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

Abstract

This composition contains a compound (A) having a structure obtained using an esterification reaction of a polybasic acid anhydride with an epoxy addition compound having a structure in which an unsaturated monobasic acid has been added to an epoxy compound represented by general formula (I), an epoxy compound (B), a thiol compound (C), a quaternary ammonium salt (D), a black pigment (E), and a polymerization initiator (F). The epoxy equivalent of the epoxy compound (B) is preferably 80 g / eq. to less than 300 g / eq. (See the description for the symbols in the formula.)

Description

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

[0001] The present invention relates to a composition containing a compound having a carboxyl group, an epoxy compound, a thiol compound, a quaternary ammonium salt, a black pigment, and a polymerization initiator.

[0002] Conventionally, a method for producing a colored layer such as a black matrix or black column spacer in a display device or the like has been adopted, for example, by applying a photosensitive colored composition containing a colorant and a polymerizable compound onto a substrate to form a coating film, irradiating (exposing) the coating to radiation through a photomask having a predetermined opening pattern, and then developing the coating to dissolve and remove the unexposed portions, thereby forming a cured pattern (i.e., a colored pattern). After pattern formation, the coating film is usually post-baked at a high temperature, for example, 200 to 250° C., for several tens of minutes or more to promote curing and increase the solvent resistance, film hardness, etc. of the film.

[0003] Post-baking at a high temperature can improve the solvent resistance of the cured pattern. On the other hand, lowering the process temperature has the advantages of reducing manufacturing costs and enabling the use of plastic substrates. Patent Documents 1 and 2 relate to compositions that contain a compound having a carboxyl group, a black pigment, and a polymerization initiator and are said to have low-temperature curing properties.

[0004] Furthermore, a cured film containing a black pigment such as a black matrix may be required to have low reflectivity.

[0005] JP 2019-70720 A JP 2022-061912 A

[0006] In the production of colored layers such as black matrices and black column spacers, there has been an increasing demand for compositions that can be cured at low temperatures. Furthermore, there has been a demand for compositions that can produce low-reflectivity cured products when cured at low temperatures. However, the photosensitive resin compositions described in Patent Documents 1 and 2 both have the problem of either poor low-temperature curing properties or, even if they have low-temperature curing properties, poor low-reflectivity cured products.

[0007] The problem to be solved by the present invention is to solve the problems of the above-mentioned conventional technologies, and to provide a polymerizable composition that is curable at low temperature and has low reflectance of the cured product and excellent patterning properties, a cured product thereof, a method for producing the cured product, and a display device using the cured product.

[0008] As a result of extensive research, the present invention has solved the above problems by providing the following [1] to

[12] .

[0009] [1] A composition containing a compound (A) having a structure obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (I) and a polybasic acid anhydride, an epoxy compound (B), a thiol compound (C), a quaternary ammonium salt (D), a black pigment (E), and a polymerization initiator (F): (wherein M represents a direct bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, -O-, -S-, -CO-, or -OCO-; a hydrogen atom in the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 40 carbon atoms represented by M may be substituted with a halogen atom; 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 the formula (I) may be substituted with a carbon-carbon unsaturated bond, -O-, or -S-, n is a number from 0 to 10, and when n≧1, there are a plurality of R １ , R ２ , R ３ , R ４ , R ５ , R ６, R ７ , R ８ and M may be the same or different.

[0010] [2] The composition according to [1], wherein M in the general formula (I) is an aromatic hydrocarbon group having 6 to 40 carbon atoms and is a group represented by the following formula (a), (b), (c), or (d): (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 the formula (I) may be substituted with a carbon-carbon unsaturated bond, —O—, or —S—; １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R ２２ and R １５ , R １５ and R １６ , R ３０ and R ２３ , R ２３ and R ２４ , R ２４ and R ２５ , R ３８ and R ３１ , R ３１ and R ３２ , R ３２ and R ３３ , R ３４ and R ３５ , R ３５ and R ３６ and R ３６ and R ３７ may bond to form a ring, and * in the groups represented by formulas (a), (b), (c) and (d) represents a bond.

[0011] [3] The composition according to [1] or [2], wherein the epoxy equivalent of the epoxy compound (B) is 80 g / eq. or more and less than 300 g / eq.

[0012] [4] The composition according to any one of [1] to [3], wherein the thiol compound (C) is a secondary thiol compound.

[0013] [5] The composition according to any one of [1] to [4], wherein the anion of the quaternary ammonium salt (D) is an anion derived from a weakly acidic compound.

[0014] [6] The composition according to any one of [1] to [5], wherein the black pigment (E) is sulfonic acid-treated carbon black.

[0015] [7] The composition according to any one of [1] to [6], wherein the polymerization initiator (F) is an oxime ester compound.

[0016] [8] The composition according to any one of [1] to [7], further containing an ultraviolet-reactive surface modifier (G).

[0017] [9] The composition according to any one of [1] to [8], further comprising an ethylenically unsaturated compound (H).

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

[0018]

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

[0019]

[12] A cured product of the composition according to any one of [1] to [8].

[0020]

[13] A display device containing the cured product according to

[12] .

[0021] The composition of the present invention enables high-precision patterning while simultaneously achieving excellent low-temperature curing properties and low reflectivity of the cured product, which have been difficult to achieve in the past. This contributes to energy savings in the manufacturing process. It can also be applied to components with poor heat resistance. It can also suppress reflection of displays from external light, improving visibility. For these reasons, the composition of the present invention is useful as a patterning material for OLEDs and quantum dot devices.

[0022] The polymerizable composition of the present invention will be described in detail below based on preferred embodiments. The composition of the present invention contains the compound (A), the epoxy compound (B), the thiol compound (C), the quaternary ammonium salt (D), the black pigment (E), and the polymerization initiator (F).

[0023] The present inventors conducted extensive research into a composition containing the above-mentioned compound (A), epoxy compound (B), black pigment (E), and polymerization initiator (F) to achieve low-temperature curing properties and low reflectance of the cured product. Surprisingly, they discovered that by further combining these compounds with a thiol compound (C) and a quaternary ammonium salt (D), high-resolution patterning is possible while achieving remarkable low-temperature curing properties and low reflectance of the cured product, which have previously been difficult to achieve. The present invention enables the curing temperature, which previously required 200 to 250°C, to be reduced to approximately 90°C in applications such as black column spacers, black matrices, and color resists, thereby reducing energy consumption in the manufacturing process and enabling the use of non-heat-resistant components, which was previously not possible. Each component is described below in order.

[0024] <Compound (A)> The compound (A) (hereinafter also referred to as "compound (A)") according to the present invention will be explained. Compound (A) is a compound having a structure obtained by esterification of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by formula (I), with a polybasic acid anhydride. As a result, the composition of the present invention has excellent patterning properties and low-temperature curing properties, and a cured product with low reflectivity can be obtained.

[0025] The weight-average molecular weight of compound (A) is preferably 1,000 to 500,000, and it is preferable to use a compound (A) with a weight-average molecular weight of 3,000 or more, and more preferably a compound (A) with a weight-average molecular weight of 4,000 to 15,000. Such a weight-average molecular weight is preferable because it provides better patterning properties and low-temperature curing properties and makes it easier to obtain a cured product with low reflectivity.

[0026] In addition, when the compound is a polymer, the molecular weight refers to the weight-average molecular weight (Mw). The weight-average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent. The weight-average molecular weight can be obtained, for example, by measuring using a GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, polystyrene standards for calibration curves with Mw of 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, and 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and a measurement column of KF-804, KF-803, or KF-802 (manufactured by Showa Denko K.K.). The measurement temperature can be 40° C., and the flow rate can be 1.0 mL / min.

[0027] The compound (A) preferably has an acid value of 5 to 200 mg KOH / g, more preferably 10 to 150 mg KOH / g, and particularly preferably 30 to 120 mg KOH / g. An acid value of 5 mg KOH / g or more facilitates alkaline developability, while an acid value of 200 mg KOH / g or less facilitates production of the polymer compound. The acid value can be calculated in accordance with JIS K0070.

[0028] An epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by formula (I) above usually has the following structure [(e)]: Furthermore, a reaction product obtained by an esterification reaction of the epoxy addition compound with a polybasic acid anhydride usually has the following structure [(f)]:

[0029] (In the formula, Y １ represents a residue of an unsaturated monobasic acid, Y ２ represents a residue of a polybasic acid anhydride, and * represents a bond.

[0030] The aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by M in formula (I) is not particularly limited, but preferred examples include an alkylene group having 1 to 20 carbon atoms, a cycloalkylalkylene group having 4 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkenylene group having 3 to 20 carbon atoms, and a cycloalkylene group having 3 to 20 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, and a cycloalkylene group having 3 to 10 carbon atoms are more preferred because they provide good sensitivity when used as compound (A).

[0031] The alkylene group having 1 to 20 carbon atoms represented by M in the above formula (I) is a divalent group obtained by removing one hydrogen atom from an alkyl group described below, and examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene, etc. Furthermore, the cycloalkylalkylene group having 4 to 20 carbon atoms is a group obtained by removing one hydrogen atom from a cycloalkylalkyl group described below, and examples thereof include cyclopropylmethylene, cyclobutylmethylene, 2-cyclopentylethylene, etc.

[0032] The alkenylene group having 2 to 20 carbon atoms represented by M in the above formula (I) is a group in which one hydrogen atom has been removed from an alkenyl group described below, and examples thereof include 1,2-ethenediyl (also referred to as ethenylene or vinylene), 2-butene-1,4-diyl, and 1,2-dimethyl-1,2-ethenediyl. Other examples include cycloalkylalkenylene groups having 2 to 20 carbon atoms such as 3-cyclohexyl-2-propene-1,2-diyl. Examples of cycloalkenylene groups having 3 to 20 carbon atoms include groups in which one hydrogen atom has been removed from a cycloalkenyl group having 3 to 20 carbon atoms described below.

[0033] The cycloalkylene group having 3 to 20 carbon atoms represented by M in the above formula (I) is a group in which one hydrogen atom has been removed from a cycloalkyl group described below, and examples thereof include cyclopropylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and ethylcyclohexylene.

[0034] Examples of the aromatic hydrocarbon group having 6 to 40 carbon atoms represented by M in the above formula (I) include an arylene group having 6 to 40 carbon atoms and an arylalkylene group having 7 to 40 carbon atoms. In particular, it is preferred that M in the above formula (I) is an aromatic hydrocarbon group having 6 to 40 carbon atoms and is a group represented by (a), (b), (c), or (d) above, since this provides an excellent light-shielding property and a cured product with high resistance.

[0035] Examples of the arylene group having 6 to 40 carbon atoms represented by M in formula (I) include groups in which one hydrogen atom has been removed from the aryl group described below. Examples include phenylene, tolylene, xylylene, naphthylene, biphenylene, fluorene, and indane. Examples of the arylalkylene group having 6 to 40 carbon atoms include groups in which one hydrogen atom has been removed from the arylalkyl group described below.

[0036] R in the above formula (I) 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 the formula (I) is not particularly limited, but preferred examples thereof include alkyl groups having 1 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, and alkenyl groups having 2 to 20 carbon atoms, as groups having a bond to a chain aliphatic group; cycloalkyl groups having 3 to 20 carbon atoms and cycloalkenyl groups having 3 to 20 carbon atoms, as groups having a bond to a cyclic aliphatic group; and aryl groups having 6 to 20 carbon atoms, as groups having a bond to an aromatic hydrocarbon ring group.

[0037] The alkyl group having 1 to 20 carbon atoms may be linear or branched, and examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl.

[0038] 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.

[0039] Examples of the arylalkyl group having 7 to 20 carbon atoms include the above-mentioned alkyl groups in which one or more hydrogen atoms have been substituted with the below-mentioned aryl group, specifically benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, naphthylpropyl, and groups in which hydrogen atoms in these rings have been substituted with the above-mentioned aliphatic hydrocarbon groups.

[0040] Examples of the alkenyl group having 2 to 20 carbon atoms include groups in which one or more carbon-carbon single bonds of the above-mentioned alkyl groups and cycloalkylalkyl groups are changed to carbon-carbon double bonds, such as chain alkenyl groups such as 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, and cycloalkylalkenyl groups such as 3-cyclohexyl-2-propenyl.

[0041] Examples of cycloalkyl groups having 3 to 20 carbon atoms are groups in which the bond is on the cycloalkyl ring, and include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl, tetradecahydroanthracenyl, etc. Examples of cycloalkenyl groups having 3 to 20 carbon atoms include a cyclopentadienyl group, etc.

[0042] 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.

[0043] In this specification, R １ ~R ８ , R １０ ~R ３８ In the hydrocarbon group represented by the formula (I), the methylene group in the group may or may not be substituted with a carbon-carbon unsaturated bond, —O—, or —S— (hereinafter also referred to as a “carbon-carbon unsaturated bond, etc.”). For example, １ ~R ８ , F １０ ~R ３８ As a group in which one or more methylene groups in a hydrocarbon group having 1 to 20 carbon atoms represented by the formula: １Examples of hydrocarbon groups having 1 to 20 carbon atoms, such as those mentioned above, include groups in which one or more methylene groups have been substituted with a carbon-carbon unsaturated bond or the like.

[0044] Furthermore, in this specification, when two or more methylene groups in a hydrocarbon group such as an alkyl group or a heterocyclic group are substituted with a divalent group selected from a carbon-carbon unsaturated bond, etc., the oxygen atoms are not adjacent to each other, and preferably the divalent groups selected from a carbon-carbon unsaturated bond, -O-, and -S- are not adjacent to each other. The same applies when methylene groups in a hydrocarbon group or a heterocyclic group are substituted with a divalent group selected from <Group B> or <Group 2> described below.

[0045] R １ The hydrocarbon group having 1 to 20 carbon atoms, which may have a methylene group substituted with a carbon-carbon unsaturated bond or the like, may have a hydrogen atom substituted or unsubstituted. When a hydrogen atom in the hydrocarbon group is substituted, the substituent is preferably selected from the following Substituent Group 1.

[0046] 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, and heterocyclic groups having 2 to 20 (preferably 2 to 10) carbon atoms.

[0047] The heterocyclic group in Substituent Group 1 is a group in which a bond is located on a heterocycle. Examples of the heterocyclic group include a group in which one hydrogen atom has been removed from a heterocyclic compound (hereinafter, the heterocyclic group is also referred to as "heterocyclic group I"). The heterocyclic group I is not particularly limited, but examples thereof include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, cinnolyl, phthalazyl, puryl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, Examples include thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, isoxazolyl, indolyl, benzoxazolyl, benzotriazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl, isocyanuric, and 1,3-dioxolanyl.

[0048] The heterocyclic group may be a group in which one or more hydrogen atoms on the heterocycle of the heterocyclic group I are substituted with a hydrocarbon group. Such a heterocyclic group is also referred to as a "heterocyclic group II". The hydrocarbon group referred to here is a heterocyclic group represented by the above R １ Among the groups exemplified as hydrocarbon groups having 1 to 20 carbon atoms, such as those represented by the following formulae, those which satisfy the requirement for the number of carbon atoms in the heterocyclic group after substitution can be mentioned.

[0049] In this specification, halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0050] In this specification, the number of carbon atoms of the group substituted by the substituent is within the definition of the annotation of the general formula. For example, R １ When a hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms, such as a substituted hydrocarbon group, is substituted with a group containing a carbon atom as a substituent, the number of carbon atoms in the substituted hydrocarbon group, including the number of carbon atoms in the substituent, is calculated as R １The number of carbon atoms in the hydrocarbon group represented by the formula (I) is 1 to 20.

[0051] 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 by the following formula (I) has good sensitivity when used as compound (A). Therefore, 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 is more preferred because it has excellent alkali developability.

[0052] R １ ~R ８ and R １０ ~R ３８ Examples of the carbon-carbon unsaturated bond that may substitute for the methylene group in the group represented by the formula: include --C.dbd.C-- and --C.ident.C--.

[0053] R in the above formulas (a) to (d) １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R ２２ and R １５ , R １５ and R １６ , R ３０ and R ２３ , R ２３ and R ２４ , R ２４ and R ２５ , R ３８ and R ３１ , R ３１ and R ３２ , R ３２ and R ３３ , R ３４ and R ３５ , R ３５ and R ３６ and R ３６ and R ３７Examples of the ring formed by bonding include 5- to 7-membered rings such as cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone rings, and lactam rings, and fused rings such as naphthalene and anthracene.

[0054] In particular, from the viewpoint of easily obtaining a composition that has excellent low-temperature curing properties and patterning properties and that gives a cured product with low reflectivity, it is preferable that M is a substituent represented by formula (b) or (d) among those in formula (I). Furthermore, from the viewpoint of easy availability of compound (A) and excellent heat resistance of the cured product obtained, it is preferable to use a compound represented by formula (I) in which M is a substituent represented by formula (b) or (d). １ ~R ８ 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. １０ ~R ３８ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and even more preferably a hydrogen atom or an aryl group having 6 to 8 carbon atoms.

[0055] The unsaturated monobasic acid refers to an acid having a carbon-carbon unsaturated bond in its structure and one hydrogen atom per molecule that can ionize to form a hydrogen ion. Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, and dicyclopentadiene maleate.

[0056] Furthermore, examples of the polybasic acid anhydride to be reacted after the reaction with the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylhimic anhydride.

[0057] From the viewpoint of good alkali developability, it is preferable that the reaction molar ratios of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride are as follows. That is, the epoxy addition compound is preferably added so that the ratio of carboxyl groups of the unsaturated monobasic acid to one epoxy group of the epoxy compound is 0.1 to 1.0, and more preferably 0.2 to 1.0. Furthermore, the compound (A) is preferably added so that the ratio of acid anhydride structures of the polybasic acid anhydride to one hydroxyl group of the epoxy adduct is 0.1 to 1.0, and more preferably 0.2 to 1.0. The reaction of the epoxy compound represented by formula (I), the unsaturated monobasic acid, and the polybasic acid anhydride can be carried out according to a conventional method.

[0058] Compound (A) may be a compound obtained by esterifying an epoxy addition compound with a polybasic acid anhydride and then further reacting the compound with a monofunctional or polyfunctional epoxy compound (hereinafter referred to as compound (A2)). To distinguish it from compound (A2), the compound obtained by esterifying an epoxy addition compound with a polybasic acid anhydride is also referred to as compound (A1). Use of compound (A2) makes it possible to adjust the acid value of the composition of the present invention, and adjusting the acid value allows fine adjustment of the alkaline developability (development rate, pattern shape, etc.). It is preferable that the acid value of the solid content of compound (A) be within the above range because this results in good alkaline developability, and the amount of monofunctional or polyfunctional epoxy compound used is preferably selected so that compound (A2) satisfies the above acid value. Furthermore, the solid content referred to in the present invention refers to the content excluding the solvent described below.

[0059] Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether. Examples of suitable epoxy compounds include propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, and the following epoxy compounds No. E1 and No. E2.

[0060]

[0061]

[0062] As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, since this makes it possible to obtain a cured product with good heat resistance. As the bisphenol-type epoxy compound, an epoxy compound represented by the above formula (I) can be used, and also bisphenol-type epoxy compounds such as hydrogenated bisphenol-type epoxy compounds can be used. Examples of the glycidyl ethers that can be used include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, and 1,1,1,1-tetra(glycidyloxymethyl)methane.Other examples include novolac epoxy compounds (such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, and dicyclopentadiene novolac epoxy compounds); and alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane. glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester; glycidyl amines such as tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol, and N,N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene-type epoxy compounds; triphenylmethane-type epoxy compounds; and dicyclopentadiene-type epoxy compounds.

[0063] In the composition of the present invention, a composition containing 20 to 90 parts by mass of compound (A) per 100 parts by mass of the total amount of compound (A), epoxy compound (B), thiol compound (C), quaternary ammonium salt (D), black pigment (E), and polymerization initiator (F) is preferred from the viewpoints of making it easier to obtain a cured product with high-resolution patterns and low reflectivity, and of making it easier to obtain low-temperature curing properties, and a content of 25 to 75 parts by mass is more preferred, and 25 to 50 parts by mass is particularly preferred. Compound (A) is preferably the component with the largest mass among the solid contents of the composition, excluding the colorant.

[0064] In the composition of the present invention, the content of compound (A) is preferably 20 to 85 parts by mass, more preferably 25 to 75 parts by mass, and particularly preferably 30 to 60 parts by mass, per 100 parts by mass of the solid content of the composition (excluding the colorant).

[0065] <Epoxy Compound (B)> The epoxy compound (B) (hereinafter also referred to as "compound B") according to the present invention means a compound that does not fall under the category of compound (A) and has one or more epoxy groups. Low-temperature curing properties can be obtained by using an epoxy compound. Examples of compound (B) include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds.

[0066] (B-1) Aromatic Epoxy Compounds Aromatic epoxy compounds have an aromatic ring and an epoxy group, but do not have a cycloalkene oxide structure. Compounds having at least one aromatic hydrocarbon ring can also be used as such aromatic epoxy compounds. Examples of aromatic epoxy compounds include polyglycidyl ethers of polyhydric phenols having at least one aromatic ring, such as bisphenol A and bisphenol F, or alkylene oxide adducts thereof; 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 phenyldimethanol, phenyldiethanol, and phenyldibutanol; polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid; diepoxidized products of divinylbenzene; and glycidyl amine compounds such as N,N-diglycidylaniline and its derivatives. Further examples include compounds obtained by reacting an aromatic epoxy compound having two or more glycidyl ether groups with a main chain skeleton that contains a rubber component and includes a group capable of reacting with an epoxy group to form a covalent bond.

[0067] As the aromatic epoxy compound, commercially available products can be used, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Corporation); Oxol PG-100, Oxol EG-200, Oxol EG-210, Oxol EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Tohto Kasei Co., Ltd.); YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epicron N-665, Epicron HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501 H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901, EP-3950S, EP-3950L, EP-3980S (manufactured by ADEKA Corporation); TECHMOREVG-3101L (manufactured by Printec Co., Ltd.), and the like.

[0068] (B-2) Aliphatic Epoxy Compounds Aliphatic epoxy compounds have an epoxy group and do not contain a cycloalkene oxide structure or an aromatic ring. Specific examples of such aliphatic epoxy compounds include glycidyl ethers of aliphatic alcohols and polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts. More specific examples include glycidyl ethers of polyhydric alcohols such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and diglycidyl ether of neopentyl glycol; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin; and monoglycidyl ethers of aliphatic higher alcohols and epoxidized polybutadiene. Other examples include compounds having a tricyclodecane structure and a glycidyl ether group, such as dimethyloltricyclodecane diglycidyl ether and tricyclodecane diglycidyl ether. Other examples include compounds obtained by reacting an aliphatic glycidyl ether epoxy compound having two or more glycidyl ether groups with a main chain skeleton containing a rubber component and a group capable of reacting with an epoxy group to form a covalent bond. Furthermore, hydrogenated products of aromatic epoxy compounds, such as hydrogenated bisphenol A diglycidyl ether, can also be used as the aliphatic epoxy compound.The aliphatic epoxy compound may also be a compound having, as a constituent unit, a structure in which an oxiranyl group is directly bonded via a single bond to a cycloalkyl ring derived from an epoxycycloalkyl ring, and having, as a main chain structure, a structure in which epoxy groups of the epoxycycloalkyl ring are polymerized together, such as a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0069] As the aliphatic epoxy compound, commercially available products can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, and Denacol EX-83. 2. Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycilol ED-503, Adeka Glycilol ED-503G, Adeka Glycilol ED-506, Adeka Glycilol ED-523T (manufactured by ADEKA Corporation), and the like.

[0070] As the aliphatic epoxy compound, any of aliphatic ring-containing epoxy compounds having an aliphatic ring such as an aliphatic hydrocarbon ring or an aliphatic heterocycle, and chain aliphatic epoxy compounds having no aliphatic ring can be used.

[0071] (B-3) Alicyclic Epoxy Compounds Specific examples of alicyclic epoxy compounds include compounds containing a cycloalkene oxide structure, such as cyclohexene oxide and cyclopentene oxide, which are obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.

[0072] Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, 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, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, and the like.

[0073] Commercially available products that can be suitably used as the alicyclic epoxy compound include those described in Japanese Patent No. 6103653 and the like.

[0074] In the present invention, the epoxy equivalent of compound (B) is preferably 80 g / eq. or more but less than 300 g / eq., more preferably 250 g / eq. or less, and particularly preferably 150 g / eq. or less. This is because when the epoxy equivalent is in the above range, low-temperature curing properties are excellent. The epoxy equivalent can be measured according to Japanese Industrial Standard JIS K 7236:2001.

[0075] From the viewpoint of a balance between the patterning properties and low-temperature curing properties of the composition, it is preferable to use a compound (B) having an epoxy equivalent of 80 g / eq. or more and 150 g / eq. or less in combination with a compound (B) having an epoxy equivalent of more than 150 g / eq. and less than 300 g / eq. In this case, the content of the compound (B) having an epoxy equivalent of 80 g / eq. or more and 150 g / eq. or less is preferably 3 to 60 mass%, more preferably 5 to 40 mass%, and particularly preferably 8 to 33 mass%, relative to the total content of the compound (B).

[0076] The molecular weight of compound (B) is not particularly limited as long as the desired curability and the like are obtained, and can be, for example, from 50 to 20,000. From the viewpoints of the balance between the patterning properties and low-temperature curability of the composition as well as the ease of application and adhesion of the composition, the molecular weight is more preferably from 100 to 2,000, and even more preferably from 200 to 1,500. In the case of a polymer, the molecular weight is a weight average molecular weight, and can be measured by the same method as described in the section on compound (A).

[0077] The number of epoxy groups contained in compound (B) can be appropriately set depending on the desired curability, etc. The number of epoxy groups contained per molecule of compound (B) may be 1 or more, but can be 2 to 12, preferably 2 to 10, and most preferably 3 or more. This is because a composition using such compound (B) can easily produce a cured product with a high-resolution pattern and has good reactivity during curing and low-temperature curing properties.

[0078] Furthermore, in one embodiment of the composition of the present invention, it is preferable that the compound (B) contains a glycidyl-type epoxy compound. The glycidyl-type epoxy compound is an epoxy compound having a glycidyl group. The composition containing the glycidyl-type epoxy compound is likely to achieve low-temperature curing properties and has excellent pattern definition. In particular, the compound (B) may contain a glycidyl ether group, a glycidyl amino group, or a diglycidyl amino group as the glycidyl group. Since the low-temperature curing properties are further improved, it is preferable that the compound (B) contains a glycidyl ether group or a glycidyl amino group, and it is more preferable that the compound (B) contains a glycidyl amino group, and it is most preferable that the compound (B) contains a diglycidyl amino group, since the low-temperature curing properties are particularly excellent.

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

[0080] According to the present invention, the content of compound (B) is preferably 10 parts by mass or more and 75 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, and even more preferably 30 parts by mass or more and 65 parts by mass or less, relative to 100 parts by mass of compound (A), because the composition has an excellent balance between low reflectivity and low-temperature curing property, and makes it easier to obtain a high-resolution pattern.

[0081] From the viewpoint of a balance between the low reflectance and low-temperature curing property of the composition and the ease of obtaining a high-resolution pattern, the content of 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 35 parts by mass or less, and even more preferably 10 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the solid content of the composition (excluding the colorant). Furthermore, the solid content as referred to in the present invention refers to the content excluding the solvent described below.

[0082] From the viewpoint of a balance between the low reflectance and low-temperature curing property of the composition and the ease of obtaining a high-resolution pattern, it is preferable that compound (B) contains an aromatic epoxy compound, and the content of the aromatic epoxy compound in compound (B) is preferably 30% by mass or more, more preferably 40% by mass or more, and may be 60% by mass or more.

[0083] <Thiol Compound (C)> The thiol compound (C) according to the present invention (hereinafter also referred to as "compound (C)") means a compound that does not fall under the category of component (A), does not have an epoxy group, and has one or more thiol groups.

[0084] In the present invention, it is preferable to use compounds represented by the following formulas (C1) to (C6) as examples of compound (C). This is because the composition has excellent low-temperature curing properties. In addition, these compounds are preferable in terms of availability and the balance between the patterning properties and curing properties of the composition.

[0085] (In the formula, L １１ , L １２ , L ２１ , L ２２ , L ２３ , L ３１ , L ３２ , L ３３ , L ３４ , L ４１ , L ４２ , L ４３ , L ４４ , L ４５ , L ４６ , L ５１ , L ５２ , L ５３ , L ６１ , L ６２ , L ６３ and L ６４ (Hereinafter referred to as “L １１ ~L ６４ ") each independently represent a linear or branched alkylene group having 1 to 10 carbon atoms. R ６４ , R ６５ and R ６６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a21 represents an integer of 1 to 20.

[0086] The above L １１ ~L ６４ Examples of the alkylene group having 1 to 10 carbon atoms represented by the formula (I) include a divalent group having a structure in which one hydrogen atom has been removed from an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include the above-mentioned R １ Among alkyl groups having 1 to 20 carbon atoms, those having a predetermined number of carbon atoms can be used. ６４ , R ６５ and R ６６ The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in R １ Among the hydrocarbon groups having 1 to 20 carbon atoms in the above, those corresponding to aliphatic hydrocarbon groups (groups corresponding to the aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by M) can be used. １１ ~L ６４ and an alkylene group having 1 to 10 carbon atoms represented by R ６４ , R ６５ and R ６６ The aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is unsubstituted or one or more hydrogen atoms in the group are substituted, and when substituted, the substituents are the same as those in the above R １ The substituents may be the same as those that can substitute one or more hydrogen atoms of the hydrocarbon group represented by the formula (I) or (II).

[0087] In terms of the balance between the patterning properties and low-temperature curing properties of the composition, 11 ~L 64 is preferably an alkylene group having 1 to 5 carbon atoms, and particularly preferably a linear alkylene group having 1 to 3 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms, and particularly preferably a branched alkylene group having 3 to 5 carbon atoms, because the composition has an excellent balance between patterning properties and low-temperature curing properties.

[0088] The above L 11 ~L 64 Specific examples of the linear alkylene group having 1 to 3 carbon atoms represented by the formula (I) include methylene, ethylene (ethane-1,2-diyl), propylene (propane-1,3-diyl), etc.11 ~L 64 Specific examples of the branched alkylene group having 3 to 5 carbon atoms represented by the formula (I) 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.

[0089] L in (C1) 11 and L 12 may be the same group or different groups, but from the viewpoint of ease of synthesis, it is preferable that they are the same group. This is because the composition has an excellent balance between low-temperature curing properties and ease of availability. This is because L 21 ~L 23 , (C3) L 31 ~L 34 , (C4) L 41 ~L 46 , (C5) L 51 ~L 53 , (C6) L 61 ~L 64 The same is true for .

[0090] In the present invention, the above R 64 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms, because the composition has an excellent balance between patterning properties and low-temperature curing properties.

[0091] From the viewpoint of the balance between the patterning properties and curability of the composition, the molecular weight of compound (C) is preferably from 100 to 1,000, more preferably from 300 to 900, and particularly preferably from 350 to 800. This is because the composition has an excellent balance between the patterning properties and the low-temperature curability.

[0092] In the present invention, a primary thiol compound, a secondary thiol compound, a tertiary thiol compound, or the like can be used as the compound (C).From the viewpoint of improving the storage stability of the composition and achieving an excellent patterning shape, the compound (C) is preferably a secondary thiol compound.For example, when the compound (C) contains a secondary thiol compound, the content of the secondary thiol compound contained in the compound (C) is preferably 30% by mass or more, more preferably 40% by mass or more.

[0093] Compound (C) may be monofunctional or polyfunctional. Compound (C) is preferably polyfunctional in order to enhance the effects of excellent patterning properties and 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, even more preferably 4 to 6, and particularly preferably 4. This is because, when the number of thiol groups contained in the molecule of compound (C) is within the above range, the composition will have excellent low-temperature curing properties and patterning properties.

[0094] As the compound (C), a commercially available product may be used. Examples of commercially available 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 K.K.), 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 K.K.), Karenz MT (registered trademark) PE (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis(3-mercaptobutyrate), Showa Denko K.K.), and EGMP-4 (trade name, bifunctional thiol compound, tetraethyl Examples of suitable thiol compounds include ethylene glycol bis(3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TMMP (trade name, trifunctional thiol compound, trimethylolpropane tris(3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TEMPIC (trade name, trifunctional thiol compound, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, SC Organic Chemical Co., Ltd.), PEMP (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis(3-mercaptopropionate), SC Organic Chemical Co., Ltd.), and DPMP (trade name, hexafunctional thiol compound, dipentaerythritol hexakis(3-mercaptopropionate), SC Organic Chemical Co., Ltd.).

[0095] The content of compound (C) is more preferably 1 part by mass or more and 40 parts by mass or less, even more preferably 1.5 parts by mass or more and 20 parts by mass or less, and particularly preferably 2 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the solid content of the composition (excluding the colorant), because the composition has an excellent balance of low reflectivity, low-temperature curing property, and patterning property.

[0096] The content of compound (C) is preferably 1 part by mass or more and 400 parts by mass or less, more preferably 3 parts by mass or more and 250 parts by mass or less, even more preferably 7 parts by mass or more and 150 parts by mass or less, and particularly preferably 10 parts by mass or more and 90 parts by mass or less, relative to 100 parts by mass of epoxy compound (B), because the composition has an excellent balance between low reflectivity and low-temperature curing property, and makes it easy to obtain a high-resolution pattern.

[0097] The content of compound (C) is more preferably 3 parts by mass or more and 65 parts by mass or less, still more preferably 4 parts by mass or more and 40 parts by mass or less, and particularly preferably 5 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of compound (A), because the composition has an excellent balance between low reflectivity and low-temperature curing property, and a high-resolution pattern can be easily obtained.

[0098] <Quaternary ammonium salt (D)> The quaternary ammonium salt (hereinafter also referred to as "compound (D)") according to the present invention does not fall under the category of component (A) and does not have an epoxy group or a thiol group in the molecule. Furthermore, it is preferable that the quaternary ammonium salt does not fall under the category of a polymer obtained by polymerizing a monomer having a quaternary ammonium group with a terminal double bond. By using a quaternary ammonium salt in the composition of the present invention, it is possible to cure at low temperatures and obtain a cured product with low reflectivity.

[0099] Examples of the quaternary ammonium salt include those represented by the following formula (D). In the formula, R １０１ , R １０２ , R １０３ and R １０４ each independently represents an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a group in which a methylene group in the alkyl group, alkenyl group, aryl group, or arylalkyl group has been substituted with a divalent group selected from the following <Group 2>. - represents a monovalent anion. <Group 2>: -NRCO-, -CONR-, -COO-, -OCO- and -O-. R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0100] R １０１ , R １０２ , R １０３ and R １０４ The alkyl group, alkenyl group, aryl group and arylalkyl group represented by R １ Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R include R １ Among the groups exemplified as hydrocarbon groups having 1 to 20 carbon atoms and represented by the formula (I), those having the predetermined number of carbon atoms can be mentioned. From the viewpoint of the balance between low reflectivity and low-temperature curing property of the cured product, R １０１ , R １０２ , R １０３ , R １０４ The number of carbon atoms in each of R is independently preferably 1 to 30, more preferably 1 to 20, further preferably 2 to 10, and particularly preferably 3 to 8. From the viewpoint of the balance between low reflectivity and low-temperature curing property of the cured product, R １０１ , R １０２ , R １０３ , R １０４ is preferably an alkyl group, an alkenyl group, or a group in which a methylene group in these groups has been substituted with a divalent group selected from Group 2.

[0101] The alkyl group, alkenyl group, aryl group, and arylalkyl group mentioned in the annotation of formula (D) may have one or more hydrogen atoms substituted. Examples of the substituents that can be substituted include those selected from the above-mentioned Substituent Group 1.

[0102] Y - Examples of the anion represented by the formula (I) include a halide ion, an inorganic halide anion, a sulfonate anion, a sulfate anion, a phosphate anion, an imide ion, a borate anion, a carboxylate anion, a dithiocarbamate anion, an organic sulfonylmethide ion, a thiocyanate anion, and a dithiocarbamate anion.

[0103] Examples of the halide ions include chlorine anions, bromine anions, iodine anions, and fluorine anions. Examples of the inorganic halide anions include perchlorate anions, chlorate anions, thiocyanate anions, hexafluorophosphate anions, antimony hexafluoride anions, arsenic hexafluoride anions, and boron tetrafluoride anions. Examples of the sulfonate anions include methanesulfonate ions, fluorosulfonate ions, benzenesulfonate anions, 1-naphthylsulfonate anions, trifluoromethanesulfonate anions, N-alkyl (or aryl)diphenylamine-4-sulfonate anions, 2-amino-4-methyl-5-chlorobenzenesulfonate anions, 2-amino-5-nitrobenzenesulfonate anions, camphorsulfonate anions, and fluorobenzenesulfonate anions. Examples of the sulfate anions include ethyl sulfate anions.

[0104] Examples of the phosphate anion include octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion. Examples of the imide ion include saccharin anion, bis(trifluoromethanesulfone)imide ion, bis(pentafluoroethanesulfone)imide ion, phthalimide ion, o-sulfobenzimid, bis(heptafluoropropanesulfone)imide ion, bis(nonafluorobutanesulfone)imide ion, bis(undecafluoropentanesulfone)imide ion, bis(pentadecafluoroheptanesulfone)imide ion, bis(tridecafluorohexanesulfone)imide ion, bis(heptadecafluorooctanesulfonimide) ion, and (trifluoromethanesulfone)(nonafluorobutanesulfone)imide ion. Examples of the borate anion include organic anions in which an alkyl group and / or an aryl group is bonded to one of the bonds of a boron atom. Specific examples of the borate anion include tetrakis(pentafluorophenyl)borate anion, tetrakis(4-fluorophenyl)borate anion, tetraphenylborate anion, tetraarylborate anion, and triarylalkylborane anion. Specific examples of the carboxylate anion include benzoate anion, formate anion, acetate anion, propionate anion, butyrate anion, and lactate anion. Specific examples of the methide ion include organic sulfonyl methide ions such as tris(trifluoromethanesulfonyl)methide and tris(methanesulfonyl)methide. Specific examples of the dithiocarbamate anion include N,N-diethyldithiocarbamate anion.

[0105] Specific examples of the quaternary ammonium salt (D) include tetraethylammonium salt, tetramethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetrapentylammonium salt, tetrahexylammonium salt, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium salt, N,N-diethyl-N,N-di(2-hydroxyethyl)ammonium salt, dodecyldimethylhydroxyethylammonium-butyl phosphate salt, tetradecyldimethylhydroxyethylammonium-butyl phosphate salt, dodecyldimethylhydroxyethylammonium-ethyl phosphate salt, tetradecyldimethylhydroxyethylammonium- Examples thereof include ethyl phosphate salts, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, lauryltrimethylammonium bromide, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin, diPOE stearylmethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and behenyltrimethylammonium methylsulfate.

[0106] A preferred quaternary ammonium salt is a quaternary ammonium salt having an alkyl group (hereinafter also referred to as "alkyl quaternary ammonium salt"). Examples of alkyl quaternary alkyl ammonium include mono-, di-, tri-, and tetra-alkyl ammonium salts, depending on the number of alkyl groups bonded to the nitrogen atom, which is 1 to 4. Examples of the mono-, di-, tri-, and tetra-alkyl ammonium salts include those represented by the formula (D) above, where R １０１ ~R １０４Examples of suitable quaternary ammonium salts include compounds in which one, two, three, or four of the alkyl groups selected from the group consisting of alkyl groups are alkyl groups. The alkyl groups may be the same or different, and are preferably linear alkyl groups having 1 to 20 carbon atoms, more preferably alkyl groups having 2 to 10 carbon atoms, and particularly preferably alkyl groups having 3 to 8 carbon atoms. This is because the use of such quaternary ammonium salts allows for the production of a cured product with low reflectance.

[0107] Among alkyl quaternary ammonium salts, at least one selected from trialkyl ammonium salts and tetraalkyl ammonium salts is preferred, and tetraalkyl ammonium salts are preferred. By using such a quaternary ammonium salt, a cured product having excellent low-temperature curing properties and low reflectance can be obtained. As the trialkyl ammonium salt, for example, in the formula (D), R １０２ , R １０３ and R １０４ The tetraalkylammonium salts include compounds in which R １０１ , R １０２ , R １０３ and R １０４ are each an alkyl group.

[0108] Among the alkyl quaternary ammonium salts, compounds in which the alkyl group is an unsubstituted alkyl group or a hydroxyalkyl group are preferred because of their excellent solubility, and compounds in which the alkyl group is an unsubstituted alkyl group are particularly preferred.

[0109] Preferably, alkyl quaternary ammonium salts are used, more preferably trialkyl quaternary ammonium salts and tetraalkyl quaternary ammonium salts, and particularly preferably tetraalkyl quaternary ammonium salts, because the use of such alkyl quaternary ammonium salts provides a cured product that is excellent in low-temperature curing properties and has low reflectance.

[0110] Compositions in which the anion of the quaternary ammonium salt is an anion derived from a weak acidic compound are preferred because they have excellent low-temperature curing properties and can produce cured products with low reflectivity. The term "weakly acidic compound-derived anion" refers to an anion obtained by removing one hydrogen ion from a weak acid. The weak acid is an acid with a pKa of 2 or more. A weak acid with a pKa of 3 or more and 5 or less is particularly preferred because it is easier to produce cured products with low reflectivity. In the case of polybasic acids, the pKa referred to here refers to pKa1. Examples of weak acids include carboxylic acids and phosphoric acids, with carboxylic acids being preferred because they can be cured at low temperatures and produce cured products with low reflectivity. Therefore, a carboxylic acid anion obtained by removing one hydrogen atom from the carboxyl group of a carboxylic acid is preferred as the anion derived from a weakly acidic compound. Among these, monocarboxylic acid anions with 7 or fewer carbon atoms are more preferred, and monocarboxylic acid anions with 4 or fewer carbon atoms are particularly preferred. Formate, acetate, and propionate anions are particularly preferred, with acetate being the most preferred. By using a quaternary ammonium salt having such an anion, low temperature curing is possible, and a low reflectance cured product can be more easily obtained.

[0111] The content of the quaternary ammonium salt (D) is more preferably from 1 to 25 parts by mass, even more preferably from 2 to 15 parts by mass, and particularly preferably from 3 to 10 parts by mass, per 100 parts by mass of the solid content of the composition (excluding the colorant), because the composition has an excellent balance of low reflectivity, low-temperature curing property, and patterning property.

[0112] The content of the quaternary ammonium salt (D) is preferably 3 parts by mass or more and 70 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, even more preferably 10 parts by mass or more and 50 parts by mass or less, and particularly preferably 20 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the epoxy compound (B), because the composition has an excellent balance between low reflectivity and low-temperature curing property, and makes it easy to obtain a high-resolution pattern.

[0113] The content of the quaternary ammonium salt (D) is more preferably 3 parts by mass or more and 70 parts by mass or less, still more preferably 5 parts by mass or more and 45 parts by mass or less, and particularly preferably 10 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the compound (A), because the composition has an excellent balance between low reflectivity and low-temperature curing property, and a high-resolution pattern can be easily obtained.

[0114] <Black Pigment (E)> The black pigment used in the composition of the present invention means a black colorant that is insoluble in a solvent, which will be described later, and includes inorganic or organic coloring materials that are insoluble in a solvent, and inorganic or organic dyes that have been converted into lakes. Compounds that fall under the group consisting of compound (A), epoxy compound (B), thiol compound (C), quaternary ammonium salt (D), and polymerization initiator (F) are not considered to be black pigment (E).

[0115] Examples of the black pigment include carbon black, activated carbon, carbon fiber, carbon nanotubes, carbon microcoils, carbon nanohorns, carbon aerogel, fullerene, aniline black, synthetic iron black, pigment black 7, titanium black, lactam black, and perylene black. Examples of the carbon black include carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black, or lamp black, the carbon black prepared or coated with an epoxy resin, the carbon black prepared by dispersing the carbon black in a resin in a solvent and coating it with 20 to 200 mg / g of resin, the carbon black subjected to an acidic or alkaline surface treatment, carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and the carbon black containing CO and CO in the volatile matter at 950°C. ２ The total amount of oxygen calculated from the surface area of ​​100 m ２ Examples of suitable carbon black include carbon black and graphitized carbon black, each of which has a particle size of 9 mg or more per particle.

[0116] The black pigments can be divided into organic black pigments and inorganic black pigments. Organic black pigments are organic black pigments, such as lactam black and perylene black, while inorganic black pigments are inorganic black pigments, such as the various carbon blacks mentioned above.

[0117] In the present invention, it is preferable that the colorant is a black pigment because it has excellent light-blocking properties. Among black pigments, carbon black is more preferable because it has even better light-blocking properties. In the present invention, it is preferable to use surface-treated carbon black because it can provide a composition with excellent storage stability and a cured product with excellent electrical properties (high resistivity, dielectric constant properties). As the type of surface treatment, sulfonic acid treatment is preferable because it can provide a composition with excellent storage stability and has high light-blocking properties. In this specification, sulfonic acid-treated carbon black is also referred to as sulfonic acid-treated carbon black.

[0118] The method for treating carbon black with sulfonic acid is a treatment for disposing sulfonic acid groups on the surface of the carbon black, and examples thereof include (1) a method in which carbon black is oxidized with peroxodisulfuric acid or a salt thereof, and (2) a method in which carbon black is treated with a sulfonating agent.

[0119] The method (1) of oxidizing carbon black with peroxodisulfuric acid or a salt thereof can be carried out by any known method. For example, it can be carried out 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 dispersant as necessary, heating the mixture at less than 100°C, preferably 40 to 90°C, for less than 24 hours, preferably 2 to 20 hours, and neutralizing it to a pH of 7 as necessary. Examples of the salt of peroxodisulfuric acid include metal salts such as lithium, sodium, potassium, and aluminum, as well as ammonium salts. The amount of peroxodisulfuric acid or a salt thereof used is preferably in the range of 0.5 to 5 parts by mass per part by mass of carbon black.

[0120] The method (2) of treating carbon black with a sulfonating agent can be carried out by any known method, for example, by mixing carbon black and a sulfonating agent or dissolving them in a solvent and stirring the mixture at 200° C. or less, preferably 0 to 100° C. Examples of the sulfonating agent include concentrated sulfuric acid, oleum, sulfur trioxide, halogenated sulfuric acid, amidosulfuric acid, hydrogen sulfite, sulfite, SO ３ -dioxane complex, SO ３ Examples of the solvent include water; acidic solvents such as sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid, and acetic anhydride; basic solvents such as pyridine, triethylamine, and trimethylamine; ethers such as tetrahydrofuran, dioxane, and diethyl ether; polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane, nitromethane, acetone, acetonitrile, and benzonitrile; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, xylene, and nitrobenzene; alcoholic solvents such as methanol, ethanol, and isopropanol; and chlorinated solvents such as chloroform, trichlorofluoromethane, methylene chloride, and chlorobenzene. Mixed solvents of these may also be used. The amount of sulfonating agent used is preferably in the range of 0.5 to 20 parts by mass per part by mass of carbon black. When multiple sulfonating agents are used, the total amount of the agents preferably falls within the above range. In order to suppress the formation of known sulfones as a side reaction of the sulfonation reaction, a known sulfone inhibitor, such as a fatty acid, an organic peracid, an acid anhydride, acetic acid, or a ketone, may be added in an amount of 0.01 to 5% within a range that does not inhibit the reaction.

[0121] In the composition of the present invention, a cured product obtained from a composition in which the content of the black pigment (E) is 10 to 300 parts by mass relative to 100 parts by mass of the compound (A) is preferable because it has excellent light-shielding properties and allows the formation of a cured product with a high-resolution pattern. The content of the colorant is more preferably 30 to 250 parts by mass, particularly preferably 60 to 200 parts by mass, and most preferably 80 to 160 parts by mass relative to 100 parts by mass of (A).

[0122] <Polymerization initiator (F)> As the polymerization initiator (F) used in the composition of the present invention, a conventionally known radical polymerization initiator can be used. Note that compounds corresponding to the compounds (A), (B), thiol compounds (C), and (D) are not considered to be polymerization initiators (F). In the present invention, a cured product with low reflectance can be obtained by combining the compound (A), the quaternary ammonium salt (D), and the polymerization initiator (F).

[0123] The radical polymerization initiator includes a photoradical polymerization initiator and a thermal radical polymerization initiator, with a photoradical polymerization initiator being more preferred due to its high reactivity.

[0124] The photoradical polymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light, and any conventionally known compound can be used. Preferred examples of the photoradical polymerization initiator include acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, and oxime ester compounds.

[0125] Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclo ... hexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

[0126] The benzyl compounds include benzyl and the like.

[0127] 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.

[0128] Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0129] In the present invention, a composition in which the polymerization initiator (F) is an oxime ester compound is preferred because it has excellent low-temperature curing properties and patterning characteristics. Examples of the oxime ester compound include compounds having a group represented by the following formula (III):

[0130]

[0131] (In the formula, R ４１ and R ４２ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or the heterocyclic group has been substituted with a divalent group selected from the following <Group B>, <Group B> being -O-, -CO-, -COO-, -OCO-, -NR ４３ -, -NR ４３ CO-, -S-, -CS-, -SO ２ -, -SCO-, -COS-, -OCS- and CSO-, R ４３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, m represents 0 or 1, and * in the formula represents a bond.

[0132] R in the above formula (III) ４１ , R ４２ and R ４３ Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) are R １As examples of the hydrocarbon group having 1 to 20 carbon atoms, those mentioned above can be used.

[0133] R in the above formula (III) ４１ and R ４２ Examples of the heterocyclic group having 2 to 20 carbon atoms represented by the following formula are the same as the heterocyclic groups having 2 to 20 carbon atoms given as examples of the heterocyclic group in the above-mentioned Substituent Group 1.

[0134] R ４１ and R ４２ The hydrocarbon group having 1 to 20 carbon atoms, the heterocyclic group having 2 to 20 carbon atoms, and the group in which a methylene group in the hydrocarbon group or the heterocyclic group is substituted with a group selected from <Group B> may have a hydrogen atom substituted or may be unsubstituted. If substituted, the substituent is preferably selected from the following Substituent Group 2, and is particularly preferably a halogen atom. When a hydrogen atom in a heterocyclic group or a group in which a methylene group in a heterocyclic group is substituted with a divalent group is substituted with a group selected from the following Substituent Group 2, the substituent is selected from groups other than heterocyclic groups in Substituent Group 2. R ４３ The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) may have a hydrogen atom substituted or may be unsubstituted. When substituted, the substituent is preferably selected from the following Substituent Group 2, and a halogen atom is particularly preferred. Substituent Group 2: Halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group, and heterocyclic group having 2 to 20 carbon atoms. The explanation of these is the same as for Substituent Group 1.

[0135] Among the compounds having a group represented by formula (III) above, the compound represented by formula (IV) below has particularly high sensitivity and makes it easier to obtain a good pattern shape, and is therefore preferably used in the composition of the present invention.

[0136]

[0137] (In the formula, R ４１ , R ４２ and m are R in formula (III),４１ , R ４２ and m, 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 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or heterocyclic group is substituted with —O— or —CO—; X ２ is an oxygen atom, a sulfur atom, a selenium atom, CR ５３ R ５４ , CO, NR ５５ or PR ５６ represents R ５３ , R ５４ , R ５５ and R ５６ (Hereinafter, R ５１ and R ５２ Combined with "R ５１ ~R ５６ ") each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or heterocyclic group is substituted with -O- or -CO-; R ５１ , and R ５２ may each independently combine with either of the adjacent benzene rings to form a ring, g represents a number from 0 to 5, and h represents a number from 0 to 4. When g is 2 or more, multiple R ５１ may be the same or different. When h is 2 or more, a plurality of R ５２ may be the same or different. ５１ , R ５２ , R ５３ , R ５４ , R ５５ and R ５６ The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) or the hydrocarbon group in which a methylene group is substituted with -O- or -CO- may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or a heterocyclic group having 2 to 20 carbon atoms. ５１ , R５２ , R ５３ , R ５４ , R ５５ and R ５６ or a group in which a methylene group in the heterocyclic group is substituted with —O— or —CO— may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, or an isocyanate group.

[0138] A composition in which the polymerization initiator (F) is a compound having an indole skeleton, particularly a compound having a group represented by the above formula (III) and having an indole skeleton, is also preferred because it has excellent patterning properties. Examples of the compound having a group represented by the above formula (III) and having an indole skeleton include oxime ester compounds represented by the following general formula (V).

[0139] (In the formula, R ４１ , R ４２ and m are R in formula (III), ４１ , R ４２ and m, R ３０３ represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or heterocyclic group is substituted with —O— or —CO—; R ３０３ and R ３０７ and R ３０３ and R ３０８ may be joined together to form a ring, and R ３０４ , R ３０５ , R ３０６ and R ３０７ are each independently -R ２１１ , -OR ２１１ , -SR ２１１ , -COR ２１４ , -CONR ２１５ R ２１６ , -NR ２１２ COR ２１１ , -OCOR ２１１ , -COOR ２１４ , -SCOR ２１１ , -OCSR２１１ , -COSR ２１４ , -CSOR ２１１ , a hydroxyl group, —CN or a halogen atom; R ３０４ and R ３０５ , R ３０５ and R ３０６ and R ３０６ and R ３０７ may be joined together to form a ring, and R ３０８ is -R ２１１ , -OR ２１１ , -SR ２１１ , -COR ２１１ , -CONR ２１２ R ２１３ , -NR ２１２ COR ２１１ , -OCOR ２１１ , -COOR ２１１ , -SCOR ２１１ , -OCSR ２１１ , -COSR ２１１ , -CSOR ２１１ , a hydroxyl group, —CN or a halogen atom; R ２１１ , R ２１２ and R ２１３ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or heterocyclic group is substituted with —O— or —CO—; R ２１４ , R ２１５ and R ２１６ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ３０３ , R ２１１ , R ２１２ and R ２１３ A hydrogen atom of the group represented by R may be further substituted with a group selected from <Substituent Group 3>, ３０４ , R ３０５ , R ３０６ and R ３０７ The hydrogen atom of the group represented by the formula (I) may be further substituted with a group selected from <Substituent Group 3>. <Substituent Group 3>: -R ２２１ , -OR ２２１ , -COR ２２１ , -SR ２２１ , -NR ２２２ R ２２３, -CONR ２２２ R ２２３ , -NR ２２２ OR ２２３ , -NCOR ２２２ OCOR ２２３ , -NR ２２２ COR ２２１ , -OCOR ２２１ , -COOR ２２１ , -SCOR ２２１ , -OCSR ２２１ , -COSR ２２１ , -CSOR ２２１ , a hydroxyl group, a nitro group, —CN, a halogen atom, and —COOR ２２１ .R ２２１ , R ２２２ and R ２２３ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group or heterocyclic group is substituted with —O— or —CO—; R ２２１ , R ２２２ and R ２２３ The hydrogen atoms of the group represented by the formula (I) may be further substituted with a hydroxyl group, a nitro group, —CN, a halogen atom, a hydroxyl group, or a carboxyl group.

[0140] R in the above formula (IV) ５１ ~R ５６ and R in the above formula (V) ３０３ , R ２１１ ~R ２１６ , R ２２１ ~R ２２３ The hydrocarbon group represented by the formula (I) is １ As examples of the hydrocarbon group having 1 to 20 carbon atoms, those mentioned above can be used.

[0141] R in the above formula (IV) ５１ ~R ５６ and R in the above formula (V) ３０３ , R ２１１ ~R ２１３ , R ２２１ ~R ２２３ The heterocyclic group having 2 to 20 carbon atoms represented by the formula (I) is １The heterocyclic groups having 2 to 20 carbon atoms are the same as those described as the substituents in the hydrocarbon groups represented by R ５１ ~R ５６ Examples of the heterocyclic group having 2 to 20 carbon atoms as a substituent to replace a hydrogen atom in the group represented by formula (I) include R １ and the like.

[0142] R ５１ ~R ５６ The hydrocarbon groups having 1 to 30 carbon atoms, heterocyclic groups having 2 to 20 carbon atoms, and groups in which a methylene group in these groups is substituted with -O- or -CO- may further have a substituent, or may be unsubstituted. When substituted, 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, or a heterocyclic group having 2 to 10 carbon atoms. However, the substituent substituting a hydrogen atom in the heterocyclic group is a group selected from the above-mentioned substituent group 2 other than a heterocyclic group. R ５１ , and R ５２ are each independently combined with either adjacent benzene ring to form a ring, X ２ (oxygen atom, sulfur atom, selenium atom, CR ５３ R ５４ the carbon atom of CO, the carbon atom of NR ５５ or a nitrogen atom of PR ５６ and a phosphorus atom of the aryl group, which forms a ring with two benzene rings to form a tricyclic fused ring. Examples of such a tricyclic fused ring include R ５１ or R ５２ is attached to the adjacent benzene ring, and R ５１ and R ５２ and two carbon atoms in each of the two benzene rings to which X is bonded. ２ and a 5-membered ring is formed, whereby the two benzene rings in formula (IV) and the 5-membered ring form a fused ring. An example of such a ring is a carbazole ring.

[0143] Preferred examples of the polymerization initiator (F) include compound Nos. F1 to F17 shown below, and examples of the compound represented by formula (IV) above include compound Nos. F1 and F3 to F15 shown below. Examples of the compound represented by formula (V) above include compound Nos. F16 and F17 shown below. However, the polymerization initiator (F) used in the present invention is not limited in any way by the following compounds.

[0144]

[0145]

[0146]

[0147] A composition using a compound having a carbazole skeleton as the polymerization initiator (F) is preferred because it has excellent curability. In particular, it is preferred to use a polymerization initiator (F) having a carbazole structure and a nitro group.

[0148] From the above viewpoint, among the compounds represented by formula (IV), X ２ NR ５５ Those represented by NR are preferred because they have high sensitivity. ５５ When using R ５５ The number of carbon atoms in R is preferably 10 or less, particularly 5 or less, from the viewpoint of availability of a polymerization initiator and sensitivity. ５５ is preferably a phenyl group, an alkyl group or an alkenyl group, which may be substituted with a substituent.

[0149] Among the compounds represented by formula (IV), those in which h is 0 are preferred in terms of ease of production. Among the compounds represented by formula (IV), those in which g is 1 or more and R ５１ In particular, compounds in which g is 1 or more and R ５１ Among these, compounds in which one or more are nitro groups are preferred, and compounds having a nitro group at the 3-position of the carbazole ring are particularly preferred.

[0150] In addition, among the compounds represented by formula (V), R ３０３ In view of good sensitivity, a hydrocarbon group having 1 to 30 carbon atoms or a heterocyclic group having 2 to 10 carbon atoms is preferred, a hydrocarbon group having 1 to 30 carbon atoms is more preferred, and among hydrocarbon groups having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms is even more preferred, and an aryl group having 6 to 30 carbon atoms and having an electron-withdrawing group as a substituent is particularly preferred. The electron-withdrawing group is selected from <Substituent Group 3>, and for example, -COR ２２１ , -SR ２２１ , -NR ２２２ R ２２３ , -CONR ２２２ R ２２３ , -NR ２２２ OR ２２３ , -NCOR ２２２ OCOR ２２３ , -NR ２２２ COR ２２１ , -OCOR ２２１ , -COOR ２２１ , -SCOR ２２１ , -OCSR ２２１ , -COSR ２２１ , -CSOR ２２１ , a nitro group, —CN, a halogen atom, and —COOR ２２１ In formula (V), R ３０４ , R ３０５ , R ３０６ , R ３０７ and R ３０８ The number of carbon atoms in each of these groups is preferably 10 or less, more preferably 3 or less, and it is particularly preferred that these groups are hydrogen atoms.

[0151] In addition, in the compound having a group represented by formula (III), R ４１is preferably a linear or cyclic alkyl group, an aryl group, or an arylalkyl group, or a group in which a methylene group in any of these groups is substituted with -O-, from the viewpoint of sensitivity and ease of production, more preferably an alkyl group, an aryl group, or a group in which a methylene group in an alkyl group or aryl group is substituted with -O-, preferably a group in which a methylene group in an alkyl group or aryl group is substituted with -O-, and more preferably a group in which one or more methylene groups in the alkyl group in a phenyl group substituted with an alkyl group are substituted with -O-. ４１ The number of carbon atoms in the alkyl group is preferably 18 or less, more preferably 4 to 18, and particularly preferably 9 to 15.

[0152] Among the compounds having a group represented by formula (III), R ４２ However, those having 10 or less carbon atoms, particularly 7 or less, and particularly 3 or less carbon atoms are preferred from the viewpoint of ease of production. ４２ is preferably a substituted or unsubstituted chain alkyl or phenyl group in terms of sensitivity and ease of production, and more preferably a chain alkyl group.

[0153] Other radical polymerization initiators that can be 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-(pyr-1-yl)]titanium.

[0154] Commercially available radical polymerization initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARCLES NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (all manufactured by Tronly); and the like.

[0155] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals upon heating, and any conventionally known compound can be used. Preferred examples of the thermal radical polymerization initiator include azo compounds, peroxides, and persulfates.

[0156] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).

[0157] Examples of peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate.

[0158] Examples of persulfates include ammonium persulfate, sodium persulfate, and potassium persulfate.

[0159] The polymerization initiators exemplified above can be used alone or in combination of two or more.

[0160] A composition containing 1 to 80 parts by mass of polymerization initiator (F) relative to 100 parts by mass of compound (A) is preferred, more preferably 1 to 50 parts by mass, and particularly preferably 3 to 30 parts by mass, because it has excellent sensitivity and can produce a cured product with a high-resolution pattern even when the light-shielding property is high. From the same viewpoint, the content of 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, relative to 100 parts by mass of the solids content (excluding the colorant) of the composition.

[0161] <UV-reactive surface modifier (G)> The composition of the present invention preferably further contains an UV-reactive surface modifier (G) because the composition has high liquid repellency and therefore excellent antifouling properties. In particular, when the composition of the present invention is used as a black matrix, it is preferable because it enables the formation of a high-resolution color filter when forming pixels by printing with an inkjet printer or the like.

[0162] The ultraviolet-reactive surface modifier (G) refers to an additive that has a radically polymerizable reactive group and can impart to the coating film surface functions such as water- and oil-repellency and prevention of adhesion of stains such as fingerprints. Examples of the radically polymerizable reactive group include ethylenically unsaturated double bond groups such as acrylic groups, methacrylic groups, and vinyl groups.

[0163] The ultraviolet reactive surface modifier (G) can have a known structure that improves slipperiness. Such structures include polysiloxane structures, fluorine-containing groups (fluoro groups or organic groups substituted with fluoro groups), etc. For example, silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. In addition, compounds having a fluorine-containing poly(meth)acrylate skeleton and containing the above-mentioned polymerizable group can also be mentioned.

[0164] Among the ultraviolet-reactive surface modifiers (G), fluorine-containing ultraviolet-reactive surface modifiers are preferred because they produce cured products with excellent patterning properties due to minimal dripping during inkjet printing. Among the fluorine-containing ultraviolet-reactive surface modifiers, fluorine-containing non-silicone oligomers or polymers are particularly preferred. When the ultraviolet-reactive surface modifier (G) is an oligomer or polymer, the weight-average molecular weight (Mw: polystyrene equivalent) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 10,000. The weight-average molecular weight can be determined in the same manner as above. Examples of fluorine-containing non-silicone oligomers include those having a repeating unit represented by the following formula (G1) and a repeating unit represented by formula (G2) or formula (G3):

[0165] In formulas (G1) to (G3), R ２００ , R２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ , R ２０６ , R ２０７ , R ２０８ , R ２０９ , R ２１０ and R ２１１ (Hereinafter referred to as “R ２００ ~R ２１１ ") each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom. ２０１ , L ２０２ , L ２０３ , L ２０４ (Hereinafter referred to as “L ２０１ ~L ２０４ ") each independently represent a single bond or a divalent linking group. X ２０１ represents an acryloyloxy group or a methacryloyloxy group, and X ２０２ represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom, or an aryl group having 6 to 20 carbon atoms substituted with a fluorine atom; X ２０３ represents a divalent linking group.

[0166] In formulas (G1) to (G3), R ２００ ~R ２１１ are preferably each independently a hydrogen atom or an alkyl group. ２００ ~R ２１１ When R represents an alkyl group, it is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. ２００ ~R ２１１ When L represents a halogen atom, it is preferably a fluorine atom. ２０１ ~L ２０４ represents a divalent linking group, examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR ２１２ --, --CONR ２１２ -, -CO-, -COO-, -OCO-, SO ２ NR ２１２ -, -O-, -S-, -SO ２Among these, at least one selected from the group consisting of alkylene groups having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms, which may be substituted with a halogen atom, and arylene groups having 6 to 20 carbon atoms, particularly 6 to 12 carbon atoms, which may be substituted with a halogen atom, or a combination of these groups and —NR ２１２ --, --CONR ２１２ -, -CO-, -COO-, -OCO-, SO ２ NR ２１２ -, -O-, -S-, and SO ２ and a group consisting of a combination of at least one group selected from the group consisting of an alkylene group having 2 to 10 carbon atoms which may be substituted with a halogen atom, —COO—, —OCO—, —O—, —CO—, —CONR ２１２ - or a group consisting of a combination of these groups is more preferred. ２１２ represents a hydrogen atom or a methyl group. ２０１ ~L ２０４ When the divalent linking group represented by the formula (I) contains an alkylene group which may be substituted with a halogen atom, the alkylene group may be further substituted with a hydroxyl group. ２０３ is -(Z-O)z １ A group represented by - is preferred, and Z represents an alkylene group substituted with a fluorine atom. １ represents an integer of 1 or more. The number of carbon atoms in the alkylene group is more preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkylene group substituted with a fluorine atom may contain an oxygen atom.

[0167] Commercially available ultraviolet-reactive surface modifiers (G) include, for example, RS-56, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90, and RS-72-K (all manufactured by DIC Corporation).

[0168] The content of compound (G) in a composition is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of compound (A), since a cured product having high sensitivity and excellent chemical resistance can be obtained, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass.

[0169] <Ethylenically Unsaturated Compound (H)> The composition of the present invention preferably further contains an ethylenically unsaturated compound (H) (hereinafter also referred to as "compound (H)"), since this improves the patterning properties of the composition and also improves low-temperature curing properties. The ethylenically unsaturated compound (H) refers to a compound having one or more ethylenically unsaturated bond groups and not corresponding to any of the above-mentioned components (A) to (F). In the present invention, the use of a compound (H) having a molecular weight of 1,000 or less is preferred because it further enhances sensitivity. In the case of a polymer, the molecular weight is the weight-average molecular weight, which is determined by the same method as above. Examples of the compound (H) include t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butyl, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (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,Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols, such as 6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester(meth)acrylate oligomers; metal salts of unsaturated polybasic acids, such as zinc (meth)acrylate and magnesium (meth)acrylate; Amides of unsaturated monobasic acids and polyvalent amines such as (meth)acrylamide, methylene bis-(meth)acrylamide, diethylenetriamine tris(meth)acrylamide, xylylene bis(meth)acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl (meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene unsaturated aromatic compounds such as vinyl ether, vinyl phenol, vinyl sulfonic 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;Examples of suitable compounds include aliphatic conjugated dienes such as 3-butadiene, isoprene, and chloroprene; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, tricyclododecane diacrylate, divinyl succinate, diallyl phthalate, triallyl phosphate, vinyl imidazole, vinyloxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers, and vinyl urethane compounds of polyisocyanate compounds. In the present invention, from the viewpoint of low-temperature curing properties, it is preferable to use an ester of an unsaturated monobasic acid with a polyhydric alcohol or a polyhydric phenol. The compound (H) can be used alone or in combination of two or more.

[0170] As the compound (H), commercially available products can also be used. Examples of such commercially available products include KAYARAD DPHA, DPEA-12, PEH400DA, THE-330, RP-1040, NPHDA, PET30, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-215 and M-350 (all manufactured by Toagosei Co., Ltd.); and NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPH, and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0171] Compound (H) having a molecular weight of 1,000 or less has excellent sensitivity, and the resulting cured product has excellent chemical resistance. From this point of view, compound (H) having a molecular weight of 200 or more and 800 or less is particularly preferred.

[0172] In the present invention, the number of ethylenically unsaturated bond groups contained in the molecule of compound (H) is preferably 3 to 10, more preferably 4 to 8, and particularly preferably 4 to 6. When the number of ethylenically unsaturated bond groups contained in the molecule of compound (H) is within the above range, the composition will have excellent low-temperature curing properties.

[0173] As the compound (H), a urethane acrylate having a structure obtained by reacting an alcohol having an ethylenically unsaturated bond with a polyfunctional isocyanate compound having two or more isocyanate groups can also be preferably used. Compositions containing such urethane acrylates are preferred because they have excellent sensitivity and the resulting cured products have excellent chemical resistance.

[0174] A composition in which the content of compound (H) is 2 to 120 parts by mass per 100 parts by mass of compound (A) is preferred because a cured product having high sensitivity and excellent chemical resistance can be obtained, more preferably 3 to 100 parts by mass, and particularly preferably 5 to 50 parts by mass.

[0175] A solvent can be further added to the composition of the present invention. The solvent is a compound that is liquid at 25°C under 1 atmosphere and does not fall under the above-mentioned (A) to (G). As the solvent, a solvent that can dissolve or disperse the above-mentioned components ((A) to (F)) and, if necessary, (G), etc., can usually be 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 ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGM EA), ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; paraffinic solvents such as mineral spirits and Swazol #310 (all manufactured by Cosmo Matsuyama Oil); and Solvesso #100 (all manufactured by Exxon Chemical). Solvents include halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water, and these solvents can be used alone or in combination. Among these, ketones and ether ester-based solvents, particularly PGMEA and cyclohexanone, are preferred because of their good compatibility with the resist and polymerization initiator in the composition.

[0176] In the composition of the present invention, the content of the solvent is not particularly limited, but is preferably 30 to 95 mass %, more preferably 50 to 95 mass %, relative to 100 mass % of the total amount of the composition. A solvent content within the above range is preferred because it results in a composition that is excellent in handleability (viscosity and wettability of the composition), reduced unevenness during drying, and liquid stability (no precipitation or sedimentation of components contained in the composition), and it allows for appropriate control of the thickness of the cured product when it is obtained.

[0177] To the composition of the present invention, conventional additives may be further added, as necessary, such as dispersants, organic polymers, inorganic compounds other than pigments, coupling agents, chain transfer agents, sensitizers, surfactants, leveling agents, thermal polymerization inhibitors such as melamine compounds, p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; adhesion promoters; fillers; antifoaming agents; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-aggregating agents; catalysts; curing accelerators; crosslinking agents; and thickeners.

[0178] The dispersant may be any dispersant capable of dispersing and stabilizing the black pigment (E), and commercially available dispersants, such as the BYK series manufactured by BYK Chemie, can be used. Polymer dispersants made of polyester, polyether, or polyurethane having a basic functional group, and those having a nitrogen atom as the basic functional group, where the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and having an amine value of 1 to 100 mg KOH / g are preferably used.

[0179] The content of the dispersant in the solid content of the composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass.

[0180] Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, etc. By using the organic polymer together with the compound (A), the properties of the cured product can also be improved.

[0181] Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based compounds, manganese-based compounds, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper; and among these, titanium oxide, silica, layered clay minerals, and silver are preferred, with silica being more preferred.

[0182] As the silica, either dry silica or wet silica can be used. Furthermore, powdered silica or colloidal silica can also be used. The particle size of the silica is preferably 5 to 45 nm, and even more preferably 10 to 40 nm. The particle size of the silica referred to here is the average particle size, and can be measured with a dynamic light scattering particle size analyzer. For example, a Zetasizer Nano (manufactured by the Malvern Division of Spectris Co., Ltd.) can be used.

[0183] When the inorganic compound is contained, the content thereof is preferably 1 to 65 parts by mass relative to 100 parts by mass of the compound (A), more preferably 7 to 55 parts by mass, and particularly preferably 15 to 50 parts by mass, from the viewpoints of the storage stability of the cured product and the development adhesion of the cured product to the substrate.

[0184] Examples of the coupling agent include alkyl-functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane; epoxy-functional alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane; amino-functional alkoxysilanes such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; and γ-mercaptopropyltrimethoxysilane. Examples of suitable alkoxysilanes include mercapto-functional alkoxysilanes, isocyanate-functional alkoxysilanes such as 3-isocyanatepropyltriethoxysilane, ureido-functional alkoxysilanes such as 3-ureidopropyltrialkoxysilane, isocyanurate-functional alkoxysilanes such as tris-(trimethoxysilylpropyl)isocyanurate, titanium alkoxides such as titanium tetraisopropoxide and titanium tetra-normal-butoxide, titanium chelates such as titanium dioctyloxybis(octylene glycolate) and titanium diisopropoxybis(ethylacetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium acylates such as zirconium tributoxymonostearate, and isocyanate silanes such as methyltriisocyanatesilane. The addition of a coupling agent is preferred because it improves adhesion between the cured product and the substrate.

[0185] Commercially available coupling agents can be used, such as KA-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-6123, and KBE-5. 85, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE-103, HMDS-3, KBM-3063, KBM-3103C, KPN-3504 and KF-99 (all manufactured by Shin-Etsu Silicones).

[0186] Examples of the surfactant that can be used include anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halogen salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; and silicone surfactants.

[0187] The leveling agents can be broadly classified into silicone-based leveling agents, acrylic-based leveling agents, fluorine-based leveling agents, vinyl-based leveling agents, etc. For example, fluorine-based leveling agents include leveling agents having a fluoroaliphatic hydrocarbon skeleton and leveling agents having a polyfluoroalkylene ether skeleton, which is a repeating unit formed via an ether bond. The inclusion of a leveling agent is preferred in that a uniform cured product can be obtained.

[0188] As the leveling agent, commercially available products can be used, and examples thereof include F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, and the like from the "Megafac" series manufactured by DIC Corporation.

[0189] When the composition contains a leveling agent, the amount of the leveling agent is preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 15 parts by mass, per 100 parts by mass of the solids in the composition (excluding the colorant), in order to enhance the above-mentioned effect of containing the leveling agent.

[0190] In the composition of the present invention, the content of the optional components other than the above-described components (A) to (H) and the solvent is appropriately selected depending on the intended use, and is not particularly limited as long as the effects of the present invention are not impaired. Preferably, however, the total content is 20 parts by mass or less per 100 parts by mass of the total of the above-described components (A) to (H).

[0191] The composition of the present invention and its cured product can be used in a wide range of applications, including curable paints, varnishes, curable adhesives, printed circuit boards, displays (color filters in color display liquid crystal display panels for color televisions, PC monitors, personal digital assistants, digital cameras, etc., color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent displays, plasma display panels, and black partition walls for organic EL), powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electrical and electronic components, solder resists, and magnetic recording materials. The present invention can be used in a variety of applications, including, but not limited to, photoresists for forming dielectric layers in the sequential lamination of printed circuit boards, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, and photoresist materials and protective films used in forming dielectric layers in the sequential lamination of printed circuit boards. The present invention is particularly suitable for use in display devices. In particular, when used as a black matrix, the present invention advantageously achieves the effects of enabling high-precision patterning while simultaneously achieving excellent low-temperature curability and low reflectivity of the cured product, which have been difficult to achieve in the past.

[0192] A method for producing a cured product using the composition of the present invention will be described in detail below. The composition of the present invention can be applied to a supporting substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, or plastic by known means such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, or dipping. In addition, after being applied to a supporting substrate such as a film, it can also be transferred to another supporting substrate, and there is no limitation on the application method.

[0193] The light source of the energy rays used to cure the composition of the present invention can be high-energy rays such as electromagnetic wave energy having a wavelength of 2,000 to 7,000 angstroms, electron beams, X-rays, and radioactive rays, which can be 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. Ultra-high pressure mercury lamps and LEDs emitting light with a wavelength of 300 to 450 nm are preferred, as they provide high productivity and high-quality cured products.

[0194] Furthermore, a laser direct writing method, in which an image is formed directly from digital information from a computer or the like without using a mask by using a laser beam as an exposure light source, is useful because it not only improves productivity but also improves resolution and positional accuracy. Light with a wavelength of 340 to 430 nm is preferably used as the laser beam. For example, lasers that emit light in the visible to infrared region, such as excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, and YAG lasers, are also used. When using these lasers, a sensitizing dye that absorbs light in the relevant visible to infrared region is added.

[0195] The cured product of the present invention is preferably formed by the steps of (1) forming a coating film of the composition of the present invention on a substrate, (2) irradiating the coating film with radiation through a mask having a predetermined pattern, (3) baking the exposed coating film, (4) developing the baked coating film, and (5) heating the developed coating film. As the mask, a multi-tone mask such as a halftone mask or a grayscale mask can also be used.

[0196] The display device of the present invention has the same configuration as a conventionally known display device except that it is provided with the cured product of the present invention. In particular, when the cured product is a BCS, the BCS is preferably provided between cells.

[0197] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0198] [Production Example 1] Production of Alkali-Developable Compound A-1 184 g of 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]-3-phenylindane, 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide, and 105 g of PGMEA were charged and stirred for 16 hours at 120° C. The reaction solution was cooled to room temperature, and 160 g of PGMEA, 59 g of biphthalic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added, followed by stirring at 120° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120°C for 4 hours, 100°C for 3 hours, 80°C for 4 hours, 60°C for 6 hours, and 40°C for 11 hours, and then 128 g of PGMEA was added to obtain an alkali-developable compound A-1 as a PGMEA solution (Mw=5000, Mn=2100, acid value (solids content) 92.7 mg KOH / g). The content of the alkali-developable compound in the alkali-developable compound PGMEA solution A-1 was 45% by mass.

[0199] [Production Example 2] Production of Alkali-Developable Compound A-2 75.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 23.8 g of acrylic acid, 0.273 g of 2,6-di-t-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA were charged and stirred at 90°C for 1 hour, at 100°C for 1 hour, at 110°C for 1 hour, and at 120°C for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100°C for 5 hours. Further, 30.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA were added, and the mixture was stirred at 90°C for 90 minutes and then at 120°C for 4 hours. Then, 122.2 g of PGMEA was added, and the target alkali-developable compound A-2 was obtained as a PGMEA solution (Mw=4190, Mn=2170, acid value (solids content) 52 mg KOH / g). The content of the alkali-developable compound in the alkali-developable compound PGMEA solution A-2 was 45% by mass.

[0200] [Production Example 3] Production of Carbon Black No. 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3,000 ml of a deionized aqueous solution of sodium peroxodisulfate (concentration 2.0 N) were mixed and stirred at 60°C for 10 hours. After filtration, the resulting slurry was neutralized with sodium hydroxide and treated by diafiltration. The resulting solid was dried at 75°C overnight to obtain Carbon Black No. 1 as a black powder.

[0201] [Examples 1 to 12 and Comparative Examples 1 to 9] Preparation of Compositions According to the formulations in Tables 1 and 2, the components were mixed to a solids content of 15% by mass, propylene glycol monomethyl ether acetate (PGMEA) 21.4% by mass, and cyclohexanone (ANONE) 63.6% by mass, to obtain compositions (Examples 1 to 12 and Comparative Examples 1 to 9). The numerical values ​​for the formulations in the tables represent parts by mass. The amounts of each component in Tables 1 and 2 indicate the amount of solids. The symbols for each component in the tables represent the following components. The procedure for preparing a composition using Carbon Black No. 1 involved mixing carbon black with a portion of Compound (A) (A'-1 in Comparative Example 1), dispersant (J-1), and PGMEA in a solvent, followed by processing in a bead mill to prepare a carbon black dispersion (solids content 20% by mass), which was then mixed with the other components. Here, the amount of compound (A) used to prepare the dispersion was 15 parts by mass relative to 100 parts by mass of carbon black. Furthermore, PGMEA was used as the solvent in preparing the dispersion, and the solids concentration was adjusted to 20% by mass. The procedure for preparing a composition using carbon black No. 2 was the same as above, except that a carbon black dispersion, M8252 (untreated carbon black, 20% by mass of dispersant (J-1), 3% by mass of dispersant (J-1), 77% by mass of PGMEA) manufactured by Tokushiki Corporation, was mixed with the other components.

[0202] A-1: Alkali developable compound PGMEA solution A-1 A-2: Alkali developable compound PGMEA solution A-2 A'-1: SPC3000 (manufactured by Showa Denko K.K., alkali developable compound content: 55% by mass, MW: 8100, acid value (solids content): 81 mg KOH / g) B-1: Compound represented by formula (b1) below (molecular weight: 1,000 to 1,500) B-2: Compound represented by formula (b2) below B-3: Compound represented by formula (b3) below B-4: Compound represented by formula (b4) below

[0203]

[0204]

[0205]

[0206]

[0207] C-1: A compound represented by the following formula (c1):

[0208]

[0209] D-1: A compound represented by the following formula (d1):

[0210]

[0211] D'-1: Compound represented by the following formula (d'1) D'-2: Compound represented by the following formula (d'2) D'-3: EH-2021 (manufactured by ADEKA Corporation: imidazole-based latent curing agent)

[0212]

[0213]

[0214] E-1: Carbon Black No. 1 (sulfonic acid-treated carbon black) E-2: Carbon Black No. 2 (Tokushiki M8252 carbon black without surface treatment)

[0215] F-1: Compound No. F9 above F-2: Compound No. F17 above F-3: Compound represented by the following formula (f3)

[0216] G-1: RS-72-K (DIC)

[0217] H-1: Dipentaerythritol hexaacrylate J-1: BYK-167 (BYK-Chemie) J-2: PMA-ST (nanosilica, Nissan Chemical Co., Ltd.) J-3: Fluorine leveling agent (DIC F-554)

[0218] [Evaluation of Compositions] The compositions of Examples 1 to 12 and Comparative Examples 1 to 9 were evaluated for patterning properties, coating surface reflectance, 90°C curability (low-temperature curability), solvent contact angle, and storage stability according to the following procedures. The results are shown in Tables 1 and 2.

[0219] <Patterning Properties> The compositions obtained in the Examples and Comparative Examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater, and then prebaked at 70°C for 120 seconds to obtain a coating film with a thickness of 1.0 µm. The obtained coating film was exposed to light at a dose of 50 mJ / cm through a 20 µm hole mask (holes). ２ The pattern was exposed to light at 1000 W. A Proximity Liner (product name: TME-150R, manufactured by Topcon) was used as the light source. The exposed coating was developed by immersing it in a 0.4% by mass aqueous solution of potassium hydroxide at 25°C for 60 seconds and then thoroughly rinsed with water. After rinsing and drying, the coating was further baked at 120°C for 30 minutes. It can be determined that the closer the line width of the pattern is to the mask width of 20 μm, the more highly precise patterning is possible. A pattern line width of 19 μm or more and less than 21 μm was evaluated as A, 18 μm or more and less than 19 μm or 21 μm or more and less than 22 μm was evaluated as B, and less than 18 μm or 22 μm or more was evaluated as C.

[0220] <Coating Surface Reflectance> The compositions obtained in the Examples and Comparative Examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater, and then prebaked at 70°C for 120 seconds to obtain a coating film having a thickness of 1.0 µm. The obtained coating film was irradiated with an irradiation dose of 50 mJ / cm without using a photomask. ２ The coating was exposed to light at 1000 W. A mirror projection aligner (product name: TME-150RAK, manufactured by Topcon) was used as the light source. After exposure, the coating was developed by immersing it in a 0.4% by mass aqueous solution of potassium hydroxide at 23°C for 60 seconds and then thoroughly rinsed with water. After rinsing and drying, the coating was further post-baked (90°C x 1 hour) to obtain a cured product. The coating reflectance of the obtained cured product was measured as luminous reflectance (400 to 740 nm) using a spectrophotometer (product name: CM-5, manufactured by Konica Minolta). A coating reflectance of less than 4% was evaluated as A, 4% to 4.5% was evaluated as B, and 4.5% or more was evaluated as C.

[0221] <90°C Curability> The compositions obtained in the Examples and Comparative Examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 70°C for 120 seconds to obtain a coating film having a thickness of 1.0 µm. The obtained coating film was exposed to light through a 20 µm hole mask (holes) at a dose of 50 mJ / cm. ２The coating was exposed to light with a 1000 Watt (W) laser. A mirror projection aligner (product name: TME-150RAK, manufactured by Topcon) was used as the light source. The exposed coating was developed by immersing it in a 0.4% by weight aqueous solution of potassium hydroxide at 23°C for 60 seconds and then thoroughly rinsed with water. After rinsing and drying, the coating was further post-baked (90°C x 1 hour) to obtain a cured product. A chemical resistance test was performed on the resulting cured product by wiping it with a clean cloth immersed in PGMEA or acetone under a 300 g load. After each wipe with the clean cloth, the cured product was visually inspected for changes such as peeling or thinning of the film thickness (a maximum of 50 wipes for acetone and a maximum of 100 wipes for PGMEA). The number of wipes with the cloth when peeling or thinning of the film thickness occurred was used as the evaluation result of the chemical resistance test. The higher the number of wipes, the better the low-temperature curing properties.

[0222] <Solvent Contact Angle> The compositions obtained in the Examples and Comparative Examples were applied to a glass substrate (100 mm x 100 mm) using a spin coater, and then prebaked at 70°C for 120 seconds to obtain a coating film having a thickness of 1.0 µm. The obtained coating film was irradiated with a dose of 50 mJ / cm without using a photomask. ２ The coating was exposed to light at 1000 K. A mirror projection aligner (product name: TME-150RAK, manufactured by Topcon) was used as the light source. After exposure, the coating film was developed by immersing it in a 0.4% by mass aqueous solution of potassium hydroxide at 23°C for 60 seconds and then thoroughly rinsed with water. After rinsing and drying, the coating was further post-baked (90°C x 1 hour) to obtain a cured product. The PGMEA contact angle of the obtained cured product was measured using a contact angle meter (Matsubo PG-X). The PGMEA contact angle is preferably 40° or more, and particularly preferably 45° or more. The higher the PGMEA contact angle, the better the antifouling properties.

[0223] <Storage Stability> The compositions obtained in the Examples and Comparative Examples were stored at room temperature (23°C, 40% (RH)) or -18°C, and the change in development time was evaluated. Specifically, the compositions stored for a certain period of time at room temperature or -18°C (evaluation was carried out in 1-day increments up to 10 days at room temperature, and in 10-day increments up to 150 days at -18°C) were applied to a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 70°C for 120 seconds to obtain a coating film with a thickness of 1.0 μm. The obtained coating film was exposed to light through a 20 μm hole mask (holes) at an irradiation dose of 50 mJ / cm. ２ The exposure was performed with a Mirror Projection Aligner (product name: TME-150RAK, manufactured by Topcon Corporation) as the light source. The exposed coating film was immersed in an aqueous solution of 0.4% by mass of potassium hydroxide, and the development time (the time it took for the coating film to dissolve) was measured. The development time of a coating film produced using the composition immediately after production was used as the standard, and the number of days until the development time exceeded 110% was measured. If the storage stability is poor, the components will react in the system and polymerize. As a result, the components will become less soluble in the solvent, and the development time will be longer. In general photolithography, compositions with development times exceeding 110% will not allow stable pattern formation.

[0224]

[0225]

[0226] As is clear from Tables 1 and 2, the compositions of each example containing compound (A), compound (B), compound (C), quaternary ammonium salt (D), black pigment (E), and polymerization initiator (F) exhibited excellent 90°C curability, low reflectivity of the cured product, and enabled high-resolution patterning. In contrast, Comparative Examples 1 to 9, which did not contain any of components (A) to (G), were inferior in any of the patterning properties, low-temperature curing properties, and low reflectivity of the cured product. From the above results, it is clear that the compositions of the present invention exhibit excellent patterning properties, low-temperature curing properties, and low reflectivity of the cured product.

Claims

1. A composition containing a compound (A) having a structure obtained by esterification reaction between an epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following general formula (I) and a polybasic acid anhydride, an epoxy compound (B), a thiol compound (C), a quaternary ammonium salt (D), a black pigment (E), and a polymerization initiator (F). (In the formula, M represents a direct bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, -O-, -S-, -CO-, or -OCO-; a hydrogen atom in the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon group having 6 to 40 carbon atoms represented by M may be substituted with a halogen atom; 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 the formula (I) may be substituted with a carbon-carbon unsaturated bond, -O- or -S-, n is a number from 0 to 10, and when n is 1 or more, there are a plurality of R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ and M may be the same or different.

2. The composition according to claim 1, wherein M in the above general formula (I) is an aromatic hydrocarbon group having 6 to 40 carbon atoms and is a group represented by the following formula (a), (b), (c) or (d): (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 the formula (I) may be substituted with a carbon-carbon unsaturated bond, -O- or -S-; １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R ２２ and R １５ , R １５ and R １６ , R ３０ and R ２３ , R ２３ and R ２４ , R ２４ and R ２５ , R ３８ and R ３１ , R ３１ and R ３２ , R ３２ and R ３３ , R ３４ and R ３５ , R ３５ and R ３６ and R ３６ and R ３７ may be bonded to form a ring, and * in the groups represented by formulae (a), (b), (c) and (d) represents a bond.

3. The composition according to claim 1, wherein the epoxy equivalent of the epoxy compound (B) is 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 anion of the quaternary ammonium salt (D) is an anion derived from a weakly acidic compound.

6. The composition according to claim 1, wherein said black pigment (E) is a 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 of claim 1, further comprising an ultraviolet light reactive surface modifier (G).

9. The composition according to claim 1, further comprising an ethylenically unsaturated compound (H).

10. A black matrix comprising the composition according to any one of claims 1 to 9.

11. A method for producing a cured product, comprising the step of irradiating the composition according to any one of claims 1 to 9 with light.

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

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

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