TW202225336A - Pigment dispersion composition for black matrix, resist composition for black matrix and black matrix - Google Patents

Abstract

The present invention provides a pigment dispersion composition for a black matrix capable of forming black matrix having a higher surface resistance value. The pigment dispersion composition for the black matrix of the present invention contains a black coloring agent, a sulfonated compound of copper phthalocyanine, and an amine compound, and the above amine compound is selected from at least one of the following (A) and (B), wherein (A) is an amine compound having a secondary or higher carbon atom within three atoms from the nitrogen atom of the amino group, and (B) is an amine compound in which the amino group is connected to one or more aromatic rings via a hydrocarbon group having three or less carbon atoms.

Description

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

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

In the image display device using liquid crystal or plasma, etc., a light-shielding film (black matrix) is provided in the gap of the coloring pattern in the display area of the screen or the edge of the peripheral portion of the display area. In addition, in the liquid crystal display using TFT, A light-shielding film (black matrix) is provided on the outside light side of the TFT, etc. In addition, regarding the function of the light-shielding film, in the liquid crystal display device, the leakage of light from the backlight source is mainly prevented from being reflected on the screen, and in the plasma display device, the color bleeding caused by the turbidity of each color light is mainly prevented from being reflected on the screen. , thereby improving display characteristics (contrast and color purity).

For example, a color filter for converting white light of a backlight source of a liquid crystal display device into colored light is usually produced by the following method, that is, on the surface of a transparent substrate such as a glass or a plastic sheet on which a black matrix is formed, a strip of Pixels of different hues of red, green, and blue are formed in sequence in a pattern such as a shape or a mosaic shape.

In addition, in a touch panel formed by combining an image display device and a position input device, a color filter formed with a black matrix as a light-shielding film is similarly used. Conventionally, it has been generally formed between the sensor substrate and the sensor substrate through a cover glass. opposite side. However, with the increasing demand for the light weight of the touch panel, the technology of forming the light-shielding film and the touch sensor on the same side of the cover glass at the same time is being actively developed, so as to achieve a lighter weight.

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

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

In the black matrix, a higher surface resistance value is required in order to prevent short circuit or current leakage. However, in Patent Document 1, the surface resistance value is not sufficiently studied, and there is still room for further improvement. [Prior Art Literature] [Patent Literature]

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

[The problem to be solved by the invention]

Therefore, the objective of this invention is to provide the pigment dispersion composition for black matrices which can form the black matrix which has a high surface resistance value. [Technical means to solve the problem]

The inventors of the present invention found that by further including a specific amine compound in the pigment dispersion composition for black matrices containing a black colorant and a sulfonated compound of copper phthalocyanine, a black matrix capable of forming a black matrix having a high surface resistance value can be obtained The pigment dispersion composition for a matrix has completed the present invention.

That is, the present invention is a pigment dispersion composition for a black matrix, which contains a black colorant, a sulfonated compound of copper phthalocyanine, and an amine compound, wherein the amine compound is at least one selected from the following (A) and (B) kind; (A) Amine compounds having two or more carbon atoms within 3 atoms from the nitrogen atom of the amine group, (B) An amine compound in which an amine group is linked to one or more aromatic rings via a hydrocarbon group having 3 or less carbon atoms. The above-mentioned amine compound is preferably at least one selected from the group consisting of 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine, and triisobutylamine. Moreover, it is preferable that the sulfonate of the said copper phthalocyanine has 0.5-3 sulfonic acid groups in a molecule|numerator, and it is more preferable that it has 0.5-1.5 sulfonic acid groups. Moreover, it is preferable that the said black coloring agent contains carbon black. Moreover, it is preferable that the said carbon black is acidic carbon black. Moreover, this invention is also the photoresist composition for black matrices obtained from the said pigment dispersion composition for black matrices. Moreover, the present invention is also a black matrix formed from the above-mentioned photoresist composition for a black matrix. [Effect of invention]

According to the present invention, it is possible to provide a pigment dispersion composition for a black matrix capable of forming a black matrix having a high surface resistance value.

<Pigment dispersion composition for black matrix> The pigment dispersion composition for black matrix of the present invention contains a black colorant, a sulfonated compound of copper phthalocyanine, and an amine compound, and the amine compound is at least one selected from the following (A) and (B); (A) Amine compounds having two or more carbon atoms within 3 atoms from the nitrogen atom of the amine group, (B) An amine compound in which an amine group is linked to one or more aromatic rings via a hydrocarbon group having 3 or less carbon atoms.

(black colorant) The pigment dispersion composition for black matrices of the present invention contains a black colorant. As said black coloring agent, it is preferable to contain carbon black, and it is more preferable that the said carbon black is acid carbon black. The carbon black is preferably an average primary particle size of 20 to 60 nm, and more preferably neutral carbon black with an average primary particle size of 20 to 60 nm and/or acid carbon black with an average primary particle size of 20 to 60 nm. When the primary particle size of the black colorant is less than 20 nm or more than 60 nm, there are cases where it does not have sufficient light-shielding properties or has poor storage stability. In addition, the said average primary particle diameter is the value of the arithmetic mean diameter obtained by electron microscope observation.

It is preferable that the said black coloring agent contains only acidic carbon black from a viewpoint of providing a surface resistance value favorably. On the other hand, when the neutral carbon black and the acid carbon black are used in combination, the neutral carbon black is preferably 85% by mass or less, more preferably the total mass of the neutral carbon black and the acid carbon black. It is 75 mass % or less. When the content of the neutral carbon black in the above-mentioned carbon black exceeds 85% by mass, the sealing strength may decrease.

The above-mentioned acidic carbon black and neutral carbon black will be described. According to the surface structure, carbon black can be roughly divided into acidic carbon black and neutral carbon black. Acid carbon black refers to a natural or artificially oxidized carbonaceous material that exhibits 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 above neutral carbon black, the pH is preferably in the range of 8.0 to 10.0, and specific examples include: PRINTEX 25 (average primary particle size 56 nm, pH 9.5), PRINTEX 35 (average primary particle size 31 nm) manufactured by Orion Engineered Carbons nm, pH9.5), PRINTEX 65 (average primary particle size 21 nm, pH9.5); MA#20 (average primary particle size 40 nm, pH8.0) manufactured by Mitsubishi Chemical Corporation, MA#40 (average primary particle size) diameter 40 nm, pH 8.0), MA#30 (average primary particle size 30 nm, pH 8.0), etc.

Regarding the above acid carbon black, the pH is preferably in the range of 2.0 to 4.0, and specific examples include: Raven 1080 (average primary particle size: 28 nm, pH 2.4), Raven 1100 (average primary particle size: 32 nm, pH 2.4) manufactured by Columbia Chemical Co., Ltd. pH2.9); MA-8 (average primary particle size: 24 nm, pH3.0), MA-100 (average primary particle size: 22 nm, pH3.5) manufactured by Mitsubishi Chemical; SPECIAL BLACK manufactured by Orion Engineered Carbons 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), NEROX 305 (average primary particle size 25 nm, pH 4.0) The primary particle size is about 28 nm, and the pH is about 2.8).

The above-mentioned black colorant is preferably SPECIAL BLACK 250 or NEROX 305 from the viewpoint of imparting good dispersibility or surface resistance to the pigment.

In addition, regarding the above pH, 1 g of carbon black was added to 20 ml of distilled water (pH 7.0) from which carbonic acid was removed, mixed with a magnetic stirrer to prepare an aqueous suspension, and measured at 25°C using a glass electrode ( German Industrial Standard DIN ISO 787/9).

The content of the black colorant is preferably 3 to 70% by mass, more preferably 10 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. When the content of the black colorant is less than 3% by mass, the light-shielding property when forming a black matrix may decrease, and when the content of the black colorant exceeds 70% by mass, the pigment may be difficult to disperse.

(Sulfonate of copper phthalocyanine) The pigment dispersion composition for black matrices of the present invention contains a sulfonated compound of copper phthalocyanine. In the step of micronizing or dispersing the above-mentioned copper phthalocyanine in the above-mentioned black colorant, part of the basic skeleton is adsorbed on the surface of the pigment, and the sulfonic acid group increases the affinity with the organic solvent or pigment dispersant, thereby improving the above-mentioned black color. The effect of miniaturization when the colorant is dispersed, or dispersion stability after dispersion, etc.

The copper phthalocyanine in the above-mentioned sulfonated copper phthalocyanine is not particularly limited, and the copper phthalocyanine skeleton may have 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 the ease of introducing a sulfonic acid group, a structure having no substituent is preferred.

The sulfonated compound of the above-mentioned copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in the molecule. By having 0.5 to 3 sulfonic acid groups in the molecule in this way, it is possible to obtain a composition for a black matrix that can obtain a coating film having an excellent surface resistance value. The sulfonated compound of the above-mentioned copper phthalocyanine more preferably has 0.5 to 1.5 sulfonic acid groups, and more preferably 0.7 to 1.5 sulfonic acid groups in the molecule. Furthermore, the number of sulfonic acid groups contained in the above-mentioned molecule can be calculated based on the ratio of sulfur atoms to copper atoms obtained by elemental analysis.

As a sulfonate of the said copper phthalocyanine, a commercial item can also be used, for example, Solsperse 12000 (both are manufactured by Japan Lubrizol Corporation), and the de-sodium product of VALIFAST BLUE 1605, etc. are mentioned.

It is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said black coloring agents, and, as for content of the said copper phthalocyanine sulfonate, it is more preferable that it is 1-15 mass parts.

(amine compound) The pigment dispersion composition for black matrices of the present invention contains an amine compound. The above-mentioned amine compound is at least one selected from the following (A) and (B); (A) Amine compounds having two or more carbon atoms within 3 atoms from the nitrogen atom of the amine group, (B) An amine compound in which an amine group is linked to one or more aromatic rings via a hydrocarbon group having 3 or less carbon atoms. By containing such an amine compound, whether it is the above (A) or (B), the electron pair on the nitrogen atom is buried by the bulky substituent, and as a result, between the amine compound and the sulfonic acid and the neutralization, the ion Since the ionicity becomes moderate, it is considered that energization due to the ionicity can be suppressed. In addition, it is considered that the steric hindrance by the bulky substituent prevents the pigment particles from approaching each other. However, the present invention can also be explained without being limited to the above-mentioned mechanism.

The above-mentioned amine compounds having carbon atoms of secondary or higher order within 3 atoms from the nitrogen atom of the amine group are preferably carbon atoms of secondary or higher order within 3 atoms of the nitrogen atoms of all amine groups present in the amine compound. , specifically: 1,1,3,3-tetramethylbutylamine, diisopropylamine, triisopropylamine, diisobutylamine, triisobutylamine, diisoamylamine, Triisoamylamine, tris(2-ethylhexyl)amine, and the like. In addition, the so-called within 3 atoms from the nitrogen atom of the amine group means that the atom adjacent to the nitrogen atom of the amine group is counted as 1, the atom adjacent to the above-mentioned atom adjacent to the nitrogen atom is counted as 2, and the atom adjacent to the above-mentioned nitrogen atom is counted as 2. An atom adjacent to an atom adjacent to a nitrogen atom is counted as 3.

Examples of the amine compound in which the above-mentioned amine group is linked to one or more aromatic rings via a hydrocarbon group having 3 or less carbon atoms include 3-phenylpropylamine, 2-phenylpropylamine, 1-phenylpropylamine, 2-phenylpropylamine, and 2-phenylpropylamine. - Phenylethylamine, 1-phenylethylamine, phenylmethylamine, triphenylmethylamine, etc.

As said amine compound, it is preferable to be selected from 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine, and triisobutyl from the viewpoint of improving the surface resistance value favorably. At least one of the amines.

It is preferable that it is 5-100 mass parts with respect to 100 mass parts of sulfonates of the said copper phthalocyanine, and, as for the said amine compound, it is more preferable that it is 20-60 mass parts.

(Organic solvents) It is preferable that the pigment dispersion composition for black matrices of this invention contains an organic solvent. As said organic solvent, the organic solvent conventionally used in the field of liquid crystal black matrix photoresist is used suitably.

Specific examples of the organic solvent include ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, and aromatic hydrocarbon-based organic solvents having a boiling point of 100 to 250°C under normal pressure (1.013×10 ² kPa). Organic solvents, nitrogen-containing organic solvents, etc. When a large amount of the above-mentioned organic solvent having a boiling point exceeding 250°C is contained, there is a case where, when the coating film formed by coating the photoresist composition for black matrix obtained from the pigment dispersion composition for black matrix of the present invention is subjected to During pre-baking, the organic solvent is not sufficiently evaporated and remains in the dry coating film, resulting in a decrease in the heat resistance of the dry coating film. Moreover, when a large amount of the organic solvent whose boiling point is less than 100 degreeC is contained, it may become difficult to apply uniformly without unevenness, and a coating film excellent in surface smoothness may not be obtained.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. 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 and other ether-based organic solvents; Methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other ether ester organic solvents; methyl isobutyl Ketone-based organic solvents such as ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate ester, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ester-based organic solvents such as ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate, etc.; alcohol-based solvents such as methanol, ethanol, isopropanol, butanol; N-methylpyrrole Nitrogen-containing organic solvents such as pyridone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These can be used individually or in mixture of 2 or more types.

Among the above-mentioned organic solvents, from the viewpoints of solubility, dispersibility, coatability, etc., diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and ethylene glycol monomethyl ether acetic acid are preferred Esters, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutane propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc., more preferably propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

(pigment dispersant) The pigment dispersion composition for a black matrix of the present invention preferably contains a pigment dispersant. The above-mentioned pigment dispersant is a basic group-containing pigment dispersant, which can be used: anionic surfactant, basic group-containing polyester pigment dispersant, basic group-containing acrylic pigment dispersant, basic group-containing pigment dispersant, etc. urethane-based pigment dispersant, basic group-containing carbodiimide-based pigment dispersant, acidic group-containing polymer pigment dispersant, etc. These basic group-containing pigment dispersants may be used alone or in combination of two or more. Among them, a polymer pigment dispersant containing a basic group is preferable in terms of obtaining good pigment dispersibility.

Specific examples of the above-mentioned basic group-containing polymer pigment dispersants include: (1) The amine group and/or imine group of the polyamine compound (for example, poly(lower alkylene amine) such as polyallylamine, polyvinylamine, polyethylenepolyimine, etc.) The reaction product of at least one of the group consisting of ester, polyamide and polyesteramide (Japanese Patent Laid-Open No. 2001-59906); (2) Reaction products of low-molecular amine compounds such as poly(lower) alkylene imines, methyliminobispropylamine and polyesters with free carboxyl groups (Japanese Patent Laid-Open No. 54-37082, Japanese Japanese Unexamined Patent Publication No. 01-311177); (3) The isocyanate group of the polyisocyanate compound is sequentially combined with alcohols such as methoxy polyethylene glycol or polyesters having 1 hydroxyl group such as caprolactone polyester, and 2 to 3 isocyanate groups Compounds with reactive functional groups and reaction products obtained from the reaction of aliphatic or heterocyclic hydrocarbon compounds with isocyanate reactive functional groups and tertiary amine groups (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 amine group; (5) The reaction product formed by adding a polyether chain to a low molecular amine compound; (6) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amine 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 a secondary amine group (Japanese Patent Laid-Open No. 09-87537); (8) The reaction product of a polycarbonate compound having a functional group that can react with an amine group at one end and a polyamine compound (Japanese Patent Laid-Open No. 09-194585); (9) selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, At least one of methacrylates or acrylates such as propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, acrylamide, methacrylate, N-methylolamide, vinyl At least one of basic group-containing polymerizable monomers such as imidazole, vinylpyridine, monomers having an amino group and polycaprolactone skeleton, and at least one of styrene, styrene derivatives, and other polymerizable monomers Species of copolymer (Japanese Patent Laid-Open No. 01-164429); (10) Basic group-containing carbodiimide pigment dispersant (International Publication No. WO04/000950); (11) Block copolymers composed of blocks having basic groups such as tertiary amine groups and quaternary ammonium salt groups and blocks having no functional groups (refer to the description of Japanese Patent Laid-Open No. 2005-55814) ; (12) A pigment dispersant obtained by a Michael addition reaction between polyallylamine and a polycarbonate compound (Japanese Patent Laid-Open No. 09-194585); (13) Carbodiimide-based compounds having at least one polybutadiene chain and at least one basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-257243); (14) A carbodiimide-based compound having at least one side chain having an amide group and at least one basic nitrogen-containing group in the molecule (Japanese Patent Laid-Open No. 2006-176657); (15) A polyurethane-based compound having a structural unit containing an ethylene oxide chain and a propylene oxide chain and having an amine group quaternized by a quaternizing agent (Japanese Patent Laid-Open No. 2009-175613); (16) Obtained by reacting the isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with the active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and/or an azobenzene skeleton Compounds, in the molecule of the compound, with respect to the sum of isocyanate groups derived from isocyanate compounds having an isocyanurate ring and urethane bonds and urea bonds generated by the reaction of isocyanate groups with active hydrogen groups For example, the number of carbazole ring and azobenzene skeleton is 15-85% (Japanese Patent Application No. 2009-220836); (17) A graft copolymer or the like obtained by introducing a polyether or polyester side chain into an acrylate polymer having an amine group.

Among the above-mentioned basic-group-containing polymer pigment dispersants, more preferred are basic-group-containing urethane-based polymer pigment dispersants, basic-group-containing polyester-based polymer pigment dispersants, and basic-group-containing polymer pigment dispersants. The acrylic polymer pigment dispersant is further preferably an amine group-containing urethane polymer pigment dispersant, an amine group-containing polyester polymer pigment dispersant, and an amine group-containing acrylic polymer pigment dispersant. Among the above-mentioned basic group-containing polymer pigment dispersants, it is particularly preferred to have at least one basic group-containing group (amine group) selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains. ) of the polymer pigment dispersant.

As content of the said pigment dispersing agent, 1-200 mass parts is preferable with respect to 100 mass parts of said black coloring agents, More preferably, it is 5-100 mass parts.

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

As said binder resin, a thermosetting resin, a thermoplastic resin, a photopolymerizable compound, an alkali-soluble resin, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Examples of the above-mentioned thermosetting resin or thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer. polyvinyl acetate, polyurethane resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose , polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, etc.

As said photopolymerizable compound, the monomer which has 1 or 2 or more of photopolymerizable unsaturated bonds in a molecule|numerator, the oligomer which has a photopolymerizable unsaturated bond, etc. are mentioned.

As the monomer having one photopolymerizable unsaturated bond in the molecule, for example, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, and butyl acrylate can be used. , 2-ethylhexyl acrylate and other alkyl methacrylates or alkyl acrylates; benzyl methacrylate, benzyl acrylate and other aralkyl methacrylates or aralkyl acrylates; butoxy methacrylate Ethyl methacrylate, butoxyethyl acrylate and other alkoxyalkyl methacrylates or alkoxyalkyl acrylate; N,N-dimethylaminoethyl methacrylate, N,N-dimethacrylate Aminoalkyl methacrylates such as methylaminoethyl ester or aminoalkyl acrylate; polyalkylene glycols such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether Methacrylates or acrylates of monoalkyl ethers; methacrylates or acrylates of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether; ester; glycerol methacrylate or glycerol acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, etc.

As the monomer having two or more photopolymerizable unsaturated bonds in the molecule, for example, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol can be used. Alcohol Dimethacrylate, Diethylene Glycol Dimethacrylate, Glycerin Dimethacrylate, Neopentyl Glycol Dimethacrylate, Polyethylene Glycol Dimethacrylate, Polypropylene Glycol Dimethacrylate Esters, Tetraethylene Glycol Dimethacrylate, Trimethylolpropane Trimethacrylate, Neotaerythritol Trimethacrylate, Neotaerythritol Tetramethacrylate, Dipionaerythritol Tetramethyl Base Acrylates, Dipivalerythritol Hexamethacrylate, Dipivalerythritol Pentamethacrylate, Epoxy Methacrylate, Bisphenol A Diacrylate, 1,4-Butanediol Diacrylate , 1,3-Butanediol Diacrylate, Diethylene Glycol Diacrylate, Glycerin Diacrylate, Neopentyl Glycol Diacrylate, Polyethylene Glycol Diacrylate, Polypropylene Glycol Diacrylate, Tetraethylene Diacrylate Alcohol Diacrylate, Trimethylolpropane Triacrylate, Neotaerythritol Triacrylate, Neotaerythritol Tetraacrylate, Dipionaerythritol Tetraacrylate, Dipionaerythritol Hexacrylate, Dipentaerythritol Pentaerythritol pentaacrylate, epoxy acrylate, etc.

As the oligomer having the above-mentioned photopolymerizable unsaturated bond, an oligomer obtained by appropriately polymerizing the above-mentioned monomer can be used. The above-mentioned binder resins may be used alone or in combination of two or more.

As said binder resin, epoxy acrylate resin is preferable from a viewpoint of heat resistance and developability.

The above-mentioned alkali-soluble resin will be described later.

It is preferable that content of the said binder resin is 3-50 mass % in mass fraction with respect to the total solid content of the pigment dispersion composition for black matrices of this invention.

(Manufacturing method of pigment dispersion composition for black matrix) As a manufacturing method of the pigment dispersion composition for black matrices of this invention, it can be obtained by adding the above-mentioned various components, mixing and grinding. The above-mentioned grinding method is not particularly limited. For example, a bead mill, a ready mill, an ultrasonic homogenizer, a high pressure homogenizer, a paint shaker, a ball mill, Roll mill, sand mill, sand grinder, dyno-mill, dispermat, SC mill, nanomizer, etc., and use What is necessary is just to grind it by a well-known method.

<Photoresist composition for black matrix> The present invention is also a photoresist composition for black matrix, which is obtained from the pigment dispersion composition for black matrix of the present invention.

(Pigment dispersion composition for black matrix) The photoresist composition for black matrices of the present invention contains the above-described pigment dispersion composition for black matrices of the present invention. As content of the said pigment dispersion composition for black matrices, based on the total mass of the photoresist composition for black matrices of this invention, it is preferable that it is 30-80 mass %, and it is more preferable that it is 40-75 mass %.

、2-氯9-氧硫

、1-羥基環己基苯基酮、第三丁基蒽醌、1-氯蒽醌、2,3-二氯蒽醌、3-氯-2-甲基蒽醌、2-乙基蒽醌、1,4-萘醌、1,2-苯并蒽醌、1,4-二甲基蒽醌、2-苯基蒽醌、2-甲基-1[4-(甲硫基)苯基]-2-

啉基丙烷-1-酮等二苯甲酮系、9-氧硫

系、蒽醌系、三

系等之光聚合起始劑等。 上述光聚合起始劑可單獨使用，或組合2種以上使用。 (Photopolymerization Initiator) The photoresist 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 by irradiating active energy rays such as ultraviolet rays or electron beams. For example, 1-[9-ethyl-6 -(2-Methylbenzyl)-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, benzalkonium dimethyl ketal, α-hydroxyisobutyl phenone, 9-oxysulfur

, 2-chloro-9-oxosulfur

, 1-hydroxycyclohexyl phenyl ketone, tert-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl] -2-

Benzophenones such as linopropane-1-one, 9-oxosulfur

series, anthraquinone series, three

Such as photopolymerization initiators, etc. The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

The content of the above-mentioned photopolymerization initiator is preferably 1 to 20% by mass in terms of mass fraction relative to the total solid content of the photoresist composition for a black matrix of the present invention.

(Photopolymerizable compound) It is preferable that the photoresist composition for black matrices of this invention contains a photopolymerizable compound. As said photopolymerizable compound, the photopolymerizable compound described in the said pigment dispersion composition for black matrices can be suitably selected and used.

It is preferable that content of the said photopolymerizable compound is 0.1-50 mass % in mass fraction with respect to the total solid content of the photoresist composition for black matrices of this invention.

(alkali-soluble resin) The photoresist composition for a black matrix 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 a developer, especially an alkaline developer, used in the development process when a black matrix is produced.

A block copolymer can also be used as the said alkali-soluble resin. By using the block copolymer, the pigment dispersion can be improved compared to other copolymers, and the solubility in PGMEA or alkaline developer can be imparted. Among the block copolymers, a block copolymer having the following blocks is preferred: a block composed of an ethylenically unsaturated monomer having one or more carboxyl groups, and a block composed of other copolymerizable ethylenic monomers Blocks of unsaturated monomers.

It does not specifically limit as said block copolymer, The block copolymer conventionally used can be used. Among them, a copolymer of an ethylenically unsaturated monomer having a carboxyl group, such as acrylic acid and methacrylic acid, and at least one ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer having a carboxyl group can be mentioned. At least one ethylenically unsaturated monomer copolymerized with an ethylenically unsaturated monomer having a carboxyl group is selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, methyl methacrylate Allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide , polystyrene giant monomer, polymethyl methacrylate giant monomer, carboxylate diacrylate and other monomers and oligomers. Among them, it is preferable not to use N-vinylpyrrolidone and a monomer containing a sulfur element. As the above-mentioned block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used. A part of block sites of the above-mentioned block copolymer may be constituted by a random copolymer.

As said alkali-soluble resin, an alkali-soluble Cardo resin can also be used. Examples of the above alkali-soluble cardo resin include epoxy (meth)acrylates having a perylene skeleton, which are addition products of perylene epoxy (meth)acrylic acid derivatives and dicarboxylic anhydride and/or tetracarboxylic dianhydride. Acid adducts, etc. Moreover, this alkali-soluble resin may have a photopolymerizable functional group.

The acid value of the above-mentioned alkali-soluble resin is preferably 5 to 300 mgKOH/g, more preferably 5 to 250 mgKOH/g, further preferably 10 to 200 mgKOH/g, particularly preferably 5 to 300 mgKOH/g from the viewpoint of developing characteristics. It is 60～150 mgKOH/g. In addition, in this specification, the said acid value is a theoretical acid value, and it is a value calculated|required arithmetically based on the ethylenically unsaturated monomer which has a carboxyl group, and its content.

From the viewpoint of developing characteristics or solubility in organic solvents, the weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and still more preferably 5,000 to 30,000. In addition, in this invention, the said weight average molecular weight is based on the weight average molecular weight of the polystyrene conversion obtained by GPC. In this specification, Water 2690 (manufactured by Waters Corporation) was used as an apparatus for measuring the above-mentioned weight average molecular weight, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies Corporation) was used as a column.

1-200 mass parts is preferable with respect to 100 mass parts of said black coloring agents, and, as for content of the said alkali-soluble resin, 10-150 mass parts is more preferable. In this case, if the content of the above-mentioned alkali-soluble resin is less than 1 part by mass, the developing characteristics may decrease, and if the content of the above-mentioned alkali-soluble resin exceeds 200 parts by mass, the concentration of the above-mentioned black colorant will relatively decrease, Therefore, there are cases where it is difficult to achieve the target color density as a thin film.

As said alkali-soluble resin, it is preferable that it does not contain any amine group among a primary amine group, a secondary amine group, and a tertiary amine group, and also does not contain a quaternary ammonium group. Furthermore, it is more preferable not to contain a basic group. Furthermore, in the range which does not impair the effect achieved by this invention, the alkali-soluble resin which has a structure other than a block copolymer can also be blended.

(Organic solvents) As said organic solvent, the organic solvent described in the said pigment dispersion composition for black matrices can be suitably selected and used.

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

(other additives) The photoresist composition for black matrices of the present invention may appropriately use various additives such as thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants as necessary.

化合物等。 (Manufacturing method of photoresist composition for black matrix) As a manufacturing method of the photoresist composition for black matrix of the present invention, for example, it can be produced by producing the pigment dispersion composition for black matrix of the present invention, After that, the remaining materials are added and stirred and mixed using a stirring device or the like. The above-mentioned stirring and mixing methods are 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. Moreover, you may filter with a filter after the said stirring and mixing. Furthermore, when preparing the photoresist composition for black matrix of the present invention, the above-mentioned black colorant, the above-mentioned epoxy resin, the above-mentioned black colorant described in the pigment-dispersed composition for black matrix of the present invention can also be added as needed.

compounds, etc.

＜Black Matrix＞ The black matrix of the present invention is formed from the photoresist composition for a black matrix of the present invention.

The method for forming the black matrix of the present invention is not particularly limited. For example, the black matrix can be formed by a method such as coating the photoresist composition for the black matrix of the present invention on a transparent substrate, drying it, and forming a coating film. , a photomask is placed on the above-mentioned coating film, image exposure and development are carried out through the photomask, and photohardening is carried out if necessary.

The methods of coating, drying, exposing, and developing the photoresist composition for black matrix of the present invention can be appropriately selected from known methods. Moreover, as said transparent substrate, a well-known transparent substrate, such as a glass substrate and a plastic substrate, can be suitably selected and used.

The thickness of the coating film is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and still more preferably 1 to 4 μm in terms of the film thickness after drying. By setting it as the range of the said thickness, a predetermined pattern can be developed favorably, and a predetermined optical density can be given favorably.

The black matrix of the present invention was coated on a glass substrate (EAGLE XG) with a film thickness of 1 μm by a spin coater, pre-baked at 100° C. for 3 minutes, and then exposed by a high-pressure mercury lamp (UV cumulative light intensity). 80 mJ/cm ² ), and then post-baked at 230°C for 60 minutes to form a black photoresist pattern formed only by the solid portion, and the surface resistance value at this time is preferably 2.0×10 ⁹ Ω/□ or more, More preferably, it is 5.0×10 ⁹ Ω/□ or more, and still more preferably 9.0×10 ⁹ Ω/□ or more. When the above-mentioned surface resistance value is 2.0×10 ⁹ Ω/□ or more, short-circuit and current leakage can be prevented well. In addition, the above-mentioned surface resistance value can be measured by main body: Micro-galvanometer R8340, option: shielding box R12702A (both are manufactured by ADVANCE).

Since the pigment dispersion composition for black matrix, the photoresist composition for black matrix, and the black matrix of the present invention have the above-mentioned characteristics, they are suitable for use as a black matrix of an image display device, a touch panel, or the like. [Example]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples unless it deviates from the gist and scope of application of the present invention. In addition, in this Example, unless otherwise specified, "part" and "%" represent "mass part" and "mass %", respectively.

Various materials used in the following Examples and Comparative Examples are as follows. ＜Black colorant＞ Carbon black (trade name "NEROX 305", average primary particle size about 28 nm, pH about 2.8, manufactured by Orion Engineered Carbons) ＜Pigment dispersant＞ DISPERBYK-167 (solid content 52% by mass, manufactured by BYK-Chemie) <Amine compound> 3-Phenylpropylamine (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.) ＜Binder resin＞ ZCR-1569H (epoxy acrylate resin, solid content 70% by mass, manufactured by Nippon Kayaku Co., Ltd.) ＜Organic solvent＞ PGMEA (Propylene Glycol Monomethyl Ether Acetate) <Photopolymerization initiator> OXE 02 (product name "Irgacure OXE 02", 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyl Oxime) ethyl ketone, manufactured by BASF Corporation) <Photopolymerizable compound> DPHA (Diponeaerythritol Hexacrylate) ＜Alkali-soluble resin＞ WR-301 (product name "WR-301", Cardo-based resin, acid value 100 mgKOH/g, solid content 45% by mass, manufactured by ADEKA Corporation)

<Preparation of composition for dispersion> (Dispersion Composition 1) Solsperse 12000 (a sulfonated compound of copper phthalocyanine (containing about 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol, Japan) and 3-phenylpropylamine were mixed in a mass ratio of 25:8 to obtain a dispersion composition 1. (Dispersion Composition 2) Solsperse 12000 (sulfonate of copper phthalocyanine (containing about 0.9 sulfonic acid groups in 1 molecule), manufactured by Lubrizol, Japan) and 1,1,3,3-tetramethylbutylamine in a mass ratio of 10:3 By mixing, the composition 2 for dispersion was obtained. (Dispersion Composition 3) Solsperse 12000 (a sulfonated compound of copper phthalocyanine (containing about 0.9 sulfonic acid groups per molecule), manufactured by Lubrizol, Japan) and triisobutylamine were mixed at a mass ratio of 25:11 to obtain a dispersion composition 3.

＜Material for dispersion＞ Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Lubrizol, Japan) Solsperse 5000 (quaternary ammonium salt of copper phthalocyanine sulfonate, (contains about 0.9 sulfonic acid groups in 1 molecule), manufactured by Lubrizol, Japan) VALIFAST BLUE 1605 (VB 1605, sodium neutralization product of copper phthalocyanine sulfonate, manufactured by Orient Chemical Industries, Ltd.)

<Preparation of pigment dispersion composition for black matrix> Each material was mixed so that it might become the composition of Table 1, and it knead|mixed with a bead mill all day and night, and it was set as the pigment dispersion composition for black matrices.

[Table 1] Pigment dispersion composition for black matrix 1 2 3 4 5 6 black colorant carbon black 25.0 25.0 25.0 25.0 25.0 25.0 Pigment Dispersant DISPERBYK-167 (solid content 52% by mass) 5.8 5.8 5.8 5.8 5.8 5.8 composition for dispersion Dispersion composition 1 1.0 - - - - - Dispersion composition 2 - 1.0 - - - - Dispersion composition 3 - - 1.0 - - - material for dispersion Solsperse 12000 - - - 1.0 - - Solsperse 5000 - - - - 1.0 - VB1605 - - - - - 1.0 adhesive resin ZCR-1569H (solid content 70% by mass) 5.4 5.4 5.4 5.4 5.4 5.4 Organic solvents PGMEA 62.8 62.8 62.8 62.8 62.8 62.8 total 100.0 100.0 100.0 100.0 100.0 100.0

<Production of photoresist composition for black matrix> 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 so as to have the composition shown in Table 2. Filtered with a 3 μm filter to obtain photoresist compositions for black matrices of Examples and Comparative Examples.

<Evaluation Test> (Surface Resistance Value) Using a spin coater, the pigment-dispersed photoresist compositions for black matrices of Examples and Comparative Examples were applied on a glass substrate (EAGLE XG) so that the film thickness might be 1 μm. , after pre-baking at 100°C for 3 minutes, exposed with a high-pressure mercury lamp (UV cumulative light amount of 80 mJ/cm ² ), and then post-baking at 230°C for 60 minutes to make a black photoresist formed only by the solid part pattern (black matrix). The surface resistance value of each black photoresist pattern produced was measured by the main body: micro current meter R8340, option: shielding box R12702A (both manufactured by ADVANCE). The results are shown in Table 2.

[Table 2] Photoresist composition for black matrix Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment dispersion composition for black matrix 1 63.6 - - - - - 2 - 63.6 - - - - 3 - - 63.6 - - - 4 - - - 63.6 - - 5 - - - - 63.6 - 6 - - - - - 63.6 photopolymerization initiator OXE 02 1.0 1.0 1.0 1.0 1.0 1.0 photopolymerizable compound DPHA 1.0 1.0 1.0 1.0 1.0 1.0 Alkali Soluble Resin WR-301 (solid content 45% by mass) 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 total 100.0 100.0 100.0 100.0 100.0 100.0 Evaluation results Surface resistance (Ω/□) 5.9×10 ⁹ 2.9×10 ⁹ 9.8×10 ⁹ 1.1×10 ⁸ 4.7×10 ⁷ 4.0×10 ⁸

In the example using the pigment dispersion composition for black matrices containing a black colorant, a sulfonated compound of copper phthalocyanine, and a specific amine compound, it was confirmed that a black matrix having a high surface resistance value could be formed. [Industrial Availability]

According to the present invention, it is possible to provide a pigment dispersion composition for a black matrix capable of forming a black matrix having a high surface resistance value.

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Claims (8)

A pigment dispersion composition for a black matrix, which contains a black colorant, a sulfonated compound of copper phthalocyanine, and an amine compound, and The above-mentioned amine compound is at least one selected from the following (A) and (B); (A) Amine compounds having two or more carbon atoms within 3 atoms from the nitrogen atom of the amine group, (B) An amine compound in which an amine group is linked to one or more aromatic rings via a hydrocarbon group having 3 or less carbon atoms. The pigment dispersion composition for a black matrix according to claim 1, wherein the amine compound is selected from the group consisting of 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine, and triisobutylamine at least one of them. The pigment dispersion composition for black matrices according to claim 1 or 2, wherein the sulfonated compound of copper phthalocyanine has 0.5 to 3 sulfonic acid groups in the molecule. The pigment dispersion composition for black matrices according to claim 3, wherein the sulfonated compound of copper phthalocyanine has 0.5 to 1.5 sulfonic acid groups in the molecule. The pigment dispersion composition for a black matrix according to any one of claims 1 to 4, wherein the black colorant contains carbon black. The pigment dispersion composition for a black matrix according to claim 5, wherein the carbon black is acid carbon black. A photoresist composition for a black matrix obtained from the pigment dispersion composition for a black matrix according to any one of claims 1 to 6. A black matrix is formed by the photoresist composition for black matrix of claim 7.