Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix

Abstract

The present invention provides a pigment dispersion composition for a black matrix, which can form a black matrix with excellent adhesion to a substrate. The pigment dispersion composition for a black matrix comprises a black colorant, a sulfonate of copper phthalocyanine and an amine compound, wherein the amine compound is at least one selected from the following compounds (A) to (D): (A) an amine compound having a pyridine skeleton; (B) an amine compound having an aniline skeleton; (C) an amine compound having a carbazole skeleton; (D) an amine compound having a straight-chain alkyl group with 8 or more carbon atoms and a total carbon atom number of 20 or less.

Description

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS]

[0002] This application claims the priority of invention patent application "Japanese Patent Application No. 2020-195210" filed with the Japan Patent Office on November 25, 2020, and all contents disclosed in that application are hereby incorporated as a whole into the description of this application. Technical Field

[0003] The present invention relates to a pigment dispersion composition for a black matrix, a resist composition for a black matrix, and a black matrix. Background Art

[0004] In image display devices using liquid crystal, plasma, etc., a light-shielding film (black matrix, also called "black matrix") is provided in the gaps between colored patterns in the screen display area and at the edges of the peripheral parts of the display area, and also on the external light side of the TFT in a liquid crystal display using TFT.

[0005] Furthermore, in liquid crystal display devices, it is mainly used to prevent leakage from backlight from entering the screen, and in plasma display devices, it is mainly used to prevent bleeding caused by the confusion of different color lights from entering the screen, thereby helping to improve display characteristics (contrast and color purity).

[0006] For example, a color filter for converting white light from the backlight source of a liquid crystal display device into colored light is usually manufactured by forming pixels of different hues of red, green, and blue in a striped or mosaic pattern on the surface of a transparent substrate such as glass or plastic sheet formed with a black matrix.

[0007] In addition, even in a touch panel that aligns an image display device with a position input device, a color filter (color filter) formed with a black matrix as a light-shielding film is similarly used, and has been generally formed on the side opposite to the sensor substrate via a glass cover (protective sheet). However, as the demand for lightweight touch panels increases, in order to achieve further lightweighting, the development of a technology for simultaneously forming a light-shielding film and a touch sensor on the same side as the glass cover is promoted.

[0008] As a method for forming such a black matrix, for example, a photolithography method (pigment method) using a pigment is used.

[0009] In this pigment method, a sulfonic acid derivative of copper phthalocyanine is sometimes used to improve the dispersibility of the pigment.

[0010] For example, Patent Document 1 discloses a pigment dispersion composition for a black matrix, characterized in that carbon black having an oil absorption of 10 to 150 ml / 100 g and a pH value greater than 9, a carbamate polymer pigment dispersant containing a basic group and a polyester chain, and a phthalocyanine derivative having a sulfonic acid group as an acid group-containing pigment derivative are dispersed in a solvent.

[0011] The black matrix needs to have close adhesion (adhesion) with respect to the substrate.

[0012] However, in Patent Document 1, the adhesion is not sufficiently studied, and there is still room for further improvement.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: International Publication No. 2008 / 066100 Summary of the invention

[0016] Technical problem to be solved by the invention

[0017] Therefore, an object of the present invention is to provide a pigment dispersion composition for a black matrix capable of forming a black matrix having excellent adhesion to a substrate.

[0018] Means used to solve problems

[0019] The present inventors have found that a black matrix pigment dispersion composition containing a black colorant and a sulfonate of copper phthalocyanine further containing a specific amine compound can provide a black matrix pigment dispersion composition capable of forming a black matrix having excellent adhesion to a substrate, thereby completing the present invention.

[0020] That is, the present invention relates to a pigment dispersion composition for a black matrix, which comprises a black colorant, a sulfonate of copper phthalocyanine and an amine compound, wherein the amine compound is at least one selected from the following compounds (A) to (D):

[0021] (A) an amine compound having a pyridine skeleton;

[0022] (B) an amine compound having an aniline skeleton;

[0023] (C) an amine compound having a carbazole skeleton;

[0024] (D) An amine compound having a linear alkyl group having 8 or more carbon atoms and a total of 20 or less carbon atoms.

[0025] The amine compound is preferably at least one selected from pyridine, p-aminoazobenzene, 9,9-Bis(4-Aminophenyl)fluorene (9,9-Bis(4-aminophenyl)fluorene), 3-amino-N-ethylcarbazole, dodecylamine, and 1-amino-3-undecyoxypropane.

[0026] In addition, the sulfonated copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in the molecule.

[0027] In addition, it is preferred that the black colorant contains carbon black.

[0028] In addition, it is preferred that the carbon black is acidic carbon black.

[0029] Furthermore, the present invention also relates to a resist composition for a black matrix obtained using the pigment dispersion composition for a black matrix.

[0030] In addition, the present invention also relates to a black matrix formed using the resist composition for a black matrix.

[0031] Effects of the Invention

[0032] According to the present invention, a pigment dispersion composition for a black matrix capable of forming a black matrix having excellent adhesion to a substrate can be provided. DETAILED DESCRIPTION

[0033] <Pigment dispersion composition for black matrix>

[0034] The pigment dispersion composition for black matrix of the present invention comprises a black colorant, a sulfonate of copper phthalocyanine and an amine compound, and the amine compound is at least one selected from the following compounds (A) to (D):

[0035] (A) an amine compound having a pyridine skeleton;

[0036] (B) an amine compound having an aniline skeleton;

[0037] (C) an amine compound having a carbazole skeleton;

[0038] (D) An amine compound having a linear alkyl group having 8 or more carbon atoms and a total of 20 or less carbon atoms.

[0039] (Black colorant)

[0040] The pigment dispersion composition for a black matrix of the present invention contains a black colorant.

[0041] As the black colorant, carbon black is preferably contained, and from the viewpoint of appropriately providing a surface resistance value, the carbon black is more preferably acidic carbon black.

[0042] The carbon black preferably has an average primary particle size of 20 to 60 nm, and more preferably is neutral carbon black having an average primary particle size of 20 to 60 nm and / or acidic carbon black having an average primary particle size of 20 to 60 nm.

[0043] When the primary particle diameter of the black colorant is less than 20 nm or greater than 60 nm, the black colorant may not have sufficient light-shielding properties and may also have poor storage stability.

[0044] The average primary particle size is a value of an arithmetic mean particle size obtained by electron microscope observation.

[0045] From the viewpoint of providing an appropriate surface resistance value, the black colorant preferably contains only acidic carbon black.

[0046] On the other hand, when neutral carbon black and acidic carbon black are used in combination, the neutral carbon black is preferably 85% by mass or less, more preferably 75% by mass or less, based on the total mass of the neutral carbon black and the acidic carbon black.

[0047] When the content of neutral carbon black in carbon black exceeds 85 mass %, the sealing strength may decrease.

[0048] The acidic carbon black and neutral carbon black are described below.

[0049] Carbon black can be roughly divided into acidic carbon black and neutral carbon black based on the surface structure. Acidic carbon black refers to a carbonaceous material that is originally oxidized or artificially oxidized, and exhibits acidity when mixed with distilled water and boiled. On the other hand, neutral carbon black is known to exhibit a neutral or higher pH when mixed with distilled water and boiled.

[0050] As the neutral carbon black, the pH is preferably in the range of 8.0 to 10.0. Specifically, examples include: PRINTEX 25 (average primary particle size of 56 nm, pH 9.5), PRINTEX 35 (average primary particle size of 31 nm, pH 9.5), and PRINTEX 65 (average primary particle size of 21 nm, pH 9.5) manufactured by Orion Engineered Carbons; MA#20 (average primary particle size of 40 nm, pH 8.0), MA#40 (average primary particle size of 40 nm, pH 8.0), and MA#30 (average primary particle size of 30 nm, pH 8.0) manufactured by Mitsubishi Chemical Corporation.

[0051] The acidic carbon black preferably has a pH in the range of 2.0 to 4.0, and specific examples thereof include Raven 10 manufactured by Columbia Chemical Company. 80 (average primary particle size is 28nm, pH2.4), Raven 1100 (average primary particle size is 32nm, pH2.9); MA-8 (average primary particle size is 24nm, pH3.0), MA-100 (average primary particle size is 22nm, pH3.5) manufactured by Mitsubishi Chemical Corporation; SpecialBlack250 (average primary particle size is 56nm, pH3.0), SpecialBlack350 (average primary particle size is 31nm, pH3.0), SpecialBlack550 (average primary particle size is 25nm, pH4.0), NEROX 305 (average primary particle size is about 28nm, pH about 2.8) manufactured by Orion Engineering Carbon Co., Ltd.

[0052] As the black colorant, SpecialBlack250 or NEROX305 is preferred from the viewpoint of providing appropriate pigment dispersibility and surface resistance value.

[0053] Alternatively, the pH can be measured by adding 1 g of carbon black to 20 ml of distilled water (pH 7.0) from which carbon dioxide has been removed, mixing with a magnetic stirrer to prepare an aqueous suspension, and measuring the pH at 25° C. using a glass electrode (German Industrial Product Standard DIN ISO 787 / 9).

[0054] The content of the black colorant is preferably 3 to 70% by mass, more preferably 10 to 50% by mass, based on the mass fraction of the total solid content of the pigment dispersion composition for a black matrix of the present invention.

[0055] When the content of the black colorant is less than 3% by mass, the light shielding property when forming a black matrix may be reduced. When the content exceeds 70% by mass, the pigment dispersion may be difficult.

[0056] (Sulfonate of copper phthalocyanine)

[0057] The pigment dispersion composition for black matrices of the present invention contains a sulfonated copper phthalocyanine.

[0058] The sulfonated copper phthalocyanine has a basic skeleton portion adsorbed on the pigment surface during the process of micronizing or dispersing the black colorant, and has the effect of improving the micronization of the black colorant during dispersion or the dispersion stability after dispersion by increasing the affinity between the sulfonic acid group and the organic solvent or pigment dispersant.

[0059] The copper phthalocyanine in the copper phthalocyanine sulfonate is not particularly limited as long as it has a copper phthalocyanine skeleton. For example, the copper phthalocyanine skeleton may have a known substituent such as an alkyl group or a halogen atom. However, from the viewpoint of easy introduction of a sulfonic acid group, a structure without a substituent is preferred.

[0060] The sulfonated copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in the molecule.

[0061] Thus, by having 0.5 to 3 sulfonic acid groups in the molecule, a black matrix composition capable of obtaining a coating film having excellent adhesion can be obtained.

[0062] The sulfonated copper phthalocyanine preferably has 0.7 to 2.5 sulfonic acid groups in the molecule, and more preferably has 0.9 to 2.0 sulfonic acid groups.

[0063] The number of sulfonic acid groups in the molecule can be determined from the ratio of sulfur atoms to copper atoms obtained by elemental analysis.

[0064] As the sulfonated copper phthalocyanine, commercially available products can be used, for example, Solsperse 12000 (both manufactured by The Lubrizol Corporation), the sodium-free product of VALIFAST BLUE 1605 (manufactured by Orient Chemical Industries Co., Ltd.), TURQUOISEEC-GN (manufactured by Huntsman Corporation), etc.

[0065] The content of the sulfonated copper phthalocyanine is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the black colorant.

[0066] (Amine compound)

[0067] The pigment dispersion composition for black matrices of the present invention contains an amine compound.

[0068] The amine compound is at least one selected from the following compounds (A) to (D):

[0069] (A) an amine compound having a pyridine skeleton;

[0070] (B) an amine compound having an aniline skeleton;

[0071] (C) an amine compound having a carbazole skeleton;

[0072] (D) An amine compound having a linear alkyl group having 8 or more carbon atoms and a total of 20 or less carbon atoms.

[0073] When such an amine compound is contained, the sensitization effect of the skeleton of each amine compound in (A) to (C) and the compatibility with the binder resin due to the appropriate number of carbon atoms of the alkyl group in (D) contribute to uniform coating film formation and even adhesion. In addition, when acidic carbon black is used as the black colorant, a black matrix with excellent surface resistance value can be formed by the sensitization effect of the skeleton of the amine compound.

[0074] However, the present invention is not limited to the above-mentioned mechanism.

[0075] As the amine compound having a pyridine skeleton, in addition to pyridine, there may be amine compounds having a pyridine skeleton having an alkyl group or an amino group, and the like.

[0076] Specifically, alkyl pyridines such as 2-methylpyridine (i.e., 2-picoline), 3-methylpyridine (i.e., 3-picoline), 4-methylpyridine (i.e., 4-picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, and 5-ethyl-2-methylpyridine; 3,4-cyclopentenolpyridine, 5,6,7,8-tetrahydroisoquinoline, isoquinoline, 5,6,7,8-tetrahydroquinoline, quinoline, 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 4-(3-phenylpropyl)pyridine, nicotinic acid, and isonicotinic acid can be mentioned. Among them, pyridine and 4-(3-phenylpropyl)pyridine are preferred.

[0077] Examples of the amine compound having an aniline skeleton include aniline, phenylenediamine, aminonaphthalene, diaminonaphthalene, 6-trimethylaniline (mesidine), methylaniline, metanilic acid (metanilic acid), aminophenol, diaminofluorene, p-aminoazobenzene, 2,4-diaminoazobenzene, 4,4-diaminoazobenzene, etc. Among them, compounds having two or more benzene rings are preferred, and p-aminoazobenzene and diaminofluorene are more preferred.

[0078] Examples of the amine compound having a carbazole skeleton include 3,6-diaminocarbazole and 3-amino-N-ethylcarbazole, of which 3-amino-N-ethylcarbazole is preferred.

[0079] The amine compound having a straight-chain alkyl group with 8 or more carbon atoms and a total carbon atom number of 20 or less may be a primary amine or a secondary amine, and specific examples thereof include octylamine, dioctylamine, nonylamine, dinonylamine, decylamine, didecylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine, nonadecanamine, eicosylamine, dimethyllaurylamine, and 1-amino-3-undecanoxypropane.

[0080] Among them, an amine compound having a straight-chain alkyl group having 10 or more carbon atoms and a total number of carbon atoms of 16 or less is preferred; specifically, dodecylamine and 1-amino-3-undecanyloxypropane are preferred.

[0081] The amine compound is preferably at least one selected from pyridine, p-aminoazobenzene, diaminefluorene, 3-amino-N-ethylcarbazole, dodecylamine, and 1-amino-3-undecyloxypropane.

[0082] Such an amine compound has a structure having a sensitizing effect or a structure having good compatibility with the binder resin, and therefore can be preferably used.

[0083] The amount of the amine compound is preferably 5 to 100 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass of the sulfonated copper phthalocyanine.

[0084] (Organic Solvent)

[0085] The pigment dispersion composition for a black matrix of the present invention preferably contains an organic solvent.

[0086] As the organic solvent, an organic solvent conventionally used in the field of liquid crystal black matrix resists can be preferably used.

[0087] Specifically, the organic solvent is a solvent at normal pressure (1.013×10 2 kPa) with a boiling point of 100 to 250° C. at 400 ° C., ester organic solvents, ether organic solvents, ether ester organic solvents, ketone organic solvents, ketone organic solvents, aromatic hydrocarbon organic solvents and nitrogen-containing organic solvents.

[0088] If a large amount of the organic solvent having a boiling point exceeding 250° C. is contained, when a coating film formed by applying the black matrix resist composition obtained from the black matrix pigment dispersion composition of the present invention is prebaked, the organic solvent is not sufficiently evaporated and remains in the dried coating film, and the heat resistance of the dried coating film may be reduced.

[0089] Furthermore, when a large amount of the organic solvent having a boiling point of less than 100° C. is contained, uniform coating without unevenness may become difficult, and a coating film having excellent surface smoothness may not be obtained.

[0090] Specifically, the organic solvent includes ether organic solvents such as 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, and diethylene glycol methyl ethyl ether; ether ester organic solvents such as 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; methyl isobutyl ketone, cyclohexanone, 2- Ketone organic solvents such as heptanone and δ-butyrolactone; ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-pentyl formate; alcohol solvents such as methanol, ethanol, isopropanol, butanol; nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These can be used alone or in combination of two or more.

[0091] Among the above-mentioned organic solvents, from the viewpoints of solubility, dispersibility, coating properties, etc., preferred are diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-pentyl formate, and more preferred are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0092] (Pigment dispersant)

[0093] The pigment dispersion composition for a black matrix of the present invention preferably contains a pigment dispersant.

[0094] As the above-mentioned pigment dispersant, which is a pigment dispersant containing a basic group, anionic surfactants, polyester pigment dispersants containing a basic group, acrylic pigment dispersants containing a basic group, polyurethane pigment dispersants containing a basic group, carbodiimide pigment dispersants containing a basic group, polymer pigment dispersants containing an acidic group, etc. can be used.

[0095] These basic group-containing pigment dispersants may be used alone or in combination of two or more. Among them, a basic group-containing polymer pigment dispersant is preferred from the viewpoint of obtaining good pigment dispersibility.

[0096] Specific examples of the above-mentioned basic group-containing polymer pigment dispersant include:

[0097] (1) a reaction product of an amino group and / or an imino group of a polyamine compound (e.g., poly(lower) alkyleneamines such as polyallylamine, polyvinylamine, and polyethylenepolyimine) and at least one selected from the group consisting of polyesters, polyamides, and polyesteramides having free carboxyl groups (Japanese Patent Application Laid-Open No. 2001-59906);

[0098] (2) Reaction products of low molecular weight amine compounds such as poly(lower) alkylene imine and methyliminodipropylamine with polyesters having free carboxyl groups (Japanese Patent Application Laid-Open No. 54-37082 and Japanese Patent Application Laid-Open No. 01-311177);

[0099] (3) A reaction product formed by reacting alcohols such as methoxypolyethylene glycol, polyesters having one hydroxyl group such as caprolactone polyester, compounds having 2 to 3 isocyanate-reactive functional groups, aliphatic or heterocyclic hydrocarbon compounds having isocyanate-reactive functional groups and tertiary amino groups, and isocyanate groups of polyisocyanate compounds in sequence (Japanese Patent Application Laid-Open No. 02-612);

[0100] (4) a compound obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group;

[0101] (5) a reaction product formed by adding a polyether chain to a low molecular weight amine compound;

[0102] (6) A reaction product formed by reacting a compound having an amino group with a compound having an isocyanate group (Japanese Patent Application Laid-Open No. 04-210220);

[0103] (7) A reaction product obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having one secondary amine group with a polyepoxide compound (Japanese Patent Application Laid-Open No. 09-87537);

[0104] (8) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound (Japanese Patent Application Laid-Open No. 09-194585);

[0105] (9) A copolymer of at least one methacrylate or acrylate selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octadecyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octadecyl acrylate, benzyl acrylate and the like, and at least one basic group-containing polymerizable monomer selected from acrylamide, methacrylamide, N-hydroxymethylamide, vinylimidazole, vinylpyridine, a monomer having an amino group and a polycaprolactone skeleton, and at least one other polymerizable monomer selected from styrene, a styrene derivative, and other polymerizable monomers (Japanese Patent Application Laid-Open No. 01-164429);

[0106] (10) Carbodiimide pigment dispersants containing basic groups (International Publication No. WO04 / 000950);

[0107] (11) A block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no functional group (see Japanese Patent Application Laid-Open No. 2005-55814);

[0108] (12) A pigment dispersant obtained by subjecting a polycarbonate compound to a polyallylamine through a Michael addition reaction (Japanese Patent Application Laid-Open No. 09-194585);

[0109] (13) Carbodiimide compounds each having at least one polybutadiene chain and a basic nitrogen-containing group (Japanese Patent Application Laid-Open No. 2006-257243);

[0110] (14) Carbodiimide compounds each having at least one side chain having an amide group and a basic nitrogen-containing group in the molecule (Japanese Patent Application Laid-Open No. 2006-176657);

[0111] (15) A polyurethane compound having a structural unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized by a quaternizing agent (Japanese Patent Application Laid-Open No. 2009-175613);

[0112] (16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in its molecule with an active hydrogen group of a compound having an active hydrogen group in its molecule and having a carbazole ring and / or an azobenzene skeleton, wherein the number of carbazole rings and azobenzene skeletons in the molecule of the compound is 15 to 85% relative to the total number of isocyanate groups derived from the isocyanate compound having an isocyanurate ring and urethane bonds and urea bonds generated by the reaction of the isocyanate groups and the active hydrogen groups (Japanese Patent Application No. 2009-220836);

[0113] (17) A graft copolymer in which a polyether or polyester side chain is introduced into an acrylate polymer having an amino group.

[0114] Among the above-mentioned polymer pigment dispersants containing basic groups, more preferred are polyurethane pigment-based polymer pigment dispersants containing basic groups, polyester-based polymer pigment dispersants containing basic groups, and acrylic-based polymer pigment dispersants containing basic groups, and further preferred are amino-containing polyurethane pigment-based polymer pigment dispersants, amino-containing polyester-based polymer pigment dispersants, and amino-containing acrylic-based polymer pigment dispersants. Among the above-mentioned polymer pigment dispersants containing basic groups, polymer pigment dispersants containing basic groups (amino groups) having at least one selected from polyester chains, polyether chains, and polycarbonate chains are particularly preferred.

[0115] The content of the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the black colorant.

[0116] (Binder resin)

[0117] The pigment dispersion composition for a black matrix of the present invention preferably contains a binder resin.

[0118] Examples of the binder resin include thermosetting resins, thermoplastic resins, photopolymerizable compounds, and alkali-soluble resins, and these may be used alone or in combination of two or more.

[0119] Examples of the thermosetting resin or thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea-formaldehyde resin (urea resin), and the like.

[0120] Examples of the photopolymerizable compound include a monomer having one or two or more photopolymerizable unsaturated bonds in the molecule, an oligomer having a photopolymerizable unsaturated bond, and the like.

[0121] As monomers having one photopolymerizable unsaturated bond in the molecule, the following can be used: alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aryl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; aminoalkyl methacrylates or acrylates such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl acrylate; methacrylates or acrylates of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; methacrylates or acrylates of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether; isobornyl methacrylate or acrylate; glyceryl methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate, etc.

[0122] As the monomer having two or more photopolymerizable unsaturated bonds in the above molecule, bisphenol A dimethacrylate, 1,4-butylene glycol 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 hexamethacrylate, dipentaerythritol tetramethacrylate, Alcohol hexamethacrylate, dipentaerythritol pentamethacrylate, epoxy methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol 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, dipentaerythritol pentaacrylate, epoxy acrylate, etc.

[0123] As the oligomer having a photopolymerizable unsaturated bond, an oligomer obtained by appropriately polymerizing the above-mentioned monomers can be used.

[0124] The above-mentioned binder resins can be used alone or in combination of two or more.

[0125] As the binder resin, epoxy acrylate resin is preferred from the viewpoint of heat resistance and developability.

[0126] The alkali-soluble resin will be described later.

[0127] As content of the said binder resin, it is preferable that it is 3-50 mass % with respect to the mass fraction of the total solid content of the pigment dispersion composition for black matrices of this invention.

[0128] (Method for producing a pigment dispersion composition for black matrix)

[0129] The pigment dispersion composition for black matrices of the present invention can be produced by adding the above-mentioned various components, mixing them, and grinding them.

[0130] There is no particular limitation on the method for performing the above-mentioned ink grinding treatment. For example, a bead mill, a ready mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roller mill, a sand mill, a sand grinder, a Dyno-Mill, a high-speed disperser (DISPERMAT), an SC mill, a high-pressure homogenizer (Nanomizer), etc. can be used, and the ink grinding treatment can be performed by a known method.

[0131] <Resist Composition for Black Matrix>

[0132] The present invention also relates to a resist composition for a black matrix obtained from the pigment dispersion composition for a black matrix of the present invention.

[0133] (Pigment dispersion composition for black matrix)

[0134] The resist composition for black matrices of the present invention contains the above-mentioned pigment dispersion composition for black matrices of the present invention.

[0135] The content of the pigment dispersion composition for a black matrix is ​​preferably 30 to 80% by mass, more preferably 40 to 75% by mass, based on the total mass of the resist composition for a black matrix of the present invention.

[0136] (Photopolymerization Initiator)

[0137] The resist composition for a black matrix of the present invention preferably contains a photopolymerization initiator.

[0138] The photopolymerization initiator is not particularly limited as long as it is a polymerization initiator that can generate free radicals or cations by irradiating active energy rays such as ultraviolet rays or electron beams, and examples thereof include: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)ethanone, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, and benzoin methyl ether. , benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl benzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, tert-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one and other benzophenone-based, thioxanthone-based, anthraquinone-based, triazine-based photopolymerization initiators, etc.

[0139] The photopolymerization initiators may be used alone or in combination of two or more.

[0140] The content of the photopolymerization initiator is preferably 1 to 20% by mass based on the total solid content of the resist composition for a black matrix of the present invention.

[0141] (Photopolymerizable compound)

[0142] The resist composition for a black matrix of the present invention preferably contains a photopolymerizable compound.

[0143] As the photopolymerizable compound, those described above for the pigment dispersion composition for black matrix can be appropriately selected and used.

[0144] The content of the photopolymerizable compound is preferably 0.1 to 50% by mass based on the total solid content of the resist composition for a black matrix of the present invention.

[0145] (Alkali soluble resin)

[0146] The resist composition for a black matrix of the present invention preferably contains an alkali-soluble resin.

[0147] The alkali-soluble resin is preferably a resin that functions as a binder for the black colorant and is soluble in a developer (particularly an alkaline developer) used in the development process when producing a black matrix.

[0148] The alkali-soluble resin may be a block copolymer. By using a block copolymer, the pigment dispersibility is improved compared with other copolymers, and solubility in PGMEA or an alkaline developer can be imparted.

[0149] Among the block copolymers, a block copolymer having a block composed of an ethylenically unsaturated monomer having one or more carboxyl groups and a block composed of another copolymerizable ethylenically unsaturated monomer is preferred.

[0150] The block copolymer is not particularly limited, and commonly used block copolymers can be used. Specifically, there can be mentioned: a copolymer of a carboxyl-containing ethylenically unsaturated monomer such as acrylic acid and methacrylic acid, and at least one ethylenically unsaturated monomer selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glyceryl monoacrylate, glyceryl methacrylate, N-phenylmaleimide, polystyrene macromonomers, and polymethyl methacrylate macromonomers that can copolymerize with the carboxyl-containing ethylenically unsaturated monomer.

[0151] However, it is preferred not to use N-vinyl pyrrolidone or a sulfur-containing monomer.

[0152] As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used.

[0153] A part of the block portion of the block copolymer may be composed of a random copolymer.

[0154] As the alkali-soluble resin, an alkali-soluble cardo resin can be used.

[0155] Examples of the alkali-soluble cardo resin include epoxy (meth)acrylate acid adducts having a fluorene skeleton, which are addition products of a fluorene epoxy (meth)acrylate derivative and dicarboxylic anhydride and / or tetracarboxylic dianhydride.

[0156] Furthermore, the alkali-soluble resin may have a photopolymerizable functional group.

[0157] The acid value of the alkali-soluble resin is preferably 5 to 300 mgKOH / g, more preferably 5 to 250 mgKOH / g, further preferably 10 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g, from the viewpoint of development properties.

[0158] In the present specification, the acid value is a theoretical acid value, which is a value obtained by calculation based on the ethylenically unsaturated monomer having a carboxyl group and its content.

[0159] The weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000, from the viewpoint of development characteristics and solubility in an organic solvent.

[0160] In the present invention, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight obtained based on GPC.

[0161] In the present specification, Water 2690 (manufactured by Waters) was used as an apparatus for measuring the weight average molecular weight, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) was used as a column.

[0162] The content of the alkali-soluble resin is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, based on 100 parts by mass of the black colorant.

[0163] At this time, if the content of the alkali-soluble resin is less than 1 part by mass, the developing characteristics may be reduced; if the content of the alkali-soluble resin exceeds 200 parts by mass, the concentration of the black colorant is relatively reduced, so it is sometimes difficult to achieve the target color concentration as a film.

[0164] The alkali-soluble resin preferably does not contain any of primary, secondary and tertiary amino groups, more preferably does not contain a quaternary ammonium group, and further preferably does not contain a basic group.

[0165] Furthermore, an alkali-soluble resin having a structure other than the block copolymer may be mixed within a range not impairing the effects of the present invention.

[0166] (Organic Solvent)

[0167] As the organic solvent, those described above for the pigment dispersion composition for black matrix can be appropriately selected and used.

[0168] As content of the said organic solvent, it is preferable that it is 1-40 mass % based on the total mass of the resist composition for black matrices of this invention, and it is more preferable that it is 5-35 mass %.

[0169] (Other additives)

[0170] The resist composition for a black matrix of the present invention may contain various additives such as a thermal polymerization inhibitor, a UV absorber, and an antioxidant as needed.

[0171] (Method for producing resist composition for black matrix)

[0172] The method for producing the resist composition for a black matrix of the present invention can be, for example, by preparing the pigment dispersion composition for a black matrix of the present invention, adding the remaining materials, and stirring and mixing them using a stirring device or the like.

[0173] The stirring and mixing method is not particularly limited, and a known method such as an ultrasonic disperser, a high-pressure emulsifier, a bead mill, a triple roll mill, a sand mill, a kneader, etc. can be used.

[0174] Alternatively, the mixture may be filtered through a filter after the stirring and mixing.

[0175] When the resist composition for a black matrix of the present invention is prepared, the black colorant, the epoxy resin, the oxazine compound, and the like described above for the pigment dispersion composition for a black matrix of the present invention may be added as necessary.

[0176] <Black Matrix>

[0177] The black matrix of the present invention is formed using the resist composition for a black matrix of the present invention.

[0178] The method for forming the black matrix of the present invention is not particularly limited. For example, the black matrix can be formed by the following method: the anti-etching composition for the black matrix of the present invention is applied on a transparent substrate, and after drying to form a coating film, a photomask is placed on the above-mentioned coating film, and an image is exposed and developed through the photomask, and photocuring is performed as needed.

[0179] As for the coating, drying, exposure, and development methods of the resist composition for a black matrix of the present invention, a known method can be appropriately selected.

[0180] As the transparent substrate, a known transparent substrate such as a glass substrate or a plastic substrate can be appropriately selected and used.

[0181] The thickness of the coating film is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm in terms of film thickness after drying.

[0182] By setting the thickness in the above range, a predetermined pattern can be appropriately developed and a predetermined optical density can be appropriately provided.

[0183] The black matrix of the present invention was coated on a glass substrate (EAGLE XG) by a spin coater to a film thickness of 1 μm, pre-baked at 100°C for 3 minutes, and exposed with a high-pressure mercury lamp (UV cumulative light dose 80 mJ / cm 2), and then post-baking at 230°C for 60 minutes to prepare a black resist pattern consisting only of a solid portion (solid portion), the surface resistance value is preferably 2.0×10 8 Ω / □ or more, more preferably 5.0×10 8 Ω / □ or more, more preferably 1.0×10 9 Ω / □.

[0184] If the surface resistance value is set to 2.0×10 8 Ω / □ or more, short circuit or current leakage can be properly prevented.

[0185] The surface resistance value can be measured using a "micro ammeter R8340" as the main body and a "shielding box R12702A" as the option (both manufactured by ADVANCE-SYA INC.).

[0186] The black matrix of the present invention was coated on a glass substrate (EAGLEXG) with a film thickness of 1 μm using a spin coater, pre-baked at 100°C for 3 minutes, and exposed with a high-pressure mercury lamp (UV cumulative light dose 40 mJ / cm 2 ), and then post-baked at 230°C for 60 minutes to produce a black resist pattern consisting only of a solid part. When the black resist pattern is attached to a stainless steel nail with a diameter of 1.6 mm through 50 mg of a sealant (trade name "XN-21S", manufactured by Mitsui Chemicals, Inc.) to produce a test piece, the sealing strength is preferably 250 N / mm 2 More than, more preferably 280N / mm 2 More than, more preferably 300N / mm 2 Above, particularly preferably 320N / mm 2 above.

[0187] If the sealing strength is 250N / mm 2 From the above, it can be said that the adhesion with respect to the substrate is sufficient.

[0188] The sealing strength can be obtained by using a load tester (LTS-200N / 500N, manufactured by Minebea) to stretch the test piece at a speed of 10 mm / min, measuring the maximum stress when the stainless steel nail is peeled off the test piece and dividing the stress by the sealant coating area to obtain the sealing strength per unit area (N / mm 2 ).

[0189] Since the pigment dispersion composition for black matrices, the resist composition for black matrices, and the black matrix of the present invention have the above-mentioned properties, they can be preferably used as a black matrix of an image display device, a touch panel, or the like.

[0190] Example

[0191] Below, the present invention is specifically described by giving examples; for the present invention, as long as it does not deviate from its main purpose and scope of application, it is not limited to these examples. It should be noted that, in the present examples, "parts" and "%" respectively represent "parts by mass" and "% by mass" unless otherwise specified.

[0192] Various materials used in the following examples and comparative examples are as follows.

[0193] <Black colorant>

[0194] Acidic carbon black (trade name: NEROX 305, average primary particle size: about 28 nm, pH: about 2.8, manufactured by Orion Engineered Carbons)

[0195] Neutral carbon black (trade name: "Printex 35", average primary particle size: 31 nm, pH: about 9.5, manufactured by Orion Engineered Carbons)

[0196] <Pigment dispersant>

[0197] DISPERBYK-167 (solid content 52 wt%, manufactured by BYK-Chemie)

[0198] <Amine compounds>

[0199] p-Aminoazobenzene (Tokyo Chemical Industry Co., Ltd.)

[0200] Dodecylamine (NISSAN AMINE (ニッサンアミン) BB, manufactured by NOF Co., Ltd.)

[0201] 1-Amino-3-undecyoxypropane (NISSAN AMINE M-14, manufactured by NOF Corporation)

[0202] Pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0203] Diamine fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

[0204] 3-Amino-N-ethylcarbazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0205] <Binder Resin>

[0206] ZCR-1569H (epoxy acrylate resin, solid content 70% by mass, manufactured by Nippon Kayaku Co., Ltd.)

[0207] <Organic solvents>

[0208] PGMEA(propylene glycol monomethyl ether acetate)

[0209] <Photopolymerization initiator>

[0210] OXE 02 (trade name: "Irgacure OXE02", 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoximo)ethanone, manufactured by BASF)

[0211] <Photopolymerizable compounds>

[0212] DPHA(Dipentaerythritol Hexaacrylate)

[0213] <Alkali-soluble resin>

[0214] WR-301 (product name: "WR-301", Cardo resin, acid value: 100 mgKOH / g, solid content: 45% by mass, manufactured by ADEKA Corporation)

[0215] <Preparation of Sulfonated Copper Phthalocyanine>

[0216] 5 parts by mass of VALIFAST BLUE 1605 (a sodium-neutralized product of a sulfonated copper phthalocyanine (containing two sulfonic acid groups in one molecule), manufactured by ORIENT CHEMICAL INDUSTRY CO., LTD.) was dissolved in 95 parts by mass of ion exchange water, and ion exchange was performed using a cation exchange resin (trade name "DOWEX MONOSPHERE 650CH Cation Exchange Resin", manufactured by Dow Chemical Company). Then, the product was dried to obtain a sodium-free product of VB 1605 (sulfonated copper phthalocyanine).

[0217] <Preparation of Dispersion Composition>

[0218] (Dispersion Composition 1)

[0219] Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Nippon Lubrizol Co., Ltd.) and dodecylamine were mixed at a mass ratio of 10:3 to obtain a dispersion composition 1.

[0220] (Dispersion Composition 2)

[0221] The sodium-free product of VB 1605 and p-aminoazobenzene were mixed at a mass ratio of 50:27 to obtain a dispersion composition 2.

[0222] (Dispersion Composition 3)

[0223] The sodium-free product of VB 1605 and dodecylamine were mixed at a mass ratio of 2:1 to obtain a dispersion composition 3.

[0224] (Dispersion Composition 4)

[0225] The sodium-free product of VB 1605 and 1-amino-3-undecyloxypropane were mixed at a mass ratio of 20:11 to obtain a dispersion composition 4.

[0226] (Dispersing composition 5)

[0227] The sodium-free product of VB 1605 and pyridine were mixed at a mass ratio of 50:11 to obtain a dispersion composition 5.

[0228] (Dispersing composition 6)

[0229] The sodium-free product of VB 1605 and diaminefluorene were mixed at a mass ratio of 25:12 to obtain a dispersion composition 6.

[0230] (Dispersion Composition 7)

[0231] The sodium-free product of VB1605 and 3-amino-N-ethylcarbazole were mixed at a mass ratio of 40:23 to obtain a dispersion composition 7.

[0232] <Dispersion Materials>

[0233] Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol Co., Ltd.) Solsperse 5000 (quaternary ammonium salt of sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol Co., Ltd.)

[0234] VALIFAST BLUE 1605 (VB 1605, sodium neutralized copper phthalocyanine sulfonate, manufactured by ORIENT CHEMICAL INDUSTRY CO., LTD.)

[0235] <Preparation of Pigment Dispersion Composition for Black Matrix>

[0236] The respective materials were mixed to form the composition shown in Table 1, and kneaded all day and night using a bead mill to prepare a pigment dispersion composition for a black matrix.

[0237] [Table 1]

[0238]

[0239] <Preparation of Resist Composition for Black Matrix>

[0240] The above-mentioned pigment dispersion composition for black matrix and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator and organic solvent) are uniformly mixed using a high-speed stirrer to form the composition of Table 2, and then filtered through a filter with a pore size of 3 μm to obtain the anti-etching composition for black matrix of the embodiment and the comparative example.

[0241] <Evaluation test>

[0242] (Surface resistance)

[0243] The pigment dispersion resist compositions for black matrices of the examples and comparative examples were applied on a glass substrate (EAGLE XG) using a spin coater to a film thickness of 1 μm, pre-baked at 100° C. for 3 minutes, and then exposed to light using a high-pressure mercury lamp (UV cumulative light dose of 80 mJ / cm 2 ), and then post-baking was performed at 230° C. for 60 minutes to prepare a black resist pattern (black matrix) formed only of a solid portion.

[0244] The surface resistance value of each prepared black resist pattern was measured using a micro ammeter R8340 as the main body and a "shielding box R12702A" as the option (both manufactured by ADVANCE Co., Ltd.).

[0245] (Seal Strength)

[0246] The pigment dispersion resist compositions for black matrices of the examples and comparative examples were applied on a glass substrate (EAGLE XG) by a spin coater to a film thickness of 1 μm, pre-baked at 100° C. for 3 minutes, and then exposed to light with a high-pressure mercury lamp (UV cumulative light dose 40 mJ / cm 2 ), and then post-baking is performed at 230°C for 30 minutes to produce a black resist pattern formed only by the solid part.

[0247] Then, the black resist pattern was bonded to a stainless steel nail having a diameter of 1.6 mm via 50 mg of a sealant (trade name "XN-21S", manufactured by Mitsui Chemicals, Inc.) to prepare a test piece.

[0248] The prepared test piece was stretched at a speed of 10 mm / min using a load tester (LTS-200N / 500N, manufactured by Minebea). The maximum stress (N) when the stainless steel nail was peeled off the test piece was measured and divided by the sealant coating area. The strength per unit area was taken as the sealing strength (N / mm 2 ). The results are shown in Table 2.

[0249] [Table 2]

[0250]

[0251] In the examples using the pigment dispersion composition for black matrix containing black colorant, sulfonated copper phthalocyanine and specific amine compound, it was confirmed that a black matrix with excellent adhesion to the substrate can be formed. In addition, it was confirmed that a black matrix with excellent surface resistance value can be formed when acidic carbon black is used as the black colorant.

[0252] Industrial Applicability

[0253] According to the present invention, a pigment dispersion composition for a black matrix capable of forming a black matrix having excellent adhesion to a substrate can be provided.

Claims

1. A pigment dispersion composition for a black matrix, wherein: The pigment dispersion composition for black matrix comprises a black colorant, a sulfonate of copper phthalocyanine and an amine compound. The amine compound is at least one selected from the following compounds (A) to (D): (A) an amine compound having a pyridine skeleton; (B) an amine compound having an aniline skeleton; (C) an amine compound having a carbazole skeleton; (D) an amine compound having a straight-chain alkyl group having 8 or more carbon atoms and a total carbon number of 20 or less; The amine compound is at least one selected from pyridine, p-aminoazobenzene, diamine fluorene, 3-amino-N-ethylcarbazole, dodecylamine, and 1-amino-3-undecyloxypropane. The sulfonated copper phthalocyanine does not contain the compound represented by the following structural formula:

2. The pigment dispersion composition for black matrix according to claim 1, wherein The sulfonated copper phthalocyanine has 0.5 to 3 sulfonic acid groups in the molecule.

3. The pigment dispersion composition for black matrix according to claim 1 or 2, wherein The black colorant includes carbon black.

4. The pigment dispersion composition for black matrix according to claim 3, wherein The carbon black is acidic carbon black. 5 . A resist composition for a black matrix, obtained from the pigment dispersion composition for a black matrix according to claim 1 . 6 . A black matrix formed from the resist composition for a black matrix according to claim 5 .

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