TWI906398B - Pigment dispersion composition for black matrix, resist composition for black matrix and black matrix - Google Patents

Abstract

This invention provides a pigment dispersion for black matrices, which can be used to obtain a photoresist composition for black matrices. This photoresist composition forms a black matrix whose surface resistivity does not decrease even after high-temperature and prolonged baking, and whose breakpoints do not change with storage time. The pigment dispersion for black matrices of this invention contains a black colorant, a sulfonated copper phthalocyanine, and an epoxy compound.

Description

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

This invention relates to a pigment dispersion composition for a black matrix, a photoresist composition for a black matrix, and a black matrix.

In image display devices using liquid crystal or plasma displays, a light-shielding film (black matrix) is provided between the colored patterns within the display area of the screen or at the edge of the display area. Furthermore, in liquid crystal displays using TFTs, a light-shielding film (black matrix) is provided on the outer light side of the TFT. Moreover, regarding the function of the light-shielding film, in liquid crystal displays, it primarily prevents light leakage from the backlight from entering the screen. In plasma displays, it primarily prevents color bleeding caused by the mixing of different colors of light from entering the screen, thereby improving display characteristics (contrast and color purity).

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

Furthermore, in touch panels that combine image display devices and position input devices, a color filter with a black matrix forming a light-shielding film is also used. Until now, this filter has generally been formed on the side opposite to the sensor substrate, separated by a covering glass. However, with increasing demands for lightweight touch panels, there is active development of technology that simultaneously forms the light-shielding film and the touch sensor on the same side of the covering glass to achieve even greater weight reduction.

One method for forming such a black matrix is, for example, photolithography using pigments (pigment method). In this pigment method, sulfonic acid derivatives of copper phthalocyanine are sometimes used to improve the dispersibility of the pigment.

For example, Patent Document 1 discloses a pigment dispersion composition for black matrix, characterized in that: carbon black with an oil absorption of 10-150 ml/100 g and a pH greater than 9 is dispersed in the solvent, an urethane-based polymeric pigment dispersant with an alkaline group having a polyester chain, and a phthalocyanine derivative with a sulfonic acid group as an acidic pigment derivative.

In recent years, image display devices have been increasingly used in various applications, including mobile devices. As the applications of these image display devices expand, there is a growing demand for more robust black matrices.

As a method to make the black matrix more stable, baking at high temperatures for a long time is sometimes used. However, Patent 1 does not fully investigate the decrease in surface resistivity caused by baking at high temperatures for a long time, leaving room for further improvement.

On the other hand, for black matrix pigment-dispersed photoresist compositions, it is necessary to ensure that the breakpoint (the time from which the unexposed portion dissolves and peels off during the developing step, and the developed pattern begins to appear) does not change over storage time. Therefore, a black matrix pigment dispersion composition capable of producing such a black matrix pigment-dispersed photoresist composition is sought. However, Patent 1 has not conducted sufficient research on this, and there is still room for further improvement. [Prior Art Documents] [Patent Documents]

[Patent Document 1] International Publication No. 2008/066100

[The problem the invention aims to solve]

Therefore, the purpose of this invention is to provide a pigment dispersion composition for black matrices, which can yield a photoresist composition for black matrices. This photoresist composition can form a black matrix whose surface resistivity does not decrease even after high-temperature and prolonged baking, and whose breakpoints do not change with storage time. [Technical Means for Solving the Problem]

The inventors have discovered that a black matrix pigment dispersion containing a black colorant, a copper phthalocyanine sulfonate, and an epoxy compound can produce a black matrix photoresist composition that can form a black matrix whose surface resistance does not decrease even after baking at high temperatures for a long time, and whose breakpoints do not change with storage time, thus completing the present invention.

That is, the present invention is a black matrix pigment dispersion comprising a black pigment, a sulfonated copper phthalocyanine, and an epoxy compound. The epoxy compound preferably has a bisphenol backbone. Furthermore, the black matrix pigment dispersion of the present invention preferably further comprises an amine compound with a molecular weight of 300 or less, wherein the amine compound with a molecular weight of 300 or less is an amine compound having at least three secondary carbon atoms counting from the nitrogen atom of the amine group and/or an amine compound in which the amine group is linked to one or more aromatic rings via an hydrocarbon group having three or fewer carbon atoms. The amine compound with a molecular weight of 300 or less is preferably selected from at least one of 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine, and triisobutylamine. Furthermore, the sulfonated copper phthalocyanine molecule preferably has 0.5 to 3 sulfonic acid groups, more preferably 0.5 to 1.5 sulfonic acid groups. Furthermore, the aforementioned black pigment preferably contains carbon black. Furthermore, the aforementioned carbon black is preferably acidic carbon black. Furthermore, this invention is also a photoresist composition for black matrices, obtained from the aforementioned pigment dispersion composition for black matrices. Furthermore, this invention is also a black matrix, formed from the aforementioned photoresist composition for black matrices. [Effects of the Invention]

According to the present invention, a black matrix pigment dispersion composition can be provided, which can obtain a black matrix photoresist composition that can form a black matrix whose surface resistance does not decrease even after baking at high temperature for a long time, and whose breakpoints do not change with storage time.

<Black Matrix Pigment Dispersion Composition> The black matrix pigment dispersion composition of this invention contains a black colorant, a sulfonated copper phthalocyanine, and an epoxy compound, and satisfies either condition (A) or (B) below. (A) It does not contain amine compounds with a molecular weight of 300 or less. (B) It further contains amine compounds with a molecular weight of 300 or less, wherein the aforementioned amine compounds with a molecular weight of 300 or less are amine compounds having at least three secondary carbon atoms counting from the nitrogen atom of the amine group and/or amine compounds in which the amine group is linked to one or more aromatic rings via an hydrocarbon group having three or fewer carbon atoms. The components are described below.

(Black Pigment Agent) The black matrix pigment dispersion of this invention contains a black pigment. Preferably, the black pigment contains carbon black, and more preferably, the carbon black is acidic carbon black. The carbon black preferably has an average primary particle size of 20–60 nm, and more preferably, it is neutral carbon black and/or acidic carbon black with an average primary particle size of 20–60 nm. When the primary particle size of the black pigment is less than 20 nm or greater than 60 nm, it may lack sufficient light-blocking properties or have poor storage stability. Furthermore, the aforementioned average primary particle size is the arithmetic mean diameter obtained by electron microscopy.

From the perspective of effectively imparting surface resistivity, the aforementioned black colorant preferably contains only acidic carbon black. On the other hand, when using both neutral and acidic carbon black, the amount of neutral carbon black is preferably 85% by mass or less, and more preferably 75% by mass or less, relative to the total mass of neutral and acidic carbon black. When the content of neutral carbon black exceeds 85% by mass, a decrease in sealing strength may occur.

The above-mentioned acidic carbon black and neutral carbon black will be explained. Based on surface structure, carbon black can be broadly classified into acidic carbon black and neutral carbon black. Acidic carbon black refers to carbonaceous substances, either naturally occurring or artificially oxidized, which exhibit acidity when mixed with distilled water and boiled. On the other hand, neutral carbon black exhibits a neutral or higher pH when mixed with distilled water and boiled.

Regarding the aforementioned neutral carbon black, the optimal pH range is 8.0–10.0. 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) 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) manufactured by Mitsubishi Chemical.

Regarding the aforementioned acidic carbon blacks, the optimal pH range is 2.0–4.0. 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 Chemical; 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 28 nm, pH 4.0) manufactured by Orion Engineered Carbons. (approximately nm, pH approximately 2.8), etc.

From the perspective of effectively imparting pigment dispersibility or surface resistivity, the aforementioned black colorant is preferably SPECIAL BLACK 250 or NEROX 305.

Furthermore, regarding the pH mentioned above, 1 g of carbon black can be added to 20 ml of distilled water (pH 7.0) after carbonation has been removed, and the mixture can be stirred using a magnetic stirrer to prepare an aqueous suspension. The pH can then be measured using a glass electrode at 25°C (German Industrial Standard DIN ISO 787/9).

The content of the aforementioned black colorant, based on the mass fraction of the total solids content of the black matrix pigment dispersion of the present invention, is preferably 3-70% by mass, more preferably 10-50% by mass. If the content of the aforementioned black colorant is less than 3% by mass, the opacity during black matrix formation may be reduced; if the content of the aforementioned black colorant exceeds 70% by mass, the pigment may be difficult to disperse.

(Sulfonated Copper Phthalocyanine) The black matrix pigment dispersion of this invention contains a sulfonated copper phthalocyanine. In the micronization or dispersion step of the aforementioned black pigment, the basic skeleton of the sulfonated copper phthalocyanine is adsorbed onto the pigment surface. The sulfonic acid groups increase the affinity with organic solvents or pigment dispersants, thereby improving the micronization during dispersion or the dispersion stability of the aforementioned black pigment.

There are no particular limitations on the copper phthalocyanine in the aforementioned copper phthalocyanine sulfonates. It is acceptable to have a structure with a copper phthalocyanine skeleton, such as alkyl or halogen atoms, which are known substituents. However, from the perspective of ease of introducing sulfonic acid groups, it is preferable to have a structure without substituents.

The aforementioned sulfonated copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in its molecule. By having 0.5 to 3 sulfonic acid groups in the molecule in this way, a black matrix composition capable of obtaining a coating film with excellent surface resistivity can be manufactured. More preferably, the aforementioned sulfonated copper phthalocyanine has 0.5 to 1.5 sulfonic acid groups in its molecule, and even more preferably, 0.7 to 1.5 sulfonic acid groups. Furthermore, the number of sulfonic acid groups in the above molecule can be calculated based on the ratio of sulfur atoms to copper atoms obtained from elemental analysis.

As sulfonates of the aforementioned copper phthalocyanine, commercially available products can also be used, such as: desodium derivatives of Solsperse 12000 (both manufactured by Lubrizol Corporation of Japan) or VALIFAST BLUE 1605, etc.

The content of the copper phthalocyanine sulfonate is preferably 0.1 to 20 parts by weight, and more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the black colorant mentioned above.

(Epoxy Compounds) The pigment dispersion composition for the black matrix of this invention contains epoxy compounds. By containing the aforementioned epoxy compounds, the functional groups present on the surface of the multifunctional epoxy resin and the carbon black interact well, thereby presumably forming a black matrix whose surface resistivity does not decrease even after high-temperature and long-term baking. However, this invention can also be interpreted in ways not limited to the above mechanism.

Examples of the aforementioned epoxides include: Epolight 4000 and Epolight 3002 (both manufactured by Kyoei Chemicals); DENACOL DLC-101, DENACOL DLC-202, DENACOL EX-141, DENACOL EX-142, DENACOL EX-145, DENACOL EX-146, and DENACOL... EX-147 (all manufactured by Nagase Kasei Corporation); GAN, GOT, NC2000-L, NC3000, NC3000-L, NC3000-H, NC3000-FH-75M, NC3100, CER3000-L, XD1000, NC7000L, NC7300L, EPPN-201, EPPN-501H, EPPN-501HY, EPPN502H, EOCN-102 0, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, RE303S-L, RE310S (all manufactured by Nippon Kayaku Co., Ltd.); jER157S70, jER828, jER1002, jER1032H60, jER1750, jER1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Mitsubishi). (Manufactured by Chemical Company); EPICLON EXA-9583, EPICLON N695, HP4032, HP5000, HP7200L (all manufactured by DIC Company); VG3101 (manufactured by Mitsui Chemicals); Epotohto YH-434L (manufactured by Toto Chemicals); VG3101L (manufactured by Air Water), etc.

The epoxy compound is preferably selected from at least one of the groups consisting of (Formula 1) to (Formula 7) below. Among the epoxy compounds mentioned above, from the viewpoint of forming a black matrix with particularly excellent surface resistance and sealing strength, it is more preferably to have a bisphenol backbone, and even more preferably to have the structure of (Formula 2) below.

Based on the mass fraction of the total solids content of the black matrix pigment dispersion of the present invention, the content of the aforementioned epoxy compound is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. Furthermore, based on the mass fraction of the total solids content of the black matrix pigment dispersion of the present invention, the content of the aforementioned epoxy resin is preferably 12.0% by mass or less, more preferably 10.0% by mass or less, and even more preferably 9.0% by mass or less.

(Amine compounds with a molecular weight of 300 or less) Based on the viewpoint of forming a black matrix with a high surface resistivity that can be maintained even after high-temperature and long-term baking, the pigment dispersion composition of the black matrix of the present invention contains an amine compound with a molecular weight of 300 or less. Preferably, the amine compound with a molecular weight of 300 or less is an amine compound having at least three secondary carbon atoms counting from the nitrogen atom of the amine group and/or an amine compound in which the amine group is linked to one or more aromatic rings via an hydrocarbon group having three or fewer carbon atoms.

The aforementioned amine compounds with a molecular weight of 300 or less are amine compounds having at least three secondary carbon atoms counting from the nitrogen atom of the amine group, and/or amine compounds in which the amine group is linked to one or more aromatic rings via an hydrocarbon group having three or fewer carbon atoms. By containing such amine compounds, the electron pair on the nitrogen atom is buried by a large substituent. As a result, in the neutralization of the aforementioned amine compound and copper phthalocyanine sulfonate, the ionicity becomes moderate, thus suppressing the electrophoresis caused by this ionicity. Furthermore, it is believed that the steric hindrance generated by the large substituent inhibits the proximity of pigment particles. However, the invention can also be interpreted in ways not limited to the above mechanism.

Regarding the aforementioned amine compounds having secondary or higher carbon atoms within three atoms of the nitrogen atom of the amine group, preferably those having secondary or higher carbon atoms within three atoms of the nitrogen atom of all amine groups present in the amine compound, examples include: 1,1,3,3-tetramethylbutylamine, diisopropylamine, triisopropylamine, diisobutylamine, triisobutylamine, diisopentylamine, triisopentylamine, tri(2-ethylhexyl)amine, etc. Furthermore, the term "within three atoms of the nitrogen atom of the amine group" refers to the atom adjacent to the nitrogen atom of the amine group as 1, the atom adjacent to the aforementioned atom adjacent to the nitrogen atom as 2, and the atom adjacent to the aforementioned atom adjacent to the atom adjacent to the nitrogen atom as 3.

Examples of amine compounds in which the above-mentioned amino group is linked to one or more aromatic rings via an amino group having three or fewer carbon atoms include: 3-phenylpropylamine, 2-phenylpropylamine, 1-phenylpropylamine, 2-phenylethylamine, 1-phenylethylamine, phenylmethylamine, triphenylmethylamine, etc.

As for the amine compound with a molecular weight of less than 300, from the viewpoint of effectively improving the surface resistance, it is preferably selected from at least one of 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine, and triisobutylamine.

Compared to 100 parts by mass of the aforementioned copper phthalocyanine sulfonate, the aforementioned amine compound with a molecular weight of less than 300 is preferably 5 to 100 parts by mass, and more preferably 20 to 60 parts by mass.

(Organic Solvent) The pigment dispersion composition for the black matrix of this invention preferably contains an organic solvent. As the aforementioned organic solvent, organic solvents conventionally used in the field of liquid crystal black matrix photoresists are suitable.

Specifically, ^the aforementioned organic solvents 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 with a boiling point of 100–250°C at atmospheric pressure (1.013 × 10² kPa). If a large amount of the aforementioned organic solvents with a boiling point exceeding 250°C is contained, the following situation occurs: when a coating film formed by applying a black matrix photoresist composition obtained from the black matrix pigment dispersion composition of the present invention is pre-baked, the organic solvents do 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 coating contains a large amount of organic solvents with a boiling point below 100°C, it will be difficult to apply the coating evenly without unevenness, resulting in the inability to obtain a coating film with excellent surface smoothness.

Specific examples of the aforementioned organic solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc., which are ether-based organic solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., which are ether-ester organic solvents; methyl isobutyl ketone, cyclohexanone, 2-heptanone. Ketone solvents such as δ-butyrolactone; ester 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 ethoxypropionate, ethyl hydroxypropionate, and n-pentyl formate; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These can be used alone or in combination of two or more.

Among the aforementioned organic solvents, based on considerations of solubility, dispersibility, and coatability, 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, and n-pentyl formate are preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being even more preferred.

(Pigment Dispersant) The pigment dispersion composition for black matrices of this invention preferably contains a pigment dispersant. The aforementioned pigment dispersant is a basic-group pigment dispersant, and can include: anionic surfactants, basic-group polyester-based pigment dispersants, basic-group acrylic-based pigment dispersants, basic-group amine ester-based pigment dispersants, basic-group carbodiimide-based pigment dispersants, and acidic polymeric pigment dispersants, etc. These basic-group pigment dispersants can be used alone, or in combination of two or more. Among these, basic-group polymeric pigment dispersants are preferred for obtaining good pigment dispersibility.

Specific examples of the above-mentioned polymeric pigment dispersants containing alkaline groups include: (1) A reaction product of an amino and/or imine group of a polyamine compound (e.g., poly(lower alkylamines) such as polyallylamine, polyethyleneamine, and polyethylene polyimide) with at least one of a group consisting of polyesters, polyamides, and polyesteramides having free carboxyl groups (Japanese Patent Application Publication No. 2001-59906); (2) A reaction product of a low-molecular-weight amino compound such as poly(lower)alkylimide or methyliminodipropylamine with a polyester having free carboxyl groups (Japanese Patent Application Publication No. Sho 54-37082, Japanese Patent Application Publication No. Hei 01-311177); (3) A reaction product obtained by sequentially reacting the isocyanate group of a polyisocyanate compound with an alcohol such as methoxy polyethylene glycol or a polyester such as caprolactone polyester having one hydroxyl group, a compound having two to three isocyanate reactive functional groups, and an aliphatic or heterocyclic hydrocarbon compound having an isocyanate reactive functional group and a tertiary amine group (Japanese Patent Application Publication No. 02-612); (4) A compound obtained by reacting a polymer of acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amine group; (5) A reaction product obtained by adding a polyether chain to a low molecular weight amine compound; (6) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amine group (Japanese Patent Application Publication No. 04-210220); (7) A reaction product formed by reacting a polyepoxide compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amine group (Japanese Patent Application Publication No. 09-87537); (8) A reaction product formed by reacting a polycarbonate compound having a single-terminal functional group capable of reacting with an amine group with a polyamine compound (Japanese Patent Application Publication No. 09-194585); (9) A copolymer selected from at least one of the following methacrylates or acrylates: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, etc.; at least one of the following polymerizable monomers containing an alkaline group: acrylamide, methacrylamide, N-hydroxymethylamide, vinylimidazole, vinylpyridine, monomers having an amino group and a polycaprolactone backbone; and at least one of the following polymerizable monomers: styrene, styrene derivatives, etc. (Japanese Patent Application Publication No. 01-164429); (10) A carbodiimide pigment dispersant containing an alkaline group (International Publication No. WO04/000950); (11) A block copolymer composed of blocks having basic groups such as tertiary amine groups and quaternary ammonium salt groups, and blocks without functional groups (see Japanese Patent Application Publication No. 2005-55814); (12) A pigment dispersant obtained by reacting polyallylamine with a polycarbonate compound via a macoric addition reaction (Japanese Patent Application Publication No. Hei 09-194585); (13) A carbodiimide compound having at least one polybutadiene chain and at least one basic nitrogen-containing group (Japanese Patent Application Publication No. 2006-257243); (14) A carbodiamide compound having at least one side chain containing a amide group and at least one basic nitrogen group (Japanese Patent Application Publication No. 2006-176657); (15) A polyurethane compound having structural units containing ethylene oxide and propylene oxide chains and having amine groups quaternized by a quaternizing agent (Japanese Patent Application Publication No. 2009-175613); (16) A compound obtained by reacting the isocyanate group of an isocyanate compound having an isocyanate ring within its molecule with the active hydrogen group of a compound having an active hydrogen group and a carbazole ring and/or an azobenzene skeleton within its molecule, wherein the amount of carbazole ring and azobenzene skeleton in the molecule of the compound is 15-85% relative to the sum of the isocyanate group derived from the isocyanate compound having an isocyanate ring and the amine ester bonds and urea bonds generated by the reaction of the isocyanate group with the active hydrogen group (Japanese Patent Application 2009-220836); (17) Graft copolymers, etc., formed by introducing polyether or polyester side chains into an acrylate polymer having an amino group.

Among the aforementioned alkaline-containing polymeric pigment dispersants, more preferably are alkaline-containing amine ester-based polymeric pigment dispersants, alkaline-containing polyester-based polymeric pigment dispersants, and alkaline-containing acrylic polymeric pigment dispersants; even more preferably are amine ester-based polymeric pigment dispersants, amine-containing polyester-based polymeric pigment dispersants, and amine-containing acrylic polymeric pigment dispersants. Among the aforementioned alkaline-containing polymeric pigment dispersants, particularly preferably are polymeric pigment dispersants having at least one alkaline-containing (amine) group selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains.

The content of the above-mentioned pigment dispersant is preferably 1 to 200 parts by weight, and more preferably 5 to 100 parts by weight, relative to 100 parts by weight of the above-mentioned black colorant.

(Adhesive Resin) The pigment dispersion composition for the black matrix of this invention preferably contains an adhesive resin.

Examples of such adhesive resins include: thermosetting resins, thermoplastic resins, photopolymerizable compounds, and alkali-soluble resins. These can be used alone or in combination of two or more.

Examples of the aforementioned thermosetting or thermoplastic resins include: butyraldehyde resin, styrene-butadiene 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, cyclic rubber, epoxy resin, cellulose resin, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, etc.

Examples of photopolymerizable compounds include monomers having one or more photopolymerizable unsaturated bonds in their molecules, and oligomers having photopolymerizable unsaturated bonds.

As monomers possessing one photopolymerizable unsaturated bond within the aforementioned molecules, examples include: methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and other alkyl methacrylates or alkyl acrylates; benzyl methacrylate, benzyl acrylate, and other aralkyl methacrylates or aralkyl acrylates; butoxyethyl methacrylate, butoxyethyl acrylate, and other alkoxyalkyl methacrylates or alkoxyalkyl acrylates; N,N-methacrylate - Dimethylaminoethyl ester, N,N-dimethylaminoethyl acrylate and other aminoalkyl methacrylates or aminoalkyl acrylates; diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether and other polyalkylene glycol monoalkyl ethers of methacrylate or acrylate; hexaethylene glycol monophenyl ether and other polyalkylene glycol monoaryl ethers of methacrylate or acrylate; isocamphene methacrylate or isocamphene acrylate; glycerol methacrylate or glycerol acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, etc.

As monomers possessing two or more photopolymerizable unsaturated bonds within the aforementioned molecules, examples include: bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl tetramethyl acrylate, neopentyl tetramethyl acrylate, dine ... Hexamethacrylate, dinepentylenetetroxide pentamethacrylate, epoxy methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, neopentylenetetroxide triacrylate, neopentylenetetroxide tetraacrylate, dinepentylenetetroxide tetraacrylate, dinepentylenetetroxide hexaacrylate, dinepentylenetetroxide pentaacrylate, epoxy acrylate, etc.

As the oligomers possessing the aforementioned photopolymerizable unsaturated bonds, oligomers obtained by appropriately polymerizing the aforementioned monomers can be used. The aforementioned adhesive resins can be used alone or in combination of two or more.

From the perspective of heat resistance and development properties, epoxy acrylate resin is preferred as the aforementioned adhesive resin.

The above-mentioned alkali-soluble resins will be explained later.

The content of the above-mentioned adhesive resin is preferably 3 to 50% by mass relative to the total solids content of the black matrix pigment dispersion of the present invention.

(Manufacturing Method of Pigment Dispersion for Black Matrix) The pigment dispersion for black matrix of this invention can be obtained by adding the aforementioned components and then mixing and milling them. The milling method is not particularly limited; for example, any bead mill, ready mill, ultrasonic homogenizer, high-pressure homogenizer, paint shaker, ball mill, roller mill, sand mill, sand grinder, dyno-mill, dispermat, SC mill, nanorizer, etc., can be used, and milling can be performed using known methods.

<Photoresist Composition for Black Matrix> This invention is also a photoresist composition for black matrix, obtained from the pigment dispersion composition for black matrix of this invention.

(Black Matrix Pigment Dispersion) The black matrix photoresist composition of the present invention contains the aforementioned black matrix pigment dispersion composition. The content of the aforementioned black matrix pigment dispersion composition, based on the total mass of the black matrix photoresist composition of the present invention, is preferably 30-80% by mass, more preferably 40-75% by mass.

(Photopolymerization Initiator) The photoresist composition for the black matrix of this invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, as long as it can generate free radicals or cations by irradiation with active energy lines such as ultraviolet light or electron beams. Examples include: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylgoxymeta-ethyl ketone), benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzene Photopolymerization initiators include azodimethyl ketone, α-hydroxyisobutyl benzophenone, 9-oxosulfur, 2-chloro-9-oxosulfur, 1-hydroxycyclohexylphenyl ketone, tributylanthraquinone, 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-linylpropane-1-one, and other benzophenone-based, 9-oxosulfur-based, anthraquinone-based, and tri-based photopolymerization initiators. The above photopolymerization initiators can be used alone or in combination of two or more.

The content of the above photopolymerization initiator is preferably 1 to 20% by mass relative to the total solids content of the photoresist composition for black matrix of the present invention.

(Photopolymerizable Compound) The photoresist composition for black matrices of this invention preferably contains a photopolymerizable compound. As the aforementioned photopolymerizable compound, a photopolymerizable compound described in the aforementioned pigment dispersion composition for black matrices may be appropriately selected.

The content of the above-mentioned photopolymerizable compound is preferably 0.1 to 50% by mass relative to the total solids content of the photoresist composition for black matrix of the present invention.

(Alkali-soluble resin) The photoresist composition for the black matrix of this invention preferably contains an alkaline-soluble resin. Preferably, this alkaline-soluble resin acts as a binder for the aforementioned black pigment and is soluble in the developing solution, especially an alkaline developing solution, used in the developing process during the manufacture of the black matrix.

The aforementioned alkaline-soluble resin can also be configured as a block copolymer. By using block copolymers, pigment dispersion is improved compared to other copolymers, thus imparting solubility in PGMEA or alkaline developing solutions. Preferably, the block copolymer is a block copolymer having blocks composed of ethylene unsaturated monomers having one or more carboxyl groups, and blocks composed of other copolymerizable ethylene unsaturated monomers.

There are no particular limitations on the block copolymers mentioned above, and conventionally used block copolymers can be used. Specifically, copolymers of carboxyl-containing ethylene unsaturated monomers such as acrylic acid and methacrylic acid, and at least one ethylene unsaturated monomer capable of copolymerizing with the carboxyl-containing ethylene unsaturated monomer, are 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-phenylcis-diimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, diacrylate carboacrylate epoxy ester, and oligomers. Ideally, N-vinylpyrrolidone and sulfur-containing monomers should not be used. The block copolymers described above can be synthesized using block resins synthesized through living radical polymerization or anionic polymerization. Some of the block sites in the aforementioned block copolymers can also be composed of random copolymers.

As the aforementioned alkali-soluble resin, alkali-soluble cardo resin can also be used. Examples of alkali-soluble cardo resins include epoxy (meth)acrylate adducts with a rudimentary skeleton, which are addition products of epoxy (meth)acrylate derivatives and dicarboxylic anhydrides and/or tetracarboxylic dianhydrides. Furthermore, this alkali-soluble resin may also possess photopolymerizable functional groups.

From a developmental perspective, the acid value of the aforementioned alkaline-soluble resin is preferably 5–300 mgKOH/g, more preferably 5–250 mgKOH/g, further preferably 10–200 mgKOH/g, and particularly preferably 60–150 mgKOH/g. Furthermore, in this specification, the above acid values are theoretical acid values, calculated arithmetically based on the content of carboxyl-containing unsaturated ethylene monomers.

Based on the viewpoint of developing properties or solubility in organic solvents, the weight-average molecular weight of the aforementioned alkaline-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. Furthermore, in this invention, the aforementioned weight-average molecular weight is based on the weight-average molecular weight of polystyrene obtained by GPC. In this specification, a Water 2690 (manufactured by Waters Corporation) is used as the apparatus for determining the aforementioned weight-average molecular weight, and a PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) is used as the column.

Relative to 100 parts by weight of the aforementioned black colorant, the content of the aforementioned alkali-soluble resin is preferably 1 to 200 parts by weight, and more preferably 10 to 150 parts by weight. In this case, if the content of the aforementioned alkali-soluble resin is less than 1 part by weight, the developing properties may decrease; if the content of the aforementioned alkali-soluble resin exceeds 200 parts by weight, the concentration of the aforementioned black colorant will relatively decrease, thus making it difficult to achieve the target color concentration for use as a film.

The aforementioned alkali-soluble resin is preferably free of any of the primary, secondary, and tertiary amino groups, and further free of quaternary ammonium groups. More preferably, it is free of alkaline groups. Furthermore, alkali-soluble resins with structures other than block copolymers may be incorporated, without impairing the effects achieved by the present invention.

(Organic Solvent) As the aforementioned organic solvent, any organic solvent described in the above-mentioned black matrix pigment dispersion composition may be appropriately selected.

The content of the aforementioned organic solvent is based on the total mass of the photoresist composition for the black matrix of the present invention, preferably 1 to 40% by mass, more preferably 5 to 35% by mass.

(Other Additives) The photoresist composition for the black matrix of this invention can be appropriately supplemented with various additives such as thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants, as needed.

(Breakpoint) The breakpoint change of the black matrix pigment-dispersed photoresist composition of this invention, immediately after fabrication and after storage at 60°C for one week, is preferably within ±3 seconds, more preferably within ±2 seconds, further preferably within ±1.5 seconds, even more preferably within ±1.0 second, and most preferably within ±0.5 seconds. If the breakpoint change is within ±3 seconds, it can be determined that it sufficiently possesses the property that the breakpoint will not change with storage time. Furthermore, the above-mentioned breakpoint change can be measured using the following method. Using a rotary coating machine, the black matrix pigment-dispersed photoresist composition is coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm, and pre-baked at 100°C for 2 minutes. Subsequently, photomasks with line patterns of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm were exposed using a high-pressure mercury lamp at a UV cumulative light intensity of 50 mJ/ ^cm² , to fabricate a photoresist film containing the exposed (cured) portion. Next, using a 0.05% potassium hydroxide aqueous solution (developer), at 23°C and a spray pressure of 1.0 kgf/ ^cm² , the time breakpoint at which the developing pattern begins to appear was measured. Using the above method, the breakpoint immediately after fabrication (BP1) and the breakpoint after storage at 60°C for one week (BP2) were measured, and ΔBP (change in breakpoint) can be calculated using the following formula: ΔBP = BP2 - BP1

(Manufacturing Method of Photoresist Component for Black Matrix) As a method for manufacturing the photoresist component for black matrix of the present invention, it can be manufactured, for example, by producing the pigment dispersion component for black matrix of the present invention, then adding the remaining material and mixing it using a stirring device or the like. The above-mentioned stirring and mixing method is not particularly limited, and known methods such as ultrasonic dispersers, high-pressure emulsifiers, bead mills, three-roll mills, granulators, and kneaders can be used. Furthermore, the mixture can also be filtered using a filter after the above-mentioned stirring and mixing. Furthermore, when manufacturing the photoresist composition for the black matrix of this invention, the aforementioned black colorant, epoxy resin, and compound described in the pigment dispersion composition for the black matrix of this invention may be added as needed.

<Black Matrix> The black matrix of this invention is formed using photoresist.

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: coating a photoresist composition of the black matrix of the present invention on a transparent substrate and drying it to form a coating film; then placing a photomask on the coating film; exposing and developing images through the photomask; and photocuring as needed.

The methods for coating, drying, exposing, and developing the photoresist composition of the black matrix of this invention can be appropriately selected from known methods. Furthermore, as the aforementioned transparent substrate, known transparent substrates such as glass substrates and plastic substrates can be appropriately used.

The thickness of the coating, measured after drying, is preferably 0.2–10 μm, more preferably 0.5–6 μm, and even more preferably 1–4 μm. By setting the thickness within the above range, the specified pattern can be well displayed, and the specified optical concentration can be well imparted.

Regarding the black matrix of this invention, it is coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm using a rotary coating machine. After pre-baking at 100°C for 2 minutes, it is exposed using a high-pressure mercury lamp (UV cumulative light intensity 50 mJ/ ^cm2 ) and then baked at 230°C for 3 hours to produce a black photoresist pattern formed only by the solid portion. The surface resistivity at this time is preferably 1.0×10 ¹⁴ Ω/□ or higher, more preferably 3.0×10 ¹⁴ Ω/□ or higher, further preferably 5.0×10 ¹⁴ Ω/□ or higher, even more preferably 9.0×10 ¹⁴ Ω/□ or higher, and most preferably 1.0×10 ¹⁵ Ω/□ or higher. If the surface resistance value is 1.0 × ^10¹⁴ Ω/□ or higher, short circuits or current leakage can be effectively prevented. Furthermore, the surface resistance value can be measured using either the main body: a micro current meter R8340, or the option: a shielded box R12702A (both manufactured by ADVANCE).

Regarding the black matrix of this invention, it is coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm using a rotary coating machine. After pre-baking at 100°C for 2 minutes, it is exposed using a high-pressure mercury lamp (UV cumulative light intensity 50 mJ/ ^cm² ), then baked at 230°C for 3 hours, followed by baking at 250°C for 1 hour, to produce a black photoresist pattern formed solely by the solid portion. The surface resistivity at this stage is preferably 1.0 × ^10¹⁴ Ω/□ or higher, more preferably 2.0 × ^10¹⁴ Ω/□ or higher, further preferably 5.0 × ^10¹⁴ Ω/□ or higher, particularly preferably 9.0 × ^10¹⁴ Ω/□ or higher, and most preferably 1.0 × ^10¹⁵ Ω/□ or higher. Ω/□ or higher. If the surface resistance value is 1.0×10 ¹⁴ Ω/□ or higher, it can still have an excellent surface resistance value even after baking at high temperature for a long time.

The black matrix pigment dispersion, black matrix photoresist composition, and black matrix of this invention, due to the aforementioned characteristics, are suitable for use as black matrices in image display devices or touch panels, etc. [Example]

The present invention will be specifically described below using embodiments. However, the present invention is not limited to these embodiments as long as they do not depart from the spirit and scope of the present invention. Furthermore, in the present embodiments, unless otherwise specified, "parts" and "%" respectively represent "parts by mass" and "% by mass".

The various materials used in the following embodiments and comparative examples are described below. <Black Pigment> Carbon Black (trade name "NEROX 305", average primary particle size approximately 28 nm, pH approximately 2.8, manufactured by Orion Engineered Carbons) <Pigment Dispersant> LPN22102 (block type pigment dispersant with amine groups, solids content 40% by mass, manufactured by BYK-Chemie) <Epoxides> VG3101L (epoxide compound with the structure of (Formula 2) above, trade name "TECHMORE VG3101L", manufactured by Printec) <Amines> 3-Phenylacetylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1,1,3,3-Tetramethylbutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) Triisobutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) <Adhesive Resins> ZCR-1569H (Epoxy acrylate resin, solids content 70% by weight, manufactured by Nippon Kayaku Co., Ltd.) <Organic Solvent> PM (Propylene Glycol Monomethyl Ether) PGMEA (Propylene Glycol Monomethyl Ether Acetate) <Photopolymerization Initiator> OXE 02 (Product name "Irgacure OXE 02", 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylatedoxime) acetone, manufactured by BASF) <Photopolymerizable Compound> DPHA (Dipentaerythritol Hexaacrylate) <Alkali-Soluble Resin> WR-301 (Product name "WR-301", calorie resin, acid value 100) (mgKOH/g, solids content 45% by weight, manufactured by ADEKA)

<Preparation of Dispersion Compounds> (Dispersion Compound 1) Solsperse 12000 (a sulfonated copper phthalocyanine compound (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Corporation, Japan) and 3-phenylpropylamine were mixed at a mass ratio of 25:8 to obtain Dispersion Compound 1. (Dispersion Compound 2) Solsperse 12000 (a sulfonated copper phthalocyanine compound (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Corporation, Japan) and 1,1,3,3-tetramethylbutylamine were mixed at a mass ratio of 10:3 to obtain Dispersion Compound 2. (Dispersion Component 3) Solsperse 12000 (a sulfonated copper phthalocyanine compound (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Corporation, Japan) was mixed with triisobutylamine at a mass ratio of 25:11 to obtain dispersion component 3.

<Dispersion Materials> Solsperse 12000 (Sulfonated copper phthalocyanine (approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Corporation, Japan) Solsperse 5000 (A quaternary ammonium salt of sulfonated copper phthalocyanine (approximately 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol Corporation, Japan) VALIFAST BLUE 1605 (VB 1605, Sodium neutralized sulfonated copper phthalocyanine, manufactured by Orient Chemical Industries, Ltd.)

<Preparation of Pigment Dispersion for Black Matrix> The materials were mixed as shown in Table 1, and then kneaded overnight using a bead mill to produce a pigment dispersion for black matrix.

[Table 1] Pigment dispersions for black matrix 1 2 3 4 5 6 7 Black colorant carbon black 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Pigment dispersants LPN22102 (Solids content 40% by mass) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Dispersible components Dispersion component 1 0.6 - - - - - 0.6 Dispersion component 2 - 0.6 - - - - - Dispersion component 3 - - 0.6 - - - - Dispersion materials Solsperse 12000 - - - 0.6 - - - Solsperse 5000 - - - - 0.6 - - VB 1605 - - - - - 0.6 - Adhesive resin ZCR-1569H (70% by weight of solids) 6.8 6.8 6.8 6.8 6.8 6.8 7.8 Epoxy compounds VG3101L 1.0 1.0 1.0 1.0 1.0 1.0 - organic solvents PM 6.0 6.0 6.0 6.0 6.0 6.0 6.0 PGMEA 61.6 61.6 61.6 61.6 61.6 61.6 61.6 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

<Preparation of Photoresist Components for Black Matrix Applications> Using a high-speed mixer, the above-mentioned black matrix pigment dispersion composition was uniformly mixed with other materials (photopolymerizable compound, alkaline soluble resin, photopolymerization initiator, and organic solvent) as shown in Table 2. The mixture was then filtered using a 3 μm pore size filter to obtain the black matrix photoresist compositions of the embodiments and comparative examples.

<Evaluation Test> (Surface Resistance Value 1) Using a rotary coating machine, the pigment-dispersed photoresist compositions of the black matrices of the embodiments and comparative examples were coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm. After pre-baking at 100°C for 2 minutes, they were exposed using a high-pressure mercury lamp (UV cumulative light intensity 50 mJ/ ^cm² ), and then baked at 230°C for 3 hours to produce black photoresist patterns (black matrices) formed only by the solid portion. The surface resistance values of the produced black photoresist patterns were measured using a micro-current meter R8340 (body) and a shielded box R12702A (optional, both manufactured by ADVANCE). The results are shown in Table 2.

(Surface Resistance Value 2) Using a rotary coating machine, the pigment-dispersed photoresist compositions of each black matrix in the embodiments and comparative examples were coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm. After pre-baking at 100°C for 2 minutes, they were exposed using a high-pressure mercury lamp (UV cumulative light intensity 50 mJ/ ^cm² ), then baked at 230°C for 3 hours, followed by baking at 250°C for 1 hour, to produce black photoresist patterns (black matrices) formed only by the solid portion. The surface resistance values of each black photoresist pattern were measured using a micro-current meter R8340 (body) and a shielded box R12702A (optional, both manufactured by ADVANCE). The results are shown in Table 2.

(Breakpoint Variation) For the black matrix pigment-dispersed photoresist compositions of the embodiments and comparative examples, the breakpoints were measured immediately after fabrication and after storage at 60°C for one week using the following method. Using a rotary coating machine, each black matrix pigment-dispersed photoresist composition was coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm, and pre-baked at 100°C for 2 minutes. Subsequently, photomasks with line patterns of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm were used for exposure using a high-pressure mercury lamp with a UV cumulative light dose of 50 mJ/ ^cm² , to fabricate a photoresist film including the exposed portion (cured portion). Next, using a 0.05% potassium hydroxide aqueous solution (developer), at a spray pressure of 1.0 kgf/ ^cm² , the time breakpoint at which the developing pattern began to appear was determined. Using the breakpoint immediately after fabrication (BP1) and the breakpoint after storage at 60°C for one week (BP2), ΔBP (change in breakpoint) was calculated using the following formula. The results are shown in Table 2. ΔBP = BP2 - BP1

[Table 2] Photoresist assemblies for black matrices Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Pigment dispersions for black matrix 1 63.6 - - - - - - 2 - 63.6 - - - - - 3 - - 63.6 - - - - 4 - - - 63.6 - - - 5 - - - - 63.6 - - 6 - - - - - 63.6 - 7 - - - - - - 63.6 Photopolymerization initiator OXE 02 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Photopolymer compounds DPHA 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Alkali-soluble resins WR-301 (solids content 45% by weight) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 organic solvents PGMEA 24.4 24.4 24.4 24.4 24.4 24.4 24.4 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Evaluation results Surface resistance 1 (Ω/□) 1.9×10 ¹⁵ 1.7×10 ¹⁵ 1.6×10 ¹⁵ 3.1×10 ¹⁴ 1.6×10 ¹³ 5.8×10 ¹³ 1.2×10 ¹⁵ Surface resistance value 2 (Ω/□) 1.5×10 ¹⁴ 1.0×10 ¹⁵ 2.0×10 ¹⁵ 2.9×10 ¹⁴ 3.0×10 ¹¹ 2.0×10 ¹³ 2.5×10 ¹² ΔBP (seconds) -1.9 -2.4 -0.2 -1.3 -5.9 -12.4 -6.6

In an embodiment using a black matrix pigment dispersion containing a black colorant, a copper phthalocyanine sulfonate, and an epoxy compound, it has been confirmed that a black matrix photoresist composition can be obtained that forms a black matrix whose surface resistivity does not decrease even after high-temperature and prolonged baking, and whose breakpoints do not change with storage time. Furthermore, it has been confirmed that by satisfying the above condition (B), a black matrix with a high surface resistivity that does not decrease even after high-temperature and prolonged baking can be formed. [Industrial Applicability]

According to the present invention, a black matrix pigment dispersion composition can be provided, which can obtain a black matrix photoresist composition that can form a black matrix whose surface resistance does not decrease even after baking at high temperature for a long time, and whose breakpoints do not change with storage time.

without

without

Claims (8)

A black matrix pigment dispersion comprising a black colorant, a sulfonated copper phthalocyanine, and an epoxy compound. The black colorant contains carbon black, and its content is 3-70% by mass relative to the total solids content of the black matrix pigment dispersion. The epoxy compound has a bisphenol skeleton, and its content is 1% to 12.0% by mass relative to the total solids content of the black matrix pigment dispersion. The content of the sulfonated copper phthalocyanine is 0.1-20 parts by mass relative to 100 parts by mass of the black colorant. For example, the black matrix pigment dispersion composition of claim 1 further contains an amine compound with a molecular weight of 300 or less, and the aforementioned amine compound with a molecular weight of 300 or less is an amine compound having a secondary or higher carbon atom within 3 atoms from the nitrogen atom of the amine group and/or an amine compound in which the amine group is linked to one or more aromatic rings by an hydrocarbon group having 3 or fewer carbon atoms. For example, in the black matrix pigment dispersion composition of claim 2, the amine compound with a molecular weight of 300 or less is selected from at least one of 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine, and triisobutylamine. For example, in the black matrix pigment dispersion composition of claim 1 or 2, the sulfonated copper phthalocyanine has 0.5 to 3 sulfonic acid groups in the molecule. For example, in the black matrix pigment dispersion composition of claim 4, the sulfonated copper phthalocyanine has 0.5 to 1.5 sulfonic acid groups in the molecule. For example, the black matrix pigment dispersion composition of claim 1 or 2, wherein the carbon black is acidic carbon black. A photoresist composition for black matrices, obtained from any one of claims 1 to 6 for a pigment dispersion composition for black matrices. A black matrix formed by using photoresist as a component of the black matrix of claim 7.