Black matrix pigment dispersion composition and manufacturing method thereof, black matrix resist composition, and black resist film

Abstract

A pigment dispersion composition for a black matrix comprising carbon black, a pigment dispersant containing a basic group, a pigment dispersion aid containing an acid group, an alkali-soluble resin, an ion capture agent, and a solvent, wherein the carbon black is acidic carbon black, the ion capture agent is an inorganic compound having a median diameter of 0.1 to 10 μm, and the composition comprises 1 to 15 parts by mass per 100 parts by mass of carbon black. The pigment dispersion composition for a black matrix has excellent optical density and fine line adhesion.

Description

Technology Field

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

[0002] In the past, a resist composition using a pigment dispersion composition for a black matrix containing carbon black, a pigment dispersant containing a basic group, a pigment dispersion aid containing an acid group, a binder resin, and a solvent was required to have high optical concentration (light-blocking properties) or fine line adhesion (resolution) (Patent Document 1), and it is also known that if the potassium ions are reduced by washing the carbon black, the optical concentration (light-blocking properties) can be improved (Patent Document 2). Prior art literature

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-38289 [Patent Document 2] Japanese Patent Publication No. 2007-316620 The problem to be solved

[0004] However, when cleaning carbon black as described above, there was a problem in that a large amount of water had to be used, and cumbersome operations such as cleaning, filtration, and drying were required. In addition, although a method of passing the composition through a resin tower equipped with ion exchange resin to remove potassium ions from the composition is known, there was a problem in that high costs were incurred for procuring and disposing of the ion exchange resin due to the use of a large amount of ion exchange resin.

[0005] The present invention was made in consideration of the above circumstances and aims to provide a pigment dispersion composition for a black matrix that yields a resist composition for a black matrix with excellent optical concentration and fine line adhesion. means of solving the problem

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

[0007] In addition, the present invention relates to a resist composition for a black matrix containing a pigment dispersion composition for the black matrix, a photopolymerizable compound, and a photopolymerization initiator.

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

[0009] In addition, the present invention relates to a method for preparing a pigment dispersion composition for a black matrix, wherein at least the carbon black is dispersed in the presence of the ion capture agent. Effects of the invention

[0010] The pigment dispersion composition for a black matrix according to the present invention comprises carbon black, a pigment dispersant containing a basic group, a pigment dispersion aid containing an acidic group, an alkali-soluble resin, an ion capture agent, and a solvent, wherein the carbon black is acidic carbon black, and the ion capture agent is an inorganic compound having a median diameter of 0.1 to 10 μm, and is 1 to 15 parts by mass per 100 parts by mass of the carbon black. Since the pigment dispersion composition for a black matrix according to the present invention can capture substances containing ions such as potassium ions incorporated during the preparation of acidic carbon black by the ion capture agent, a resist composition for a black matrix with excellent optical concentration and fine line adhesion is obtained without requiring operations such as washing of the acidic carbon black. Specific details for implementing the invention

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

[0012] Carbon Black

[0013] The above carbon black is an acidic carbon black having acidic groups such as carboxyl groups. As the above acidic carbon black, a known acidic carbon black used in pigment dispersion compositions for black matrices may be used. For example, from the perspective of improving developability and fine line adhesion, it is preferable that the pH be 5.0 or lower, more preferable that the pH be 1.0 or higher and 3.5 or lower, and it is also preferable that the DBP oil absorption amount be 80 ml / 100 g or lower, more preferable that the DBP oil absorption amount be 70 ml / 100 g or lower, and it is also preferable that the particle size be 20 to 60 nm. In addition, the above 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 distilled water (pH 7.0) excluding carbon dioxide and mixing with a magnetic stirrer (German industrial product standard DIN ISO 787 / 9). In addition, DBP oil absorption is a value measured in accordance with JIS K 6217-4, which indirectly quantifies the structure of carbon black by measuring the pore volume. Furthermore, the above particle size refers to the average primary particle size measured or calculated by microscopic observation. For commercially available products, catalog values ​​are referenced for these values. The above carbon black may be used alone or in combination of two or more types.

[0014] Specifically, the above acidic carbon blacks include Raven 1080 (pH 2.4, average primary particle size 28 nm, DBP oil absorption 60 ml / 100 g) and Raven 1100 U (pH 2.9, average primary particle size 32 nm, DBP oil absorption 72 ml / 100 g) manufactured by Columbia Chemicals, NEROX 305 (pH 2.8, average primary particle size 28 nm, DBP oil absorption 58 ml / 100 g), and NEROX 3500 (pH 3.0, average primary particle size 31 nm, DBP oil absorption 43 ml / 100 g) manufactured by Cabot Corporation, TPK 1104R (pH 3.0, average primary particle size approx. 30 nm, DBP oil absorption 38 ml / 100 g) manufactured by Mitsubishi Chemical Corporation, and MA14 (pH 2.8, average Examples include primary particle size 40 nm, DBP oil absorption 73 ml / 100 g), MA220 (pH 2.9, average primary particle size 55 nm, DBP oil absorption 93 ml / 100 g), etc.

[0015] The carbon black is preferably 3 mass% or more in terms of increasing light-blocking properties when a black matrix film is formed in the pigment dispersion composition for the black matrix, more preferably 10 mass% or more, and is preferably 70 mass% or less in terms of pigment dispersion, more preferably 50 mass% or less.

[0016] <Basic group-containing pigment dispersant>

[0017] The above-mentioned basic group-containing pigment dispersant only needs to be capable of dispersing the carbon black, and known basic group-containing pigment dispersants used in pigment dispersion compositions for black matrices may be used. 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, basic group-containing carbodiimide-based pigment dispersants, etc. As for the basic group, primary, secondary, or tertiary amino groups are particularly preferred from the view that they have excellent dispersibility. The above-mentioned basic group-containing pigment dispersant may be used alone or in combination of two or more types.

[0018] The above-mentioned basic group-containing pigment dispersant is preferably a polymeric type basic group-containing pigment dispersant in that good pigment dispersibility is obtained. Examples of the above-mentioned polymeric type basic group-containing pigment dispersant include basic group-containing urethane-based polymer pigment dispersants, basic group-containing polyester-based polymer pigment dispersants, and basic group-containing acrylic-based polymer pigment dispersants. Among these, basic group-containing urethane-based polymer pigment dispersants and basic group-containing acrylic-based polymer pigment dispersants are preferred. The above-mentioned basic group-containing urethane-based polymer pigment dispersant is more preferably a basic group-containing urethane-based polymer pigment dispersant having at least one selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains.

[0019] The above-mentioned pigment dispersant containing basic groups is preferably 5 to 50 mgKOH / g and more preferably 5 to 35 mgKOH / g in terms of being able to lower the viscosity of the pigment dispersion composition for the black matrix and to increase the concentration of carbon black in the coating film. In addition, the amine number represents the total amount of free base and base, expressed as the number of mg of an equivalent amount of potassium hydroxide relative to the hydrochloric acid required to neutralize 1 g of the sample.

[0020] The above basic group-containing pigment dispersant is preferably 1 to 100 parts by mass per 100 parts by mass of carbon black, and more preferably 2 to 50 parts by mass.

[0021] <Dispersion aid for acid-containing pigments>

[0022] The above acid group-containing pigment dispersion aid is used for the purpose of further improving the dispersibility of pigments, and examples include compounds in which acid groups such as carboxyl groups or sulfonic acid groups are introduced to pigments such as lactam black, perylene-based compounds, diketopyrrolopyrrole-based compounds, azonapthol-based compounds, dioxazine-based compounds, quinacridone-based compounds, phthalocyanine-based compounds and their metal complexes, anthraquinone, naphthalene, acridone, or triazine (pigment derivatives having acid groups), or compounds obtained by neutralizing these with organic amines. Among the above pigment derivatives having acid groups, phthalocyanine-based (having a phthalocyanine backbone) pigment derivatives having sulfonic acid groups are preferred from the perspective of good dispersibility of carbon black. The above acid group-containing pigment dispersion aid may be used alone or in combination of two or more types.

[0023] The above acidic group-containing pigment dispersion aid is preferably 0.1 to 20 parts by mass per 100 parts by mass of carbon black, and more preferably 1 to 10 parts by mass.

[0024] Alkali-soluble resin

[0025] The above alkali-soluble resin is not particularly limited as long as it can be dissolved in an alkaline developer, but a resin containing one or more types of anionic groups such as carboxyl groups, sulfonic acid groups, and phosphonic acid groups (-P(=O)(OH2)) is preferred. The above alkali-soluble resin may be used alone or in combination of two or more types.

[0026] The acid value of the above alkali-soluble resin is preferably 10 mgKOH / g or more and 300 mgKOH / g or less in terms of alkali development properties, and more preferably 20 mgKOH / g or more and 200 mgKOH / g or less.

[0027] The weight average molecular weight of the alkali-soluble resin is preferably 3,000 or more and more preferably 4,000 or more from the perspective of resist film formation. The weight average molecular weight of the alkali-soluble resin is preferably 100,000 or less and more preferably 50,000 or less from the perspective of increasing solubility in an alkaline developer.

[0028] The above weight-average molecular weight can be measured by gel permeation chromatography (GPC). As an example, the weight-average molecular weight in polystyrene equivalent can be obtained by performing chromatography using Water2690 (manufactured by Waters, Inc.) as the GPC device, PL gel, 5 μm, MIXED-D (manufactured by Polymer Laboratories, Inc.) as the column, tetrahydrofuran as the developing solvent, column temperature 25°C, flow rate 1 milliliter / min, RI detector, sample injection concentration 10 milligrams / milliliter, and injection volume 100 microliters.

[0029] Examples of the above alkali-soluble resins include alkali-soluble polyimide resin, alkali-soluble polyimide precursor, alkali-soluble polybenzoxazole resin, alkali-soluble polybenzoxazole precursor, alkali-soluble cardo resin, alkali-soluble epoxy (meth)acrylate resin, alkali-soluble polysiloxane resin, alkali-soluble novolak resin, alkali-soluble (meth)acrylate resin, alkali-soluble polyurethane resin, alkali-soluble polyester resin, etc. Among these, alkali-soluble cardo resin and alkali-soluble epoxy (meth)acrylate resin are preferred from the perspective of the heat resistance of the coating film.

[0030] The above alkali-soluble cardo resin refers to an alkali-soluble resin having a cardo skeleton, and a cardo skeleton refers to a framework 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), Ogzol CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, and CR-TR6 (all manufactured by Osaka Gas Chemical Co., Ltd.).

[0031] The above alkali-soluble epoxy (meth)acrylate resin refers to an acid-modified epoxy resin obtained by introducing an ethylenically unsaturated group by adding a ring-opening ring of a carboxyl group of an ethylenically unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, and introducing a carboxyl group by adding a polybasic carboxylic acid (or its anhydride) to at least some of the hydroxyl groups formed by the ring-opening of the epoxy group, wherein the resin does not have the above cardo skeleton and corresponds to the above alkali-soluble resin. Examples of preferred epoxy resins that serve as the matrix raw material for the above alkali-soluble epoxy (meth)acrylate resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having a biphenyl structure, phenol novolak type epoxy resin, and cresol novolak type epoxy resin. Examples of preferred epoxy acids used to modify the epoxy resin include acrylic acid and methacrylic acid. Examples of polybasic carboxylic acids (or their anhydrides) preferably include maleic anhydride, succinic anhydride, and tetrahydrophthalic anhydride. Among these, an alkali-soluble epoxy (meth)acrylate resin having a biphenyl backbone is preferred for improving fine wire adhesion. Specific examples of the alkali-soluble epoxy (meth)acrylate resin include ZAR-1494H, ZAR-2001H, ZFR-1491H, ZCR-1797H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.). Additionally, a preferred specific example is an alkali-soluble epoxy (meth)acrylate resin having a partial structure represented by any one of the following structural formulas.

[0032] [Chemical Formula 1]

[0033]

[0034] The alkali-soluble resin is preferably 1 to 70 parts by mass and more preferably 2 to 40 parts by mass per 100 parts by mass of the carbon black.

[0035] Ion Capture Agent

[0036] The above ion capture agent is an inorganic compound having a median diameter of 0.1 to 10 μm. The above ion capture agent only needs to be capable of capturing at least one of a cation and an anion, and examples include a cation capture agent, an anion capture agent, and a both ion capture agent having ion capture 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, an inorganic compound containing one or more metal atoms selected from the group consisting of bismuth, zirconium, magnesium, and aluminum is preferred. The above ion capture agent may be used alone or in combination of two or more types. In addition, the above median diameter can be measured using a laser diffraction / scattering particle diameter distribution measuring device, and in the case of commercially available products, the catalog value is referenced.

[0037] The above ion capture agent is 1 to 15 parts by mass per 100 parts by mass of the carbon black. The above ion capture agent is preferably 2 parts by mass or more and 3 parts by mass or more with respect to improving fine wire adhesion with respect to 100 parts by mass of the carbon black, and preferably 10 parts by mass or less and 8 parts by mass or less with respect to improving optical concentration.

[0038] Solvent

[0039] The above solvent may be a known solvent used in pigment dispersion compositions for black matrix. 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, a nitrogen-containing solvent, etc., in order to stably disperse the pigment and sufficiently dissolve the basic group-containing pigment dispersant or the alkali-soluble resin. The above solvent may be used alone or in combination of two or more types.

[0040] Examples of the above-mentioned ester-based solvents include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl ethoxypropionate, ethyl ethoxyacetate, hydroxyacetate ester, n-amyl formic acid, etc. Examples of the above ether-based 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 above ether ester-based solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Examples of the above ketone-based solvents include methylisobutylketone, cyclohexanone, 2-heptanone, δ-butyrolactone, etc. Examples of the above aromatic hydrocarbon-based solvents include toluene, xylene, alkylnaphthalene, etc. Examples of the above nitrogen-containing solvents include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0041] The proportion of the above solvent in the pigment dispersion composition for the black matrix is ​​preferably 40 mass% or more from the perspective of processability, more preferably 50 mass% or more, and from the perspective of dispersion stability, it is preferably 90 mass% or less, more preferably 80 mass% or less.

[0042] Epoxy Resin

[0043] In the pigment dispersion composition for the black matrix above, an epoxy resin may be used to improve fine line adhesion. In particular, for high resistance applications, it is desirable to incorporate an epoxy resin. The above epoxy resin is a polyfunctional epoxy resin having two or more epoxy groups. Examples of the above epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, trisphenolmethane type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain type epoxy resin, glycidyl ester type epoxy resin, glycidyl ether compounds of condensed products of phenol compounds (phenol, cresol, alkylphenol, catechol, bisphenol F, bisphenol A, bisphenol S, etc.) and aldehyde compounds (formaldehyde, salicylaldehyde, etc.), glycidyl ether compounds of difunctional phenols, glycidyl ether compounds of difunctional alcohols, glycidyl ether compounds of polyphenols with three or more functions, and hydrogenated derivatives or halides thereof. The above epoxy resin may be a polyfunctional epoxy resin having a cyclic or aromatic ring, or a polyfunctional epoxy resin having a dicyclopentadiene backbone which is a cyclic ring; among these, a polyfunctional epoxy resin having an aromatic ring is preferred from the perspective of improving fine wire adhesion.Specific examples of the above epoxy resins include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 (all manufactured by Kyoei Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L, Denacol EX-321L (all manufactured by Nagase Chemtex Co., Ltd.), GAN, GOT, NC3000, NC6000, EPPN502H, EPPN-503 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, and Epicoat. Examples include 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resin Co.), Epichron EXA-9583, Epichron N695, HP7200, HP4032 (all manufactured by Dainippon Inky Chemical Co.), VG3101 (manufactured by Mitsui Chemical Co.), Tepic S, Tepic G, Tepic P (all manufactured by Nissan Chemical Co.), and Photot YH-434L (manufactured by Toto Kasei Co.). Additionally, it is preferable for the above epoxy resins not to have an indan structure or a biphenyl structure in terms of reactivity and the like.

[0044] As the above epoxy resin, for example, a polyfunctional epoxy resin having an aromatic ring represented by the following formulas 1 to 7 can be preferably cited.

[0045] [Chemical Formula 2]

[0046] (Equation 1)

[0047]

[0048] (m is 0 to 20)

[0049] [Chemical Formula 3]

[0050] (Equation 2)

[0051]

[0052] [Chemical Formula 4]

[0053] (Equation 3)

[0054]

[0055] (n is 1 to 20)

[0056] [Chemical Formula 5]

[0057] (Equation 4)

[0058]

[0059] (R1~R6 are each independently saturated hydrocarbon groups with 1 to 6 carbon atoms, and n is 1 to 20)

[0060] [Chemical Formula 6]

[0061] (Equation 5)

[0062]

[0063] (n is 1 to 20)

[0064] [Chemical Formula 7]

[0065] (Equation 6)

[0066]

[0067] (R 1 ~ R 2 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, and n is 1 to 20.

[0068] [Chemical Formula 8]

[0069] (Equation 7)

[0070]

[0071] (n is 1 to 20)

[0072] The above 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, with respect to 100 parts by mass of carbon black included in the pigment dispersion composition for the black matrix or the resist composition for the black matrix described later, in terms of resistance value as a black matrix, and 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 in terms of blackness according to pigment concentration.

[0073] The pigment dispersion composition for the black matrix above may further include additives such as a leveling agent, a resin other than the epoxy resin and the alkali-soluble resin, an antioxidant, and an antifoaming agent as needed. However, from the perspective of odor properties, it is preferable not to include thiol compounds (e.g., thiol compounds with a molecular weight of 1000 or less).

[0074] In the pigment dispersion composition for the black matrix above, the ratio of the total of the carbon black, the basic group-containing pigment dispersant, the acid group-containing pigment dispersion aid, the alkali-soluble resin, the ion capture agent, and the solvent is preferably 75 mass% or more, more preferably 85 mass% or more, and even more preferably 95 mass% or more. Additionally, when the epoxy resin is incorporated, the ratio of the total of the carbon black, the basic group-containing pigment dispersant, the acid group-containing pigment dispersion aid, the alkali-soluble resin, the ion capture agent, the solvent, and the epoxy resin in the pigment dispersion composition for the black matrix is ​​preferably 75 mass% or more, more preferably 85 mass% or more, and even more preferably 95 mass% or more.

[0075] The pigment dispersion composition for the black matrix described above may be prepared by dispersing each of the above components using a roll mill, kneader, high-speed stirrer, bead mill, ball mill, sand mill, ultrasonic disperser, high-pressure dispersion device, etc. In particular, it is preferable to disperse at least the carbon black in the presence of the ion capture agent to efficiently capture substances containing ions included in the carbon black and to improve optical concentration and fine wire adhesion.

[0076] <Resist composition for black matrix>

[0077] The resist composition for a black matrix of the present invention comprises a pigment dispersion composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator. Additionally, the proportion of carbon black is preferably 30 mass% or more and 80 mass% or less of the solid content of the resist composition for a black matrix.

[0078] Photopolymerizable Compounds

[0079] The above photopolymerizable compound may be a known photopolymerizable compound used in a resist composition for a black matrix, and examples include monomers and oligomers having photopolymerizable unsaturated bonds. The above photopolymerizable compound may be used alone or in combination of two or more types.

[0080] As a monomer having one photopolymerizable unsaturated bond, examples include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; aralkyl methacrylates or acrylates such as benzyl methacrylate, benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate, butoxyethyl acrylate; aminoalkyl methacrylates or acrylates such as NN-dimethylaminoethyl methacrylate, NN-dimethylaminoethyl acrylate; and methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. Examples include 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.

[0081] As monomers having two or more photopolymerizable unsaturated bonds, examples 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 pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, Examples include glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc.

[0082] Examples of oligomers having photopolymerizable unsaturated bonds include those obtained by appropriately polymerizing the above monomer.

[0083] The above photopolymerizable compound is preferably 2 to 20 mass% of the solid content of the resist composition for the black matrix, and more preferably 4 to 15 mass%.

[0084] The above photopolymerization initiator may be a known photopolymerization initiator used in a resist composition for a black matrix, for example, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxantone, 2-chlorothioxantone, 1-hydroxycyclohexylphenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, Examples include 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiators, oxime ester-based photopolymerization initiators, etc. The above photopolymerization initiators may be used alone or in combination of two or more types.

[0085] The above photopolymerization initiator is preferably 0.1 to 15 mass% of the solid content of the resist composition for the black matrix, and more preferably 1 to 10 mass%.

[0086] The above-described resist composition for a black matrix may further add the alkali-soluble resin in terms of developability with an alkaline developer. Additionally, the total amount of the alkali-soluble resin is preferably 10 mass% or more and 50 mass% or less of the solid content of the above-described resist composition for a black matrix. Furthermore, the above-described solvent may further add to the above-described resist composition for a black matrix in terms of improving paintability. The total proportion of the solvent is preferably 50 mass% or more of the above-described resist composition for a black matrix, and more preferably 70 mass% or more.

[0087] Additives such as leveling agents, antioxidants, and defoaming agents may be further added to the above-mentioned resist composition for the black matrix as needed.

[0088] The above-mentioned resist composition for the black matrix can be prepared by mixing each component, such as the pigment dispersion composition for the black matrix, the photopolymerizable compound, and the photopolymerization initiator, by stirring using a stirring device or the like.

[0089] Black Resist

[0090] The black resist film of the present invention is obtained using the resist composition for the black matrix above. The black resist film has a surface resistance value of 5.0 × 10⁻⁶ 9 It is desirable that it be Ω / □ or greater, and 1.0×10 10 It is more desirable that it be Ω / □ or greater, and 1.0×10 11 It is more desirable that it be Ω / □ or higher. In particular, for high-resistance applications, the surface resistance value is 1.0×10 12 It is desirable that it be Ω / □ or greater, and 1.0×10 13 It is more desirable that it be greater than Ω / □.

[0091] [Example]

[0092] The present invention will be explained below by means of examples, etc., but the present invention is not limited to these.

[0093] <Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-6>

[0094] <Preparation of Pigment Dispersion Composition for Black Matrix>

[0095] Various raw materials shown in Tables 1 and 2 were mixed to form the formulation composition (mass%) shown in Tables 1 and 2, then tenderized using a bead mill to prepare the pigment dispersion composition for the black matrix of each example and comparative example.

[0096]

[0097]

[0098] 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);

[0099] TPK1104R is acidic carbon black (oil absorption capacity: 38ml / 100g, pH 3.0, average primary particle size approx. 30nm, manufactured by Cabot);

[0100] IXEPLAS B1 is a cation scavenger (zirconium / bismuth-based, median diameter 0.4㎛, manufactured by Toa Synthetic Fiber);

[0101] IXE-100 is a cation capture agent (zirconium-based, median diameter 1 µm, manufactured by Toa Synthetic Fiber);

[0102] IXE-500 is an anion capture agent (bismuth-based, median diameter 1.5㎛, manufactured by Toa Synthetic Fiber);

[0103] IXE-550 is an anion scavenger (bismuth-based, median diameter 1.5㎛, manufactured by Toa Synthetic Fiber);

[0104] IXE-600 is a cation scavenger (antimony / bismuth-based, median diameter 1 µm, manufactured by Toa Synthetic Fiber);

[0105] IXE-700F is an anion capture agent (aluminum / magnesium-based, median diameter 1.5㎛, manufactured by Toa Synthetic Fiber);

[0106] IXE-770F is an anion capture agent (aluminum / magnesium-based, median diameter 6㎛, manufactured by Toa Synthetic Fiber);

[0107] IXE-6136 is a cation scavenger (zirconium / bismuth-based, median diameter 2.1 µm, manufactured by Toa Synthetic Fiber);

[0108] DB167 is an amino group-containing polyurethane-based polymer dispersant having a polyester chain (manufactured by Big Chem, amine value of solids 25 mgKOH / g, solids 52 mass%);

[0109] SS5000S is a phthalocyanine-based pigment derivative having a sulfonic acid group (manufactured by Lubrizol Inc.);

[0110] BYK2100 is a phthalocyanine-based pigment derivative having a sulfonic acid group (manufactured by Bic Chem);

[0111] ZCR-1569H is an alkali-soluble epoxy (meth)acrylate resin having a biphenyl backbone (solid content 69%, manufactured by Nippon Kayaku Co.);

[0112] EPPN-503 is a trihydroxyphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co.);

[0113] PGMEA represents propylene glycol monomethyl ether acetate.

[0114] <Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-6>

[0115] Preparation of a Resist Composition for a Black Matrix

[0116] Various raw materials shown in Tables 3 and 4 were mixed using a high-speed stirrer to obtain the formulation composition (mass%) shown in Tables 3 and 4, and then filtered through a filter with a hole diameter of 0.5 μm to prepare the resist composition for the black matrix of each example and comparative example.

[0117] In addition, each item was evaluated according to the following evaluation method using the resist composition for the black matrix obtained above. The results are shown in Tables 3 and 4.

[0118] <Evaluation of Optical Density (OD Value) of Resist Pattern>

[0119] Each of the above resist compositions for the black matrix was applied onto a glass substrate (Corning 1737) using a spin coater to a film thickness of 1 μm, pre-baked at 100°C for 3 minutes, exposed to a high-pressure mercury lamp, and post-baked at 230°C for 30 minutes to obtain a resist film formed only on the front side (beta side). The optical density (OD value) of each obtained front side resist film was measured using a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth Corporation). An optical density (OD value) of 4.0 or higher was set as the acceptance criterion.

[0120] <Evaluation of fine wire adhesion (A) and (B) of black resist film>

[0121] Each of the above resist compositions for the black matrix was applied onto a glass substrate (EAGL XG) using a spin coater to a film thickness of 1 μm and pre-baked at 100°C for 3 minutes. Subsequently, a photomask having a line pattern with a 1 μm spacing for line widths of 1 μm to 20 μm was used, and exposure was performed using a high-pressure mercury lamp at a UV integrated light intensity of 100 mJ / cm². After that, development was initiated at the time when the development pattern began to appear (break point) in a shower development pressure of 1 kgf / cm² in a 0.05% aqueous potassium hydroxide solution at 23°C. For the evaluation of fine line adhesion (A), development was terminated at a time 1.3 times the break point, and for the evaluation of fine line adhesion (B), development was terminated at a time 30 seconds after the break point. After that, spray rinsing was performed at a pressure of 1 kgf / cm². The size (μm) of the minimum line pattern remaining on the glass substrate was evaluated. The evaluation of fine line adhesion (A) was based on a break point of 50±25 seconds and a minimum line pattern size of 10㎛ or less as the acceptance criteria. Additionally, the evaluation of fine line adhesion (B) was based on a break point of 20±10 seconds and a minimum line pattern size of 8㎛ or less as the acceptance criteria.

[0122] Measurement of Surface Resistance Value of Black Resist Film

[0123] Each of the above black matrix resist compositions was applied to a glass substrate (EAGL XG) with a spin coater to a film thickness of 1 μm, pre-baked at 100°C for 3 minutes, exposed to light (UV integrated light intensity) of 80 mJ / ㎠ with a high-pressure mercury lamp, and further post-baked at 230°C for 60 minutes to produce a black resist pattern (black matrix) formed only on the front surface. The surface resistance value of each produced black resist pattern was measured using a main unit: microammeter R8340, and an optional shield box R12702A (both manufactured by Advance).

[0124]

[0125]

[0126] In Tables 3 and 4, DPHA is dipentaerythritol hexaacrylate;

[0127] OXE02 is the oxime ester-based photopolymerization initiator "IRGACURE OXE02" (manufactured by BASF Japan);

[0128] WR-301 is an alkali-soluble cardosin "ADEKA ARKLS WR-301" (solids 44%, manufactured by ADEKA);

[0129] PGMEA represents propylene glycol monomethyl ether acetate.

Claims

Claim 1 A pigment dispersion composition for a black matrix comprising carbon black, a pigment dispersant containing a basic group, a pigment dispersion aid containing an acid group, an alkali-soluble resin, an ion capture agent, and a solvent, wherein the carbon black is acidic carbon black, the ion capture agent is an inorganic compound having a median diameter of 0.1 to 10 μm, and is characterized in that it is 1 to 15 parts by mass per 100 parts by mass of the carbon black. Claim 2 A pigment dispersion composition for a black matrix according to claim 1, wherein the carbon black has a DBP oil absorption capacity of 80 ml / 100 g or less. Claim 3 A pigment dispersion composition for a black matrix according to claim 1 or claim 2, wherein the basic group-containing pigment dispersant has an amine value of 5 to 50 mgKOH / g. Claim 4 A pigment dispersion composition for a black matrix according to claim 1 or claim 2, wherein the alkali-soluble resin is an alkali-soluble cardo resin and / or an alkali-soluble epoxy (meth)acrylate resin. Claim 5 A resist composition for a black matrix characterized by containing a pigment dispersion composition for a black matrix as described in claim 1 or claim 2, a photopolymerizable compound, and a photopolymerization initiator. Claim 6 A black resist film characterized by being obtained using the resist composition for a black matrix described in claim 5. Claim 7 A method for preparing a resist composition for a black matrix as described in claim 1 or claim 2, characterized by dispersing at least the carbon black in the presence of the ion capture agent.

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