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

Abstract

To provide a pigment dispersion composition for a black matrix, from which a black matrix having excellent adhesion to a substrate can be formed.SOLUTION: A pigment dispersion composition for a black matrix includes a black colorant, a sulfonated product of copper phthalocyanine, and at least one amine compound, selected from the following compounds (A)-(C): (A) an amine compound having a pyridine skeleton; (B) an amine compound having an aniline skeleton; and (C) an amine compound having a carbazole skeleton, where a content of the amine compound is 5-100 pts.mass relative to 100 pts.mass of the sulfonated product of copper phthalocyanine.SELECTED DRAWING: None

Description

[Technical Field]

[0001] 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 technology]

[0002] In image display devices using liquid crystal or plasma, a light-shielding film (black matrix) is provided in the gaps between colored patterns within the display area of ​​the screen, around the edges of the display area, and in liquid crystal displays using TFT, on the external light side of the TFT. In LCD displays, this mainly prevents light leakage from the backlight, and in plasma displays, this mainly prevents blurring caused by the mixing of various colored lights from appearing on the screen, thereby helping to improve display characteristics (contrast and color purity).

[0003] For example, color filters used to convert white light from the backlight of a liquid crystal display device into colored light are usually manufactured by forming pixels of different hues, red, green, and blue, in succession in a striped or mosaic pattern on the surface of a transparent substrate, such as glass or a plastic sheet, on which a black matrix has been formed.

[0004] Similarly, in touch panels that combine image display devices and position input devices, color filters with black matrices formed as light-shielding films are used, and until now, these have generally been formed on the opposite side of the cover glass from the sensor substrate. However, as demand for lighter touch panels increases, progress is being made in the development of technology that simultaneously forms the light-shielding film and touch sensor on the same side of the cover glass, which will enable even lighter panels.

[0005] As a method for forming such a black matrix, for example, a photolithography method using a pigment (pigment method) is used. In such a pigment method, a sulfonic acid derivative of copper phthalocyanine is sometimes used to improve the dispersibility of the pigment.

[0006] For example, Patent Document 1 discloses a pigment dispersion composition for black matrices, which is characterized by dispersing, in a solvent, carbon black having an oil absorption of 10 to 150 ml / 100 g and a pH of greater than 9, a basic group-containing urethane polymer pigment dispersant having a polyester chain, and a phthalocyanine derivative having a sulfonic acid group as an acid group-containing pigment derivative.

[0007] The black matrix needs to have good adhesion to the substrate. However, in Patent Document 1, sufficient consideration was not given to adhesion, and there was room for further improvement. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2008 / 066100 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, an object of the present invention is to provide a pigment dispersion composition for a black matrix that can form a black matrix that has excellent adhesion to a substrate. [Means for solving the problem]

[0010] The present inventors have discovered that by further adding a specific amine compound to a pigment dispersion composition for a black matrix containing a black colorant and a sulfonated copper phthalocyanine, a pigment dispersion composition for a black matrix capable of forming a black matrix having excellent adhesion to a substrate can be obtained, and have completed the present invention.

[0011] That is, the present invention provides a pigment dispersion composition for black matrix, which comprises a black colorant, a sulfonated copper phthalocyanine, and an amine compound, wherein the amine compound is at least one selected from the following (A) to (D): (A) Amine compound having a pyridine skeleton (B) Amine compounds having an aniline skeleton (C) Amine compound having a carbazole skeleton (D) Amine compounds having a linear alkyl group with 8 or more carbon atoms and a total of 20 or less carbon atoms The amine compound is preferably at least one selected from pyridine, p-aminoazobenzene, bisanilinefluorene, 3-amino-N-ethylcarbazole, dodecylamine, and 1-amino-3-undecanoxypropane. The sulfonated copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in the molecule. The black colorant preferably contains carbon black. The carbon black is preferably acidic carbon black. The present invention also relates to a resist composition for a black matrix obtained from the above-mentioned pigment dispersion composition for a black matrix. The present invention also relates to a black matrix formed from the above-mentioned black matrix resist composition. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a pigment dispersion composition for a black matrix that can form a black matrix that has excellent adhesion to a substrate. DETAILED DESCRIPTION OF THE INVENTION

[0013] <Pigment dispersion composition for black matrix> The pigment dispersion composition for black matrix of the present invention contains a black colorant, a sulfonated copper phthalocyanine, and an amine compound, and the amine compound is at least one selected from the following (A) to (D): (A) Amine compound having a pyridine skeleton (B) Amine compounds having an aniline skeleton (C) Amine compound having a carbazole skeleton (D) Amine compounds having a linear alkyl group with 8 or more carbon atoms and a total of 20 or less carbon atoms

[0014] (black colorant) The pigment dispersion composition for a black matrix of the present invention contains a black colorant. The black colorant preferably contains carbon black, and from the viewpoint of imparting a suitable surface resistivity, the carbon black is more preferably acidic carbon black. The carbon black preferably has an average primary particle diameter of 20 to 60 nm, and more preferably neutral carbon black with an average primary particle diameter of 20 to 60 nm and / or acidic carbon black with an average primary particle diameter of 20 to 60 nm. If the primary particle size of the black colorant is smaller than 20 nm or larger than 60 nm, the black colorant may not have sufficient light-shielding properties or may have poor storage stability. The average primary particle size is an arithmetic mean diameter determined by observation with an electron microscope.

[0015] From the viewpoint of imparting a suitable surface resistivity, the black colorant preferably contains only acidic carbon black. On the other hand, when the neutral carbon black and the acidic carbon black are used in combination, the neutral carbon black preferably accounts for 85% by mass or less, and more preferably 75% by mass or less, of the total mass of the neutral carbon black and the acidic carbon black. If the content of neutral carbon black in the carbon black is more than 85% by mass, the seal strength may decrease.

[0016] The above-mentioned acidic carbon black and neutral carbon black will now be described. Carbon black can be broadly classified into acidic carbon black and neutral carbon black depending on the surface structure. Acidic carbon black is a carbonaceous material that has been naturally or artificially oxidized and exhibits acidity when mixed and boiled with distilled water. On the other hand, neutral carbon black is known to exhibit a neutral or higher pH when mixed and boiled with distilled water.

[0017] The neutral carbon black preferably has a pH in the range of 8.0 to 10.0. Specific examples include Printex 25 (average primary particle size 56 nm, pH 9.5), Printex 35 (average primary particle size 31 nm, pH 9.5), and Printex 65 (average primary particle size 21 nm, pH 9.5), all manufactured by Orion Engineered Carbons, and MA#20 (average primary particle size 40 nm, pH 8.0), MA#40 (average primary particle size 40 nm, pH 8.0), and MA#30 (average primary particle size 30 nm, pH 8.0), all manufactured by Mitsubishi Chemical Corporation.

[0018] The acidic carbon black preferably has a pH in the range of 2.0 to 4.0. Specific examples include Raven 1080 (average primary particle size 28 nm, pH 2.4) and Raven 1100 (average primary particle size 32 nm, pH 2.9) manufactured by Columbia Chemicals; MA-8 (average primary particle size 24 nm, pH 3.0) and MA-100 (average primary particle size 22 nm, pH 3.5) manufactured by Mitsubishi Chemical; and Special Black 250 (average primary particle size 56 nm, pH 3.0), Special Black 350 (average primary particle size 31 nm, pH 3.0), Special Black 550 (average primary particle size 25 nm, pH 4.0), and NEROX 305 (average primary particle size approximately 28 nm, pH approximately 2.8) manufactured by Orion Engineered Carbons.

[0019] As the black colorant, Special Black 250 or NEROX305 is preferred from the viewpoint of providing favorable pigment dispersibility and surface resistance value.

[0020] The pH can be measured at 25°C using a glass electrode after preparing an aqueous suspension by adding 1 g of carbon black to 20 ml of decarbonated distilled water (pH 7.0) and mixing with a magnetic stirrer (German Industrial Standard DIN ISO 787 / 9).

[0021] The content of the black colorant is preferably 3 to 70 mass %, more preferably 10 to 50 mass %, as a mass fraction relative to the total solid content of the pigment dispersion composition for black matrix of the present invention. If the content of the black colorant is less than 3% by mass, the light blocking properties may be reduced when a black matrix is ​​formed, whereas if it exceeds 70% by mass, it may be difficult to disperse the pigment.

[0022] (sulfonated copper phthalocyanine) The pigment dispersion composition for black matrix of the present invention contains a sulfonated copper phthalocyanine. In the process of microparticulating or dispersing the black colorant, the sulfonated copper phthalocyanine has an effect of improving the microparticulation of the black colorant during dispersion and the dispersion stability after dispersion, because the basic skeleton portion is adsorbed to the pigment surface and the sulfonic acid group increases the affinity with the organic solvent or the pigment dispersant.

[0023] The copper phthalocyanine in the sulfonated copper phthalocyanine is not particularly limited as long as it has a structure having 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 ease of introduction of a sulfonic acid group, a structure having no substituent is preferred.

[0024] The sulfonated copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in the molecule. In this way, by having 0.5 to 3 sulfonic acid groups in the molecule, it is possible to obtain a black matrix composition that can give a coating film with excellent adhesion. The sulfonated copper phthalocyanine more preferably has 0.7 to 2.5 sulfonic acid groups in the molecule, and even more preferably has 0.9 to 2.0 sulfonic acid groups. The number of sulfonic acid groups in the molecule can be calculated based on the ratio of sulfur atoms to copper atoms determined by elemental analysis.

[0025] As the sulfonated copper phthalocyanine, commercially available products may be used, such as Solsperse 12000 (both manufactured by Lubrizol Japan), desodium-depleted VALIFAST BLUE 1605 (manufactured by Orient Chemical Industries Co., Ltd.), and TURQUOISE EC-GN (manufactured by Huntsman).

[0026] The content of the sulfonated copper phthalocyanine is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the black colorant.

[0027] (amine compounds) The pigment dispersion composition for a black matrix of the present invention contains an amine compound. The amine compound is at least one selected from the following (A) to (D): (A) Amine compound having a pyridine skeleton (B) Amine compounds having an aniline skeleton (C) Amine compound having a carbazole skeleton (D) Amine compounds having a linear alkyl group with 8 or more carbon atoms and a total of 20 or less carbon atoms The inclusion of such amine compounds is believed to contribute to the formation of a uniform coating film and, in turn, to adhesion, due to the sensitizing effect of the skeleton of each amine compound in (A) to (C), and due to the compatibility with the binder resin resulting from the appropriate carbon number of the alkyl group in (D). Furthermore, when acidic carbon black is used as the black colorant, the sensitizing effect of the skeleton of the amine compound allows the formation of a black matrix with excellent surface resistance. However, the present invention should not be construed as being limited to the above mechanism.

[0028] The amine compound having a pyridine skeleton may be pyridine, or may be an amine compound having a pyridine skeleton with an alkyl group or an amino group. Specific examples include alkylpyridines such as 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4-picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, and 5-ethyl-2-methylpyridine; 3,4-cyclopentenopyridine, 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. Of these, pyridine and 4-(3-phenylpropyl)pyridine are preferred.

[0029] Examples of the amine compound having an aniline skeleton include aniline, phenylenediamine, aminonaphthalene, diaminonaphthalene, mesidine, methylaniline, metanilic acid, aminophenol, bisanilinefluorene, p-aminoazobenzene, 2,4-diaminoazobenzene, and 4,4-diaminoazobenzene. Among these, those having two or more benzene rings are preferred, and p-aminoazobenzene and bisanilinefluorene are more preferred.

[0030] Examples of the amine compound having a carbazole skeleton include 3,6-diaminocarbazole and 3-amino-N-ethylcarbazole. Of these, 3-amino-N-ethylcarbazole is preferred.

[0031] The amine compound having a linear alkyl group having 8 or more carbon atoms and a total of 20 or less carbon atoms 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, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, dimethyllaurylamine, and 1-amino-3-undecanoxypropane. Among these, it is preferable that the amine has a linear alkyl group having 10 or more carbon atoms and a total number of carbon atoms of 16 or less, and specifically, dodecylamine and 1-amino-3-undecanoxypropane are preferred.

[0032] The amine compound is preferably at least one selected from pyridine, p-aminoazobenzene, bisanilinefluorene, 3-amino-N-ethylcarbazole, dodecylamine, and 1-amino-3-undecanoxypropane. Such amine compounds can be suitably used because they have a structure that has a sensitizing effect and a structure that has good compatibility with the binder resin.

[0033] The amount of the amine compound is preferably 5 to 100 parts by mass, more preferably 20 to 60 parts by mass, per 100 parts by mass of the sulfonated copper phthalocyanine.

[0034] (organic solvent) The pigment dispersion composition for black matrix of the present invention preferably contains an organic solvent. As the organic solvent, organic solvents that have been conventionally used in the field of liquid crystal black matrix resists can be suitably used.

[0035] Specifically, the organic solvent is a solvent that can be used under normal pressure (1.013×10 2Examples of the organic solvent include ester-based organic solvents, ether-based organic solvents, ether ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon-based organic solvents, and nitrogen-containing organic solvents, each of which has a boiling point of 100 to 250°C at 250°C (at 250°C / kPa). If a large amount of the organic solvent having a boiling point exceeding 250°C is contained, when a coating film formed by applying a resist composition for a black matrix obtained from the pigment dispersion composition for a black matrix of the present invention is prebaked, the organic solvent may not evaporate sufficiently and remain in the dried coating film, resulting in a decrease in the heat resistance of the dried coating film. Furthermore, if the composition contains a large amount of the organic solvent having a boiling point of less than 100°C, it may become difficult to apply the composition uniformly without unevenness, and a coating film having excellent surface smoothness may not be obtained.

[0036] Specific examples of the organic solvent include ether-based 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; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ... Examples of suitable organic solvents include ether ester organic solvents such as polyethylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone; ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, and n-amyl formate; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, and butanol; and nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These may be used alone or in combination of two or more.

[0037] Among the above organic solvents, in terms of solubility, dispersibility, coatability, and the like, 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-amyl formate, and the like are preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being more preferred.

[0038] (pigment dispersant) The pigment dispersion composition for a black matrix of the present invention preferably contains a pigment dispersant. The pigment dispersant is a basic group-containing pigment dispersant, and examples of the pigment dispersant that can be used 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, and acidic group-containing polymeric pigment dispersants. These basic group-containing pigment dispersants may be used alone or in combination of two or more. Among them, basic group-containing polymeric pigment dispersants are preferred because they provide good pigment dispersibility.

[0039] Specific examples of the basic group-containing polymeric pigment dispersant include: (1) A reaction product of an amino group and / or an imino group of a polyamine compound (e.g., a poly(lower alkylene amine) such as polyallylamine, polyvinylamine, or polyethylene polyimine) with at least one member selected from the group consisting of polyesters, polyamides, and polyesteramides having free carboxyl groups (Japanese Patent Laid-Open No. 2001-59906), (2) Reaction products of low molecular weight amino compounds such as poly(lower) alkyleneimines and methyliminobispropylamine with polyesters having free carboxyl groups (JP-A-54-37082, JP-A-01-311177), (3) A reaction product obtained by sequentially reacting an isocyanate group of a polyisocyanate compound with an alcohol such as methoxypolyethylene glycol, a polyester having one hydroxyl group such as caprolactone polyester, a compound having two to three isocyanate group-reactive functional groups, and an aliphatic or heterocyclic hydrocarbon compound having an isocyanate group-reactive functional group and a tertiary amino group (Japanese Patent Laid-Open No. 02-612). (4) A compound obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group; (5) A reaction product obtained by adding a polyether chain to a low molecular weight amino compound. (6) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group (Japanese Patent Laid-Open No. 04-210220). (7) A reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group (JP-A-09-87537). (8) A reaction product of a polycarbonate compound having a functional group at one end capable of reacting with an amino group with a polyamine compound (Japanese Patent Laid-Open No. 09-194585), (9) Copolymers of at least one selected from methacrylic acid esters or acrylic acid esters, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, and benzyl acrylate, at least one basic group-containing polymerizable monomer, such as acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, and a monomer having an amino group and a polycaprolactone skeleton, and at least one styrene, styrene derivative, and other polymerizable monomers (Japanese Patent Laid-Open No. 01-164429), (10) Basic group-containing carbodiimide pigment dispersants (International Publication No. WO04 / 000950), (11) Block copolymers consisting of a block having a basic group such as a tertiary amino group or a quaternary ammonium salt group and a block having no functional group (see the description in JP-A-2005-55814), (12) A pigment dispersant obtained by subjecting polyallylamine to a Michael addition reaction with a polycarbonate compound (JP-A-09-194585), (13) Carbodiimide compounds having at least one polybutadiene chain and at least one basic nitrogen-containing group (JP 2006-257243 A), (14) Carbodiimide compounds having at least one amide group-containing side chain and at least one basic nitrogen-containing group in the molecule (Japanese Patent Application Laid-Open No. 2006-176657), (15) Polyurethane compounds having structural units with ethylene oxide chains and propylene oxide chains and having amino groups quaternized with a quaternizing agent (JP 2009-175613 A), (16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with an active hydrogen group of a compound having an active hydrogen group in the 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% of the total number of isocyanate groups derived from the isocyanurate compound having an isocyanurate ring and urethane bonds and urea bonds formed by the reaction of the isocyanate groups with the active hydrogen groups (Patent Application No. 2009-220836). (17) Examples include graft copolymers in which polyether or polyester side chains are introduced into acrylate polymers having amino groups.

[0040] Among the basic group-containing polymeric pigment dispersants, basic group-containing urethane-based polymeric pigment dispersants, basic group-containing polyester-based polymeric pigment dispersants, and basic group-containing acrylic-based polymeric pigment dispersants are more preferred, and amino group-containing urethane-based polymeric pigment dispersants, amino group-containing polyester-based polymeric pigment dispersants, and amino group-containing acrylic-based polymeric pigment dispersants are even more preferred.Among the basic group-containing polymeric pigment dispersants, basic group (amino group)-containing polymeric pigment dispersants having at least one chain selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains are particularly preferred.

[0041] The content of the pigment dispersant is preferably 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the black colorant.

[0042] (binder resin) The pigment dispersion composition for a black matrix of the present invention preferably contains a binder resin.

[0043] Examples of the binder resin include thermosetting resins, thermoplastic resins, photopolymerizable compounds, alkali-soluble resins, etc. These may be used alone or in combination of two or more.

[0044] Examples of the thermosetting resins and thermoplastic resins include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, phenolic resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubbers, epoxy resins, celluloses, polybutadiene, polyimide resins, benzoguanamine resins, melamine resins, and urea resins.

[0045] Examples of the photopolymerizable compound include a monomer having one or more photopolymerizable unsaturated bonds in the molecule, and an oligomer having a photopolymerizable unsaturated bond.

[0046] Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; and amino groups such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl acrylate. Examples of usable methacrylates or acrylates include alkyl methacrylates or acrylates, 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, 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, and 2-hydroxyethyl methacrylate or acrylate.

[0047] Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule 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 hexamethacrylate, dipentaerythritol pentamethacrylate, and the like. Methacrylate, epoxy methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, epoxy acrylate, and the like can be used.

[0048] As the oligomer having a photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the above-mentioned monomers can be used. The above binder resins can be used alone or in combination of two or more kinds.

[0049] The binder resin is preferably an epoxy acrylate resin from the viewpoints of heat resistance and developability.

[0050] The alkali-soluble resin will be described later.

[0051] The content of the binder resin is preferably 3 to 50% by mass as a mass fraction relative to the total solid content of the pigment dispersion composition for black matrix of the present invention.

[0052] (Method of manufacturing pigment dispersion composition for black matrix) The pigment dispersion composition for black matrix of the present invention can be produced by adding the above-mentioned various components, mixing and kneading them. The method for the above-mentioned milling is not particularly limited, and milling may be carried out by a known method using, for example, a bead mill, a ready mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a Dyno Mill, a Dispermat, an SC Mill, a Nanomizer, or the like.

[0053] <Resist composition for black matrix> 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.

[0054] (Pigment dispersion composition for black matrix) The resist composition for a black matrix of the present invention contains the above-mentioned pigment dispersion composition for a black matrix of the present invention. The content of the pigment dispersion composition for black matrix is ​​preferably 30 to 80 mass %, and more preferably 40 to 75 mass %, based on the total mass of the resist composition for black matrix of the present invention.

[0055] (Photopolymerization initiator) The resist composition for a black matrix of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can generate radicals or cations when irradiated with active energy rays such as ultraviolet rays or electron beams. Examples of the photopolymerization initiator include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzil dimethyl ketal, α-hydroxyisopropyl benzoate, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisopropyl benzoate, benzoin methyl ether, benzoin isobutyl ether ... isobutyl ether, benzoin isobutyl ether, benzo Examples of photopolymerization initiators include benzophenone-based, thioxanthone-based, anthraquinone-based, and triazine-based photopolymerization initiators such as tert-butylanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, and 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one. The photopolymerization initiators may be used alone or in combination of two or more.

[0056] The content of the photopolymerization initiator is preferably 1 to 20% by mass as a mass fraction relative to the total solid content of the black matrix resist composition of the present invention.

[0057] (Photopolymerizable compound) The resist composition for a black matrix of the present invention preferably contains a photopolymerizable compound. As the photopolymerizable compound, any of those described above in connection with the pigment dispersion composition for black matrix can be appropriately selected and used.

[0058] The content of the photopolymerizable compound is preferably 0.1 to 50 mass % as a mass fraction relative to the total solid content of the black matrix resist composition of the present invention.

[0059] (alkali-soluble resin) The black matrix resist composition of the present invention preferably contains an alkali-soluble resin. The alkali-soluble resin preferably acts as a binder for the black colorant and is soluble in the developer, particularly the alkaline developer, used in the development process when producing the black matrix.

[0060] The alkali-soluble resin may be a block copolymer, which has improved pigment dispersibility and solubility in PGMEA and alkaline developers compared to other copolymers. Among these block copolymers, a block copolymer having a block consisting of an ethylenically unsaturated monomer having one or more carboxyl groups and a block consisting of another copolymerizable ethylenically unsaturated monomer is preferred.

[0061] The block copolymer is not particularly limited, and conventionally used ones can be used. Specific examples thereof include copolymers of an ethylenically unsaturated monomer having a carboxyl group, such as acrylic acid or methacrylic acid, with at least one ethylenically unsaturated monomer selected from the group consisting of monomers and oligomers copolymerizable with the ethylenically unsaturated monomer having a carboxyl group, such as styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, and carboepoxy diacrylate. However, it is preferable not to use N-vinylpyrrolidone or sulfur-containing monomers. As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used. A part of the block portions of the block copolymer may be composed of a random copolymer.

[0062] As the alkali-soluble resin, an alkali-soluble cardo resin can also be used. Examples of the alkali-soluble cardo resin include an epoxy(meth)acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy(meth)acrylic acid derivative and a dicarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. The alkali-soluble resin may also have a photopolymerizable functional group.

[0063] The acid value of the alkali-soluble resin is preferably from 5 to 300 mgKOH / g, more preferably from 5 to 250 mgKOH / g, further preferably from 10 to 200 mgKOH / g, and particularly preferably from 60 to 150 mgKOH / g, from the viewpoint of development properties. In this specification, the acid value is a theoretical acid value, which is a value calculated arithmetically based on the amount of ethylenically unsaturated monomer having a carboxyl group and its content.

[0064] The weight average molecular weight of the alkali-soluble resin is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000, and even more preferably from 5,000 to 30,000, from the viewpoint of development characteristics and solubility in organic solvents. In the present invention, the weight average molecular weight is a weight average molecular weight calculated in terms of polystyrene obtained based on GPC. In this specification, the weight-average molecular weight is measured using a Water2690 (manufactured by Waters Corporation) as an apparatus and a PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) as a column.

[0065] The content of the alkali-soluble resin is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the black colorant. In this case, if the content of the alkali-soluble resin is less than 1 part by mass, the development characteristics may be reduced, whereas if the content of the alkali-soluble resin is more than 200 parts by mass, the concentration of the black colorant will be relatively reduced, making it difficult to achieve the desired color density as a thin film.

[0066] The alkali-soluble resin preferably does not contain any primary, secondary, or tertiary amino group, and further preferably does not contain any quaternary ammonium group, and more preferably does not contain any basic group. An alkali-soluble resin having a structure other than that of a block copolymer may be blended within a range that does not impair the effects of the present invention.

[0067] (organic solvent) As the organic solvent, any of the organic solvents described above in connection with the pigment dispersion composition for black matrix can be appropriately selected and used.

[0068] The content of the organic solvent is preferably from 1 to 40% by mass, and more preferably from 5 to 35% by mass, based on the total mass of the black matrix resist composition of the present invention.

[0069] (Other additives) The black matrix resist composition of the present invention may contain various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, as needed.

[0070] (Method of manufacturing a resist composition for black matrix) 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, and then adding the remaining materials and stirring and mixing them using a stirring device or the like. The method of stirring and mixing is not particularly limited, and known methods such as an ultrasonic disperser, a high-pressure emulsifier, a bead mill, a three-roll mill, a sand mill, and a kneader can be used. After the stirring and mixing, the mixture may be filtered. When preparing the resist composition for a black matrix of the present invention, the black colorant, the epoxy resin, the oxazine compound, etc. described in the pigment dispersion composition for a black matrix of the present invention may be added, if necessary.

[0071] <Black matrix> The black matrix of the present invention is formed from the black matrix resist composition of the present invention.

[0072] The method for forming the black matrix of the present invention is not particularly limited, and for example, the black matrix can be formed by applying the black matrix resist composition of the present invention onto a transparent substrate, drying the composition to form a coating film, placing a photomask on the coating film, and performing image exposure through the photomask, development, and, if necessary, photocuring, or the like.

[0073] As the methods for applying, drying, exposing, and developing the black matrix resist composition of the present invention, known methods can be appropriately selected. The transparent substrate may be selected appropriately from known transparent substrates such as a glass substrate or a plastic substrate.

[0074] The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm. By setting the thickness within the above range, a predetermined pattern can be suitably developed, and a predetermined optical density can be suitably imparted.

[0075] The black matrix of the present invention was applied to a glass substrate (EAGLE XG) using a spin coater to a thickness of 1 μm, prebaked at 100° C. for 3 minutes, and then exposed to a high-pressure mercury lamp (UV integrated light amount 80 mJ / cm ). 2 ) and post-baked at 230°C for 60 minutes to create a black resist pattern consisting of only the solid area. The surface resistance was 2.0 × 10 8 Ω / □ or more is preferable, 5.0×10 8 Ω / □ or more is preferable, and 1.0×10 9 Ω / □ or more is more preferable. The surface resistance is 2.0×10 8 If the resistance is Ω / □ or more, short circuits and current leakage can be suitably prevented. The surface resistance value can be measured using a microcurrent meter R8340 as the main body and a shield box R12702A as an option (both manufactured by Advance Co., Ltd.).

[0076] The black matrix of the present invention was applied to a glass substrate (EAGLE XG) using a spin coater to a thickness of 1 μm, prebaked at 100° C. for 3 minutes, and then exposed to a high-pressure mercury lamp (UV integrated light amount 40 mJ / cm ). 2 ), and then post-baked at 230°C for 60 minutes to produce a black resist pattern consisting only of the solid area. When the black resist pattern was attached to a stainless steel nail with a diameter of 1.6 mm via 50 mg of a sealant (trade name "XN-21S", manufactured by Mitsui Chemicals, Inc.) to produce a test piece, the seal strength was 250 N / mm 2 More than 280N / mm is preferable. 2 More preferably, 300N / mm 2 More preferably, 320N / mm 2 The above is particularly preferred. The above seal strength is 250N / mm 2 If the above is true, it can be said that the adhesion to the substrate is sufficient. The seal strength was calculated by pulling the test piece at a rate of 10 mm / min using a load measuring device (LTS-200N / 500N, manufactured by Minebea), measuring the maximum stress when the stainless steel nail peeled off the test piece, and dividing this by the area of ​​the sealant coating to obtain the seal strength per unit area (N / mm 2 ) can be obtained.

[0077] The pigment dispersion composition for black matrix, the resist composition for black matrix, and the black matrix of the present invention have the above-mentioned properties and can therefore be suitably used as a black matrix for image display devices, touch panels, and the like. [Example]

[0078] The present invention will be specifically described below using examples, but the present invention is not limited to these examples as long as they do not deviate from the spirit and scope of the invention. In the examples, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0079] The various materials used in the following examples and comparative examples are as follows: <Black colorant> Acidic carbon black (product name "NEROX305", average primary particle size approximately 28 nm, pH approximately 2.8, manufactured by Orion Engineered Carbons) Neutral carbon black (trade name "Printex 35", average primary particle size 31 nm, pH approximately 9.5, manufactured by Orion Engineered Carbons) <Pigment dispersant> DISPERBYK-167 (solid content 52% by mass, manufactured by BYK) <Amine compounds> p-Aminoazobenzene (Tokyo Chemical Industry Co., Ltd.) Dodecylamine (Nissan Amine BB, manufactured by NOF Corporation) 1-amino-3-undecanoxypropane (Nissan Amine M-14, NOF Corporation) Pyridine (Tokyo Chemical Industry Co., Ltd.) Bisanilinefluorene (Osaka Gas Chemicals Co., Ltd.) 3-amino-N-ethylcarbazole (Tokyo Chemical Industry Co., Ltd.) <Binder resin> ZCR-1569H (epoxy acrylate resin, solid content 70% by mass, manufactured by Nippon Kayaku Co., Ltd.) <Organic solvents> PGMEA (Propylene Glycol Monomethyl Ether Acetate) <Photopolymerization initiator> OXE02 (product name "Irgacure OXE02", 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, manufactured by BASF) <Photopolymerizable compound> DPHA (Dipentaerythritol hexaacrylate) <Alkali-soluble resin> WR-301 (product name "WR-301", cardo resin, acid value 100 mg KOH / g, solid content 45 mass%, manufactured by ADEKA Corporation)

[0080] <Preparation of sulfonated copper phthalocyanine> Five parts by mass of VALIFAST BLUE 1605 (a sodium-neutralized sulfonated copper phthalocyanine (containing two sulfonic acid groups per molecule), manufactured by Orient Chemical Industries Co., Ltd.) was dissolved in 95 parts by mass of ion-exchanged water, and the solution was subjected to ion exchange using a cation exchange resin (trade name "DOWEX MONOSPHERE 650C H Cation Exchange Resin", manufactured by The Dow Chemical Company). The solution was then dried to obtain VB1605 Na-depleted product (a sulfonated copper phthalocyanine).

[0081] <Preparation of Dispersion Composition> (Dispersion composition 1) Dispersion composition 1 was obtained by mixing Solsperse 12000 (a sulfonated copper phthalocyanine (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Japan) and dodecylamine in a mass ratio of 10:3. (Dispersion composition 2) Dispersion composition 2 was obtained by mixing VB1605 sodium-depleted product and p-aminoazobenzene in a mass ratio of 50:27. (Dispersion composition 3) Dispersing composition 3 was obtained by mixing VB1605 sodium-depleted product and dodecylamine in a mass ratio of 2:1. (Dispersion composition 4) Dispersion composition 4 was obtained by mixing VB1605 desodium product and 1-amino-3-undecanoxypropane in a mass ratio of 20:11. (Dispersion composition 5) Dispersing composition 5 was obtained by mixing VB1605 sodium-depleted product and pyridine in a mass ratio of 50:11. (Dispersion composition 6) Dispersing composition 6 was obtained by mixing VB1605 sodium-depleted product and bisanilinefluorene in a mass ratio of 25:12. (Dispersion composition 7) Dispersing composition 7 was obtained by mixing VB1605 Na-depleted product and 3-amino-N-ethylcarbazole in a mass ratio of 40:23.

[0082] <Dispersion material> Solsperse 12000 (sulfonated copper phthalocyanine (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Japan) Solsperse 5000 (quaternary ammonium salt of sulfonated copper phthalocyanine (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Japan) VALIFAST BLUE 1605 (VB1605, sodium neutralized sulfonated copper phthalocyanine, manufactured by Orient Chemical Industries Co., Ltd.)

[0083] <Preparation of Pigment Dispersion Composition for Black Matrix> The materials were mixed to obtain the composition shown in Table 1, and kneaded overnight in a bead mill to prepare a pigment dispersion composition for black matrix.

[0084] [Table 1]

[0085] <Preparation of Black Matrix Resist Composition> Using a high-speed mixer, the above-mentioned pigment dispersion composition for black matrix and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator, and organic solvent) were uniformly mixed to the composition shown in Table 2, and then filtered through a filter with a pore size of 3 μm to obtain resist compositions for black matrix of Examples and Comparative Examples.

[0086] <Evaluation test> (surface resistance value) Each of the pigment-dispersed resist compositions for black matrix in the Examples and Comparative Examples was applied to a glass substrate (EAGLE XG) using a spin coater to a film thickness of 1 μm, prebaked at 100° C. for 3 minutes, and then exposed to a high-pressure mercury lamp (UV integrated light amount 80 mJ / cm ). 2 ) and then post-baked at 230°C for 60 minutes to produce a black resist pattern (black matrix) consisting of only the solid areas. The surface resistance of each of the prepared black resist patterns was measured using a microcurrent meter R8340 (main body) and a shield box R12702A (optional) (both manufactured by Advance Co., Ltd.). The results are shown in Table 2.

[0087] (Seal strength) Each of the pigment-dispersed resist compositions for black matrix of the Examples and Comparative Examples was applied to a glass substrate (EAGLE XG) using a spin coater to a film thickness of 1 μm, prebaked at 100° C. for 3 minutes, and then exposed to a high-pressure mercury lamp (UV integrated light dose 40 mJ / cm ). 2 ) and then post-baked at 230°C for 30 minutes to produce a black resist pattern consisting only of solid areas. Thereafter, the black resist pattern was attached 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. The prepared test specimen was pulled at a rate of 10 mm / min using a load measuring device (LTS-200N / 500N, manufactured by Minebea), and the maximum stress (N) was measured when the stainless steel nail peeled off the test specimen. This was divided by the area of ​​the sealant coating to determine the strength per unit area as the seal strength (N / mm 2 The results are shown in Table 2.

[0088] [Table 2]

[0089] In the examples using a pigment dispersion composition for a black matrix containing a black colorant, a sulfonated copper phthalocyanine, and a specific amine compound, it was confirmed that a black matrix having excellent adhesion to a substrate could be formed. Furthermore, when acidic carbon black was used as the black colorant, it was confirmed that a black matrix having excellent surface resistivity could also be formed. [Industrial Applicability]

[0090] According to the present invention, it is possible to provide a pigment dispersion composition for a black matrix that can form a black matrix that has excellent adhesion to a substrate.

Claims

1. The ink contains a black colorant, a sulfonated copper phthalocyanine, and an amine compound, The amine compound is at least one selected from the following (A) to (C): The content of the amine compound is 5 to 100 parts by mass per 100 parts by mass of the sulfonated copper phthalocyanine. Pigment dispersion composition for black matrix. (A) Amine compound having a pyridine skeleton (B) Amine compound having an aniline skeleton (C) Amine compound having a carbazole skeleton

2. 2. The pigment dispersion composition for a black matrix according to claim 1, wherein the amine compound is at least one selected from the group consisting of pyridine, p-aminoazobenzene, bisanilinefluorene, and 3-amino-N-ethylcarbazole.

3. 3. 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.

4. 4. The pigment dispersion composition for a black matrix according to claim 1, wherein the black colorant contains carbon black.

5. 5. The pigment dispersion composition for a black matrix according to claim 4, wherein the carbon black is an acidic carbon black.

6. A resist composition for black matrix obtained from the pigment dispersion composition for black matrix according to any one of claims 1 to 5.

7. A black matrix formed from the black matrix resist composition according to claim 6.

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