Pigment dispersion composition for black matrix and method for producing the same, resist composition for black matrix, and black resist film

Abstract

To provide a pigment dispersion composition for black matrix that can give a resist composition for black matrix having excellent optical density and fine line adhesion.SOLUTION: A pigment dispersion composition for black matrix contains carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersion aid, an alkali-soluble resin, an ion scavenger, and a solvent. The carbon black is acidic carbon black. The ion scavenger is an inorganic compound with a median size of 0.1-10 μm, and the content of the ion scavenger is 1-15 pts.mass relative to 100 pts.mass of the carbon black.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a pigment dispersion composition for a black matrix and a method for producing the same, a resist composition for a black matrix, and a black resist film. [Background technology]

[0002] Conventionally, resist compositions using pigment dispersion compositions for black matrices containing carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersing aid, a binder resin, a solvent, and the like are required to have high optical density (light-shielding properties) and fine line adhesion (resolution) (Patent Document 1), and it is known that the optical density (light-shielding properties) and the like can be improved by washing carbon black to reduce potassium ions (Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-38289 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-316620 Summary of the Invention [Problem to be solved by the invention]

[0004] However, washing carbon black as described above requires the use of a large amount of water and further requires complicated operations such as washing, filtration, and drying. Also, a method for removing potassium ions from a composition is generally known in which the composition is passed through a resin column equipped with an ion exchange resin, but this method requires a large amount of ion exchange resin, which results in high costs for procuring and disposing of the ion exchange resin.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a pigment dispersion composition for black matrix which can provide a resist composition for black matrix which is excellent in optical density and fine line adhesion. [Means for solving the problem]

[0006] That is, the present invention relates to a pigment dispersion composition for black matrices, which comprises carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersing aid, an alkali-soluble resin, an ion scavenger, and a solvent, wherein the carbon black is acidic carbon black, and the ion scavenger is an inorganic compound having a median diameter of 0.1 to 10 μm, and the amount of the ion scavenger is 1 to 15 parts by mass per 100 parts by mass of the carbon black.

[0007] The present invention also relates to a resist composition for a black matrix, which contains the pigment dispersion composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator.

[0008] Furthermore, the present invention relates to a black resist film obtained using the black matrix resist composition.

[0009] Furthermore, the present invention relates to a method for producing the pigment dispersion composition for a black matrix, which comprises dispersing at least the carbon black in the presence of the ion scavenger. [Effects of the Invention]

[0010] The pigment dispersion composition for black matrix of the present invention contains carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersing aid, an alkali-soluble resin, an ion scavenger, and a solvent, wherein the carbon black is acidic carbon black, and the ion scavenger is an inorganic compound having a median diameter of 0.1 to 10 μm, and is contained in an amount of 1 to 15 parts by mass per 100 parts by mass of the carbon black. The pigment dispersion composition for black matrix of the present invention uses the ion scavenger to capture substances containing ions such as potassium ions that are mixed in during the production of the acidic carbon black, thereby making it possible to obtain a black matrix resist composition that is excellent in optical density and fine-line adhesion, without requiring procedures such as washing the acidic carbon black. DETAILED DESCRIPTION OF THE INVENTION

[0011] The pigment dispersion composition for black matrix of the present invention contains carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersing aid, an alkali-soluble resin, an ion scavenger, and a solvent.

[0012] <Carbon black> The carbon black is an acidic carbon black having an acidic group such as a carboxyl group. Known acidic carbon blacks used in pigment dispersion compositions for black matrices can be used as the acidic carbon black. For example, from the viewpoint of improving developability and fine line adhesion, the acidic carbon black preferably has a pH of 5.0 or less, more preferably a pH of 1.0 to 3.5. It also preferably has a DBP oil absorption of 80 ml / 100 g or less, more preferably a DBP oil absorption of 70 ml / 100 g or less, and a particle size of 20 to 60 nm. The pH can be measured at 25°C using a glass electrode after preparing an aqueous suspension by adding 1 g of carbon black to 20 ml of decarbonated distilled water (pH 7.0) and mixing with a magnetic stirrer (German Industrial Standard DIN ISO 787 / 9). The DBP oil absorption indirectly quantifies the structure of the carbon black by measuring the void volume, and is a value measured in accordance with JIS K 6217-4. The particle size refers to the average primary particle size measured or calculated by microscopic observation. For commercially available products, the catalog values ​​are used as reference. The carbon black may be used alone or in combination of two or more types.

[0013] Specific examples of the acidic carbon black include Raven 1080 (pH 2.4, average primary particle size 28 nm, DBP oil absorption 60 ml / 100 g), Raven 1100U (pH 2.9, average primary particle size 32 nm, DBP oil absorption 72 ml / 100 g), NEROX 305 (pH 2.8, average primary particle size 28 nm, DBP oil absorption 58 ml / 100 g), and NEROX 3500 (pH Examples include Cabot Corporation's TPK1104R (pH 3.0, average primary particle diameter of approximately 30 nm, DBP oil absorption of 38 ml / 100 g), and Mitsubishi Chemical Corporation's MA14 (pH 2.8, average primary particle diameter of 40 nm, DBP oil absorption of 73 ml / 100 g) and MA220 (pH 2.9, average primary particle diameter of 55 nm, DBP oil absorption of 93 ml / 100 g).

[0014] The carbon black content in the pigment dispersion composition for black matrix is ​​preferably 3% by mass or more, and more preferably 10% by mass or more, from the viewpoint of improving the light-blocking properties when a black matrix film is formed, and is preferably 70% by mass or less, and more preferably 50% by mass or less, from the viewpoint of pigment dispersion.

[0015] <Basic group-containing pigment dispersant> The basic group-containing pigment dispersant may be any known basic group-containing pigment dispersant used in pigment dispersion compositions for black matrices, as long as it can disperse the carbon black. Examples include anionic surfactants, basic group-containing polyester-based pigment dispersants, basic group-containing acrylic-based pigment dispersants, basic group-containing urethane-based pigment dispersants, and basic group-containing carbodiimide-based pigment dispersants. Primary, secondary, or tertiary amino groups are preferred as the basic group, particularly in terms of excellent dispersibility. The basic group-containing pigment dispersants may be used alone or in combination of two or more.

[0016] The basic group-containing pigment dispersant is preferably a polymeric basic group-containing pigment dispersant because it can provide good pigment dispersibility. Examples of the polymeric basic group-containing pigment dispersant include basic group-containing urethane polymeric pigment dispersants, basic group-containing polyester polymeric pigment dispersants, and basic group-containing acrylic polymeric pigment dispersants. Among these, basic group-containing urethane polymeric pigment dispersants and basic group-containing acrylic polymeric pigment dispersants are preferred. The basic group-containing urethane polymeric pigment dispersant is more preferably a basic group-containing urethane polymeric pigment dispersant having at least one chain selected from the group consisting of a polyester chain, a polyether chain, and a polycarbonate chain.

[0017] The basic group-containing pigment dispersant preferably has an amine value of 5 to 50 mgKOH / g, more preferably 5 to 35 mgKOH / g, from the viewpoints of being able to lower the viscosity of the pigment dispersion composition for black matrix and to achieve a high concentration of carbon black in the coating film. The amine value indicates the total amount of free base and base, and is expressed as the number of milligrams of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of sample.

[0018] The amount of the basic group-containing pigment dispersant is preferably 1 to 100 parts by mass, and more preferably 2 to 50 parts by mass, relative to 100 parts by mass of the carbon black.

[0019] <Acidic group-containing pigment dispersing aid> The acidic group-containing pigment dispersing aid is used to further improve pigment dispersibility. Examples include lactam black, perylene compounds, diketopyrrolopyrrole compounds, azonaphthol compounds, dioxazine compounds, quinacridone compounds, phthalocyanine compounds and their metal complexes, anthraquinone, naphthalene, acridone, or triazine pigments, into which an acidic group such as a carboxyl group or a sulfonic acid group has been introduced (acidic group-containing pigment derivatives), and compounds obtained by neutralizing these with organic amines or the like. As the acidic group-containing pigment derivative, a sulfonic acid group-containing phthalocyanine pigment derivative (having a phthalocyanine skeleton) is preferred from the viewpoint of good dispersibility of carbon black. The acidic group-containing pigment dispersing aids can be used alone or in combination of two or more.

[0020] The amount of the acidic group-containing pigment dispersing aid is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the carbon black.

[0021] <Alkali-soluble resin> The alkali-soluble resin is not particularly limited as long as it can be dissolved in an alkaline developer, but is preferably a resin containing one or more anionic groups such as a carboxyl group, a sulfonic acid group, a phosphonic acid group (-P(=O)(OH)), etc. The alkali-soluble resins can be used alone or in combination of two or more.

[0022] From the viewpoint of alkali developability, the acid value of the alkali-soluble resin is preferably from 10 mgKOH / g to 300 mgKOH / g, and more preferably from 20 mgKOH / g to 200 mgKOH / g.

[0023] From the viewpoint of resist film formability, the weight-average molecular weight of the alkali-soluble resin is preferably 3,000 or more, and more preferably 4,000 or more, and from the viewpoint of improving solubility in an alkaline developer, the weight-average molecular weight of the alkali-soluble resin is preferably 100,000 or less, and more preferably 50,000 or less.

[0024] The weight-average molecular weight can be measured by gel permeation chromatography (GPC). For example, chromatography is performed using a Water2690 (manufactured by Waters) GPC apparatus, a PLgel 5 μm MIXED-D (manufactured by Polymer Laboratories) column, tetrahydrofuran as a developing solvent, a column temperature of 25° C., a flow rate of 1 mL / min, an RI detector, a sample injection concentration of 10 mg / mL, and an injection volume of 100 μL, and the weight-average molecular weight can be calculated as a polystyrene equivalent.

[0025] Examples of the alkali-soluble resin include alkali-soluble polyimide resins, alkali-soluble polyimide precursors, alkali-soluble polybenzoxazole resins, alkali-soluble polybenzoxazole precursors, alkali-soluble cardo resins, alkali-soluble epoxy (meth)acrylate resins, alkali-soluble polysiloxane resins, alkali-soluble novolac resins, alkali-soluble (meth)acrylic resins, alkali-soluble polyurethane resins, alkali-soluble polyester resins, etc. Among these, alkali-soluble cardo resins and alkali-soluble epoxy (meth)acrylate resins are preferred from the viewpoint of heat resistance of the coating film.

[0026] The alkali-soluble cardo resin is an alkali-soluble resin having a cardo skeleton, where the cardo skeleton is a skeleton in which two aromatic groups are connected by single bonds to a quaternary carbon atom, which is a ring carbon atom constituting a cyclic structure. Specific examples of alkali-soluble cardo resins include ADEKA ARKLS WR-301 (manufactured by ADEKA Corporation), and Oxol CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, and CR-TR6 (all manufactured by Osaka Gas Chemicals Co., Ltd.).

[0027] The alkali-soluble epoxy(meth)acrylate resin is an acid-modified epoxy resin obtained by introducing ethylenically unsaturated groups by ring-opening addition of the carboxyl groups of an ethylenically unsaturated monocarboxylic acid to the epoxy groups of an epoxy resin, and then adding a polybasic carboxylic acid (or its anhydride) to at least some of the hydroxyl groups generated by the ring-opening of the epoxy groups to introduce carboxyl groups. This resin does not have the cardo skeleton and corresponds to the alkali-soluble resin. Preferred epoxy resins used as the base material for the alkali-soluble epoxy(meth)acrylate resin include bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl-containing epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. Preferred ethylenically unsaturated monocarboxylic acids used to modify the epoxy resin include acrylic acid and methacrylic acid. Preferred examples of polybasic carboxylic acids (or anhydrides thereof) include maleic anhydride, succinic anhydride, and tetrahydrophthalic anhydride. Among these, alkali-soluble epoxy (meth)acrylate resins having a biphenyl skeleton are preferred from the viewpoint of improving fine wire adhesion. Specific examples of the alkali-soluble epoxy (meth)acrylate resins include ZAR-1494H, ZAR-2001H, ZFR-1491H, ZCR-1797H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.). Specific examples of preferred alkali-soluble epoxy (meth)acrylate resins include alkali-soluble epoxy (meth)acrylate resins having a partial structure represented by any of the following structural formulas:

[0028] [ka]

[0029] The amount of the alkali-soluble resin is preferably 1 to 70 parts by mass, and more preferably 2 to 40 parts by mass, relative to 100 parts by mass of the carbon black.

[0030] <Ion scavenger> The ion trapping agent is an inorganic compound having a median diameter of 0.1 to 10 μm. The ion trapping agent may be any agent capable of trapping at least one of cations and anions, and examples thereof include cation trapping agents, anion trapping agents, and amphoteric trapping agents having ion trapping ability. Examples of inorganic compounds include inorganic compounds containing one or more metal atoms selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. Among these, inorganic compounds containing one or more metal atoms selected from the group consisting of bismuth, zirconium, magnesium, and aluminum are preferred. The ion trapping agents can be used alone or in combination of two or more. The median diameter can be measured using a laser diffraction / scattering particle size distribution analyzer. For commercially available products, the catalog values ​​are used as a reference.

[0031] The amount of the ion scavenger is 1 to 15 parts by mass relative to 100 parts by mass of the carbon black. From the viewpoint of improving fine line adhesion, the amount of the ion scavenger is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the carbon black, and from the viewpoint of improving optical density, the amount of the ion scavenger is preferably 10 parts by mass or less, more preferably 8 parts by mass or less.

[0032] <Solvent> The solvent can be any known solvent used in pigment dispersion compositions for black matrices. From the viewpoint of stably dispersing the pigment and sufficiently dissolving the basic group-containing pigment dispersant and the alkali-soluble resin, the solvent is preferably an ester-based solvent, an ether-based solvent, an ether ester-based solvent, a ketone-based solvent, an aromatic hydrocarbon-based solvent, or a nitrogen-containing solvent. The solvents can be used alone or in combination of two or more.

[0033] Examples of the ester solvents include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid ester, n-amyl formate, etc. Examples of the ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc. Examples of the ether ester solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Examples of the ketone solvents include methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone. Examples of the aromatic hydrocarbon solvents include toluene, xylene, and alkylnaphthalene. Examples of the nitrogen-containing solvents include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0034] The proportion of the solvent in the pigment dispersion composition for black matrix is ​​preferably 40% by mass or more, and more preferably 50% by mass or more, from the viewpoint of processability, and is preferably 90% by mass or less, and more preferably 80% by mass or less, from the viewpoint of dispersion stability.

[0035] <Epoxy resin> The pigment dispersion composition for black matrices may contain an epoxy resin from the viewpoint of improving fine line adhesion. In particular, blending an epoxy resin is preferable for high-resistance applications. The epoxy resin is a multifunctional epoxy resin having two or more epoxy groups. Examples of the epoxy resin include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, trisphenolmethane epoxy resins, biphenol epoxy resins, alicyclic epoxy resins, linear aliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl ethers of condensates of phenolic compounds (phenol, cresol, alkylphenol, catechol, bisphenol F, bisphenol A, bisphenol S, etc.) with aldehyde compounds (formaldehyde, salicylaldehyde, etc.), glycidyl ethers of bifunctional phenols, glycidyl ethers of bifunctional alcohols, glycidyl ethers of trifunctional or higher polyphenols, and hydrogenated or halogenated versions of these. The epoxy resin may be a polyfunctional epoxy resin having an alicyclic or aromatic ring, or may be a polyfunctional epoxy resin having an alicyclic dicyclopentadiene skeleton. Among these, from the viewpoint of improving fine wire adhesion, a polyfunctional epoxy resin having an aromatic ring is preferred.Specific examples of the epoxy resin include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, and Epolite 3002 (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L, and Denacol EX-321L (all manufactured by Nagase ChemteX Corporation), GAN, GOT, NC3000, NC6000, and E Examples include PPN502H and EPPN-503 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, and E4275 (all manufactured by Japan Epoxy Resins Co., Ltd.), Epiclon EXA-9583, Epiclon N695, HP7200, and HP4032 (all manufactured by Dainippon Ink and Chemicals, Inc.), VG3101 (manufactured by Mitsui Chemicals, Inc.), Tepic S, Tepic G, and Tepic P (all manufactured by Nissan Chemical Industries, Ltd.), and Pototo YH-434L (manufactured by Tohto Kasei Co., Ltd.). Note that it is preferable that the epoxy resin does not have an indane structure or a biphenyl structure in terms of reactivity, etc.

[0036] Preferred examples of the epoxy resin include polyfunctional epoxy resins having aromatic rings represented by the following formulas 1 to 7.

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] The amount of the epoxy resin is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of carbon black contained in the pigment dispersion composition for a black matrix or the resist composition for a black matrix described below, from the viewpoint of the resistance value as a black matrix, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, from the viewpoint of the degree of blackness due to the pigment concentration.

[0045] The pigment dispersion composition for black matrix may further contain additives such as a leveling agent, a resin other than the epoxy resin and the alkali-soluble resin, an antioxidant, an antifoaming agent, etc. However, from the viewpoint of odor, it is preferable that the composition does not contain a thiol compound (for example, a thiol compound having a molecular weight of 1,000 or less).

[0046] In the pigment dispersion composition for black matrices, the total content of the carbon black, the basic group-containing pigment dispersant, the acidic group-containing pigment dispersing aid, the alkali-soluble resin, the ion scavenger, and the solvent is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more. Furthermore, when the epoxy resin is blended, the total content of the carbon black, the basic group-containing pigment dispersant, the acidic group-containing pigment dispersing aid, the alkali-soluble resin, the ion scavenger, the solvent, and the epoxy resin in the pigment dispersion composition for black matrices is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more.

[0047] The pigment dispersion composition for a black matrix may be prepared by dispersing the above-described components using a roll mill, kneader, high-speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high-pressure disperser, etc. In particular, from the viewpoint of efficiently capturing ion-containing substances contained in the carbon black and improving optical density and fine line adhesion, it is preferable to disperse at least the carbon black in the presence of the ion scavenger.

[0048] <Resist composition for black matrix> The black matrix resist composition of the present invention includes the pigment dispersion composition for black matrix, a photopolymerizable compound, and a photopolymerization initiator. The proportion of the carbon black is preferably 30% by mass or more and 80% by mass or less of the solid content of the black matrix resist composition.

[0049] <Photopolymerizable compound> The photopolymerizable compound can be a known photopolymerizable compound used in a black matrix resist composition, such as a monomer or oligomer having a photopolymerizable unsaturated bond. The photopolymerizable compounds can be used alone or in combination of two or more.

[0050] Examples of the monomer having one photopolymerizable unsaturated bond include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; and aminoalkyl methacrylates such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl acrylate. alkyl methacrylate or acrylate; methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.; methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate, etc.

[0051] Examples of the monomer having two or more photopolymerizable unsaturated bonds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexameth ... Examples of the copolymer include tetraethylene glycol diacrylate, tetramethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

[0052] Examples of oligomers having a photopolymerizable unsaturated bond include those obtained by appropriately polymerizing the above-mentioned monomers.

[0053] The content of the photopolymerizable compound is preferably 2 to 20 mass %, and more preferably 4 to 15 mass %, of the solid content of the black matrix resist composition.

[0054] The photopolymerization initiator can be any known photopolymerization initiator used in black matrix resist compositions, such as benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzil, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzil dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiators, and oxime ester-based photopolymerization initiators. These photopolymerization initiators can be used alone or in combination of two or more.

[0055] The content of the photopolymerization initiator is preferably 0.1 to 15 mass %, and more preferably 1 to 10 mass %, of the solid content of the black matrix resist composition.

[0056] The black matrix resist composition may further contain the above-mentioned alkali-soluble resin from the viewpoint of developability with an alkaline developer. The total amount of the alkali-soluble resin is preferably 10% by mass or more and 50% by mass or less of the solid content of the black matrix resist composition. The black matrix resist composition may further contain the above-mentioned solvent from the viewpoint of improving coatability. The total amount of the solvent is preferably 50% by mass or more, and more preferably 70% by mass or more, of the black matrix resist composition.

[0057] If necessary, additives such as a leveling agent, an antioxidant, and an antifoaming agent may be added to the black matrix resist composition.

[0058] The black matrix resist composition may be prepared by stirring and mixing the components such as the black matrix pigment dispersion composition, the photopolymerizable compound, and the photopolymerization initiator using a stirring device or the like.

[0059] <Black resist film> The black resist film of the present invention is obtained using the black matrix resist composition. The black resist film has a surface resistance of 5.0×10 9 It is preferable that the resistance is Ω / □ or more, and 1.0×10 10 It is more preferable that the resistance is Ω / □ or more, and 1.0×10 11 It is more preferable that the surface resistance is 1.0×10 Ω / □ or more. 12 It is preferable that the resistance is Ω / □ or more, and 1.0×10 13 It is more preferable that it is Ω / □ or more. [Example]

[0060] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0061] <Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-6> <Preparation of Pigment Dispersion Composition for Black Matrix> The various raw materials shown in Tables 1 and 2 were mixed to obtain the formulations (mass %) shown in Tables 1 and 2, and then the mixture was milled in a bead mill to prepare pigment dispersion compositions for black matrices of each Example and Comparative Example.

[0062] [Table 1]

[0063] [Table 2]

[0064] In Tables 1 and 2, NEROX305 is acidic carbon black (oil absorption 58 ml / 100 g, pH 2.8, average primary particle size 28 nm, manufactured by Orion Engineered Carbons); TPK1104R is an acidic carbon black (oil absorption: 38 ml / 100 g, pH 3.0, average primary particle diameter approximately 30 nm, manufactured by Cabot Corporation); IXEPLAS B1 is a dual ion trapping agent (zirconium / bismuth system, median diameter 0.4 μm, manufactured by Toagosei Co., Ltd.); IXE-100 is a cation scavenger (zirconium-based, median diameter 1 μm, manufactured by Toagosei Co., Ltd.); IXE-500 is an anion scavenger (bismuth-based, median diameter 1.5 μm, manufactured by Toagosei); IXE-550 is an anion scavenger (bismuth-based, median diameter 1.5 μm, manufactured by Toagosei Co., Ltd.); IXE-600 contains two ion trapping agents (antimony / bismuth system, median diameter 1 μm, manufactured by Toagosei Co., Ltd.); IXE-700F is an anion scavenger (aluminum / magnesium type, median diameter 1.5 μm, manufactured by Toagosei Co., Ltd.); IXE-770F is an anion scavenger (aluminum / magnesium type, median diameter 6 μm, manufactured by Toagosei Co., Ltd.); IXE-6136 is a dual ion trapping agent (zirconium / bismuth system, median diameter 2.1 μm, manufactured by Toagosei Co., Ltd.); DB167 is an amino group-containing polyurethane polymer dispersant with polyester chains (manufactured by BYK-Chemie, amine value of solids: 25 mg KOH / g, solids content: 52% by mass); SS5000S is a phthalocyanine dye derivative with a sulfonic acid group (manufactured by Lubrizol); BYK2100 is a phthalocyanine dye derivative with a sulfonic acid group (manufactured by BYK-Chemie); ZCR-1569H is an alkali-soluble epoxy (meth)acrylate resin with a biphenyl skeleton (solid content 69%, manufactured by Nippon Kayaku Co., Ltd.); EPPN-503 is a trishydroxyphenylmethane type epoxy resin (Nippon Kayaku Co., Ltd.); PGMEA stands for propylene glycol monomethyl ether acetate;

[0065] <Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-6> <Preparation of Black Matrix Resist Composition> The various raw materials shown in Tables 3 and 4 were mixed using a high-speed stirrer to obtain the formulations (mass %) shown in Tables 3 and 4, and then filtered through a filter with a pore size of 0.5 μm to prepare black matrix resist compositions for each of the Examples and Comparative Examples.

[0066] The black matrix resist composition obtained above was used to evaluate each item according to the following evaluation methods. The results are shown in Tables 3 and 4.

[0067] <Evaluation of the optical density (OD value) of the resist pattern> Each of the above black matrix resist compositions was applied to a glass substrate (Corning 1737) using a spin coater to a film thickness of 1 μm. After pre-baking at 100°C for 3 minutes, the substrate was exposed to a high-pressure mercury lamp and post-baked at 230°C for 30 minutes to obtain a resist film formed only in the solid areas. The optical density (OD value) of each of the resulting resist films in the solid areas was measured using a Macbeth densitometer (TD-931, product name, manufactured by Macbeth). An optical density (OD value) of 4.0 or higher was considered acceptable.

[0068] <Evaluation of Fine Line Adhesion (A) and (B) of Black Resist Film> Each of the above black matrix resist compositions was applied to a glass substrate (EAGLE XG) using a spin coater to a film thickness of 1 μm, and prebaked at 100° C. for 3 minutes. Next, using a photomask having a line pattern with a line width of 1 μm to 20 μm and 1 μm intervals, the resist composition was irradiated with a UV integrated dose of 100 mJ / cm using a high-pressure mercury lamp. 2 After that, the film was exposed to light at 1 kgf / cm in a 0.05% aqueous potassium hydroxide solution at 23°C. 2Development was started from the time when the development pattern began to appear (break point) at a shower development pressure of 1 kgf / cm. In the evaluation of fine line adhesion (A), development was stopped when the time reached 1.3 times the break point, and in the evaluation of fine line adhesion (B), development was stopped 30 seconds after the break point. 2 The glass substrate was then rinsed with high-pressure spray water. The size (μm) of the smallest line pattern remaining on the glass substrate was evaluated. The pass criteria for evaluation of fine line adhesion (A) were a break point of 50±25 seconds and a smallest line pattern size of 10 μm or less. The pass criteria for evaluation of fine line adhesion (B) were a break point of 20±10 seconds and a smallest line pattern size of 8 μm or less.

[0069] <Measurement of surface resistance of black resist film> Each of the above black matrix resist compositions was applied to a glass substrate (EAGLE XG) using a spin coater to a film thickness of 1 μm, prebaked at 100°C for 3 minutes, and then exposed to a high-pressure mercury lamp (UV integrated light dose 80 mJ / cm 2 ) and then post-baked at 230°C for 60 minutes to produce a black resist pattern (black matrix) consisting only of the solid area. The surface resistance of each black resist pattern was measured using a microcurrent meter R8340 and an optional shielding box R12702A (both manufactured by Advance Co., Ltd.).

[0070] [Table 3]

[0071] [Table 4]

[0072] In Tables 3 and 4, DPHA is dipentaerythritol hexaacrylate; OXE02 is an oxime ester photopolymerization initiator, "IRGACURE OXE02" (manufactured by BASF Japan); WR-301 is an alkali-soluble cardo resin "ADEKA ARKLS WR-301" (solid content 44%, manufactured by ADEKA Corporation); PGMEA stands for propylene glycol monomethyl ether acetate;

Claims

1. The ink contains carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersant, an alkali-soluble resin, an ion scavenger, and a solvent, The carbon black is an acidic carbon black, The ion scavenger is an inorganic compound having a median diameter of 0.1 to 10 μm, and is contained in an amount of 1 to 15 parts by mass relative to 100 parts by mass of the carbon black.

2. 2. The pigment dispersion composition for a black matrix according to claim 1, wherein the carbon black has a DBP oil absorption of 80 ml / 100 g or less.

3. 3. The pigment dispersion composition for a black matrix according to claim 1, wherein the basic group-containing pigment dispersant has an amine value of 5 to 50 mgKOH / g.

4. 4. The pigment dispersion composition for black matrix according to claim 1, wherein the alkali-soluble resin is an alkali-soluble cardo resin and / or an alkali-soluble epoxy (meth)acrylate resin.

5. 5. A resist composition for a black matrix, comprising the pigment dispersion composition for a black matrix according to claim 1, a photopolymerizable compound, and a photopolymerization initiator.

6. A black resist film obtained by using the resist composition for black matrix according to claim 5.

7. 5. A method for producing a pigment dispersion composition for a black matrix according to claim 1, comprising dispersing at least the carbon black in the presence of the ion scavenger.

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