. 1, 2 g of alkali-developable compound A-1, 3 g of DISPERBYK-161 (manufactured by BYK-Chemie, dispersant) and 100 g of PGMEA were weighed and mixed, and processed using a bead mill to obtain carbon black dispersion No. 1. The content of carbon black in carbon black dispersion No. 1 was 16.3% by mass.

[0325] [Manufacturing Example 5] Manufacture of Carbon Black Dispersion No. 2

[0326] 20 g of MA100 (manufactured by Mitsubishi Chemical Corporation) as carbon black, 12.5 g of BYK161 (manufactured by BYK-Chemie, dispersant) (solid content concentration 40% by mass), and 67.5 g of PGMEA were mixed and processed using a bead mill to prepare carbon black dispersion No. 2. The content of carbon black in carbon black dispersion No. 2 was 20% by mass.

[0327] [Examples 1 to 13 and Comparative Examples 1 to 6] Preparation of Compositions

[0328] The components were mixed according to the formulations of [Table 1] and [Table 2] to obtain compositions (Examples 1 to 13 and Comparative Examples 1 to 6). It should be noted that the numerical values ​​of the blends in the table represent parts by mass. In addition, the symbols of the components in the table represent the following components.

[0329] A-1: Alkaline-developable compound PGMEA solution A-1

[0330] A-2: Alkaline-developable compound PGMEA solution A-2

[0331] A-3: SPC3000 (manufactured by Showa Denko K.K., content of alkali-developable compound: 55% by mass, MW: 8100, acid value (solid content): 81 mg·KOH / g)

[0332] B-1: Compound represented by the following formula (b1) (molecular weight: 1,000 to 1,500, epoxy equivalent 280 to 290 g / eq.)

[0333] B-2: Compound represented by the following formula (b2) (epoxy equivalent 210 to 230 g / eq.)

[0334] B-3: Compound represented by the following formula (b3) (epoxy equivalent 90 g / eq.)

[0335] B-4: Compound represented by the following formula (b4) (epoxy equivalent 95 g / eq.)

[0336] [Chemical formula 13]

[0337]

[0338] [Chemical formula 14]

[0339]

[0340] [Chemical formula 15]

[0341]

[0342] [Chemical formula 16]

[0343]

[0344] C-1: Compound represented by the following formula (c1)

[0345] [Chemical formula 17]

[0346]

[0347] D-1: Compound represented by the following formula (d1)

[0348] D'-1: Compound represented by the following formula (d'1)

[0349] D'-2: Compound represented by the following formula (d'2)

[0350] D'-3: EH-2021 (manufactured by AIDICO Co., Ltd.)

[0351] [Chemical formula 18]

[0352]

[0353] [Chemical formula 19]

[0354]

[0355] [Chemical formula 20]

[0356]

[0357] E-1: Carbon black dispersion No.1

[0358] E-2: Carbon black dispersion No.2

[0359] F-1: Compound No. F9 mentioned above

[0360] F-2: Compound represented by the following formula (f1)

[0361] [Chemical formula 21]

[0362]

[0363] G-1: Dipentaerythritol hexaacrylate

[0364] G-2: Tricyclododecane diacrylate

[0365] H-1: BYK-167 (BYK-Chemie)

[0366] I-1: BYK-323 (BYK-Chemie company)

[0367] J-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0368] [Evaluation of composition]

[0369] The compositions of Examples 1 to 13 and Comparative Examples 1 to 6 were evaluated for storage stability, pattern characteristics, and low-temperature curing properties by the following procedures. The results are shown in [Table 1] and [Table 2].

[0370] <Patterning Characteristics>

[0371] The compositions obtained in the examples and comparative examples were applied to a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 70°C for 120 seconds to obtain a coating film with a thickness of 1.0 μm. The obtained coating film was irradiated at a dose of 50 mJ / cm2 through a 20 μm hole mask (hole). 2 Exposure was performed using a proximity alignment exposure device (product name: TME-150R, manufactured by TOPCON CORPORATION) as a light source.

[0372] The exposed coating film was developed by immersing in a 0.4 mass % potassium hydroxide aqueous solution at 25°C for 60 seconds, and then washed thoroughly with water. After washing and drying, it was further fired at 120°C for 30 minutes. The closer the line width of the pattern is to the mask width of 20 μm, the more high-definition patterning can be achieved.

[0373] The case where the line width of the pattern was 19 μm or more and less than 21 μm was evaluated as A, and the case where the line width was less than 19 μm or 21 μm or more was evaluated as B. Tables 1 and 2 show the results.

[0374] <90℃ Curing>

[0375] The compositions obtained in the examples and comparative examples were applied to a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 70°C for 120 seconds to obtain a coating film with a thickness of 1.0 μm. The obtained coating film was irradiated at a dose of 50 mJ / cm2 through a 20 μm hole mask (hole). 2 Exposure was performed using a mirror projection alignment exposure device (product name: TME-150RAK, manufactured by TOPCON CORPORATION) as a light source.

[0376] The exposed coating film was developed by immersing it in an aqueous solution of 0.4% by mass of potassium hydroxide at 23°C for 60 seconds and then washed thoroughly. After washing and drying, it was further post-baked (90°C × 1 hour) to obtain a cured product. The obtained cured product was immersed in PGMEA or acetone, and a chemical resistance test was performed by wiping it with a clean cloth while applying a load of 300g. Each time the cured product was wiped with a clean rag, it was visually inspected to confirm whether there was no peeling or thinning of the film thickness. At the moment when peeling or thinning of the film thickness occurred, the number of times the rag was wiped up to that moment was shown in Tables 1 and 2 as the evaluation results of the chemical resistance test.

[0377] <Storage stability>

[0378] The compositions obtained in Examples and Comparative Examples were stored at room temperature (23° C., 40% (RH)) or −18° C., and changes in development time were evaluated.

[0379] Specifically, the composition stored at room temperature or -18°C for a certain period of time (up to 150 days, evaluated at 10-day intervals) was applied to a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 70°C for 120 seconds to obtain a coating film with a thickness of 1.0 μm. The obtained coating film was irradiated with an amount of 50 mJ / cm 2 Exposure was performed using a mirror projection alignment exposure device (product name: TME-150RAK, manufactured by TOPCON CORPORATION) as a light source.

[0380] The exposed coating was immersed in a 0.4 mass % potassium hydroxide aqueous solution, and the development time (the time it takes for the coating to dissolve) was measured. The number of days until the development time exceeded 110% was measured, using the development time of the coating produced using the composition just produced as a reference. The results are shown in Tables 1 and 2.

[0381] If the storage stability is poor, the components react in the system and polymerize. As a result, the components become difficult to dissolve in the solvent and the development time becomes longer. In general photolithography, for compositions whose development time exceeds 110%, patterning cannot be performed stably.

[0382]

[0383]

[0384] As shown in Tables 1 and 2, the compositions of each embodiment containing compound (A), compound (B), compound (C), compound (D), colorant (E) and polymerization initiator (F) have excellent 90°C curing properties and storage stability, and can achieve high-definition patterning.

[0385] In contrast, the compositions of Comparative Examples 1 to 4 not containing the component (D) were poor in storage stability. Furthermore, the compositions of Comparative Examples 5 and 6 not containing the component (B) or (C) were poor in 90° C. curability.

[0386] The above results show that the composition of the present invention is excellent in patterning property, 90° C. curability, and storage stability.

[0387] Industrial Applicability

[0388] The composition of the present invention can realize high-precision patterning, and has excellent low-temperature curing and storage stability (especially storage stability at room temperature) that are difficult to obtain in the past, which helps to save energy in the manufacturing process. In addition, it can also be adapted to components with weak heat resistance, so it is useful as a patterning material for OLED and quantum dot devices.

Claims

1. A composition comprising: A compound having a carboxyl group (A), Epoxy compounds (B), Thiol compounds (C), A tertiary amine compound (D) having a condensed ring and having no NH group, Colorant (E) and A polymerization initiator (F).

2. The composition according to claim 1, wherein The compound (A) having a carboxyl group includes an unsaturated compound having a structure obtained by an esterification reaction between an epoxy addition compound and a polyacid anhydride, The epoxy addition compound has a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following formula (I), In the formula, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO2-, -SS-, -SO-, -CO-, -OCO-, or a substituent selected from the group represented by the following formulae (a), (b), (c) and (d), The hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with halogen atoms. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 The methylene group in the hydrocarbon group having 1 to 20 carbon atoms represented by is sometimes substituted with an unsaturated bond, -O- or -S-. n represents a number from 0 to 10, In the case of n ≥ 1, multiple R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 and M are sometimes the same and sometimes different. 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 hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, 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 The methylene group in the hydrocarbon group having 1 to 20 carbon atoms represented by is sometimes substituted with an unsaturated bond, -O- or -S-. R 10 With R 11 , R 11 With R 12 , R 12 With R 13 , R 13 With R 14 , R 22 With R 15 , R 15 With R 16 , R 30 With R 23 , R 23 With R 24 , R 24 With R 25 , R 38 With R 31 , R 31 With R 32 , R 32 With R 33 , R 34 With R 35 , R 35 With R 36 and R 36 With R 37 Sometimes they bond to form rings, In the groups represented by formulae (a), (b), (c) and (d), * represents a bonding site.

3. The composition according to claim 1, wherein The epoxy compound (B) has an epoxy equivalent of 80 g / eq. or more and less than 300 g / eq.

4. The composition according to claim 1, wherein The thiol compound (C) is a secondary thiol compound.

5. The composition according to claim 1, wherein The tertiary amine compound (D) is 1,8-diazabicyclo[5.4.0]undec-7-ene.

6. The composition according to claim 1, wherein The colorant (E) is sulfonic acid treated carbon black.

7. The composition according to claim 1, wherein The polymerization initiator (F) is an oxime ester compound.

8. The composition according to claim 1, wherein It further contains an ethylenically unsaturated compound (G). 9 . A black matrix comprising the composition according to claim 1 . 10 . A method for producing a cured product, comprising the step of irradiating the composition according to claim 1 with light.

11. A cured product, which is a cured product of the composition according to any one of claims 1 to 8.

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

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