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

Abstract

The present invention provides a pigment dispersion composition for a black matrix, from which a black matrix having a high surface resistance value can be formed. The pigment dispersion composition for a black matrix includes a black colorant, a sulfonate of copper phthalocyanine, and an amine compound selected from at least one of the following compounds (A) and (B): (A) an amine compound having a carbon atom of secondary or higher within 3 atoms from a nitrogen atom of an amino group; and (B) an amine compound in which an amino group is connected to one or more aromatic rings through a hydrocarbon group having 3 or fewer carbon atoms.

Description

[0001] [Cross-reference to related applications]

[0002] This application claims priority to Japanese Patent Application No. 2020-195211, filed with the Japan Patent Office on November 25, 2020, and all contents disclosed therein are incorporated herein by reference in the specification of this application. Technical Field

[0003] This invention relates to a pigment dispersion composition for black matrix, a photoresist composition for black matrix, and a black matrix. Background Technology

[0004] In image display devices that utilize liquid crystals, plasmas, etc., light-shielding films (black matrix, also known as "black substrate") are provided in the gaps of colored patterns in the display area and the edges of the area surrounding the display area, as well as on the outer light side of the TFT in a liquid crystal display using TFTs.

[0005] Furthermore, in liquid crystal display devices, it is mainly used to prevent backlight leakage from being reflected into the image. In addition, in plasma display devices, it is mainly used to prevent the bleed-in of various colors of light from being reflected into the image, thereby helping to improve display characteristics (contrast and color purity).

[0006] For example, color filters used to convert white light from the backlight of a liquid crystal display device into colored light are typically manufactured by forming pixels of different hues, such as red, green, and blue, in a pattern such as stripes or mosaics on the surface of a transparent substrate, such as glass or plastic sheet, in which a black matrix is ​​formed.

[0007] Furthermore, even in touch panels that align the image display device with the position input device, color filters (color filters) formed with a black matrix as a light-shielding film are similarly used, and have so far been formed on the side opposite to the sensor substrate, separated by a glass cover (protective sheet). However, with increasing demands for lightweight touch panels, in order to achieve further weight reduction, the development of technology that simultaneously forms the light-shielding film and the touch sensor on the same side as the glass cover is being promoted.

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

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

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

[0011] In a black matrix, a high surface resistivity is required to prevent short circuits or current leakage.

[0012] However, Patent Document 1 did not conduct sufficient research on the surface resistance value, leaving room for further improvement.

[0013] Existing technical documents

[0014] Patent documents

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

[0016] The technical problem that the invention aims to solve

[0017] Therefore, the object of the present invention is to provide a pigment dispersion composition for black matrix that is capable of forming a black matrix with a high surface resistivity.

[0018] means for solving problems

[0019] The inventors discovered that by further containing a specific amine compound in a pigment dispersion composition for a black matrix that contains a black colorant and a sulfonated copper phthalocyanine, a pigment dispersion composition for a black matrix that can form a black matrix with a high surface resistivity can be obtained, thus completing the present invention.

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

[0021] (A) Amine compounds having a second-order or higher carbon atom within three atoms after the nitrogen atom of the amino group;

[0022] (B) Amine compounds in which an amino group is attached to one or more aromatic rings via a hydrocarbon group having 3 or fewer carbon atoms.

[0023] The amine compound is preferably selected from at least one of 3-phenylpropanol, 1,1,3,3-tetramethylbutylamine and triisobutylamine.

[0024] In addition, the sulfonated phthalocyanine copper preferably has 0.5 to 3 sulfonic acid groups in the molecule, more preferably 0.5 to 1.5 sulfonic acid groups.

[0025] In addition, the black colorant preferably comprises carbon black.

[0026] In addition, the carbon black is preferably acidic carbon black.

[0027] In addition, the present invention also relates to a resist composition for black matrix obtained by the aforementioned pigment dispersion composition for black matrix.

[0028] In addition, the present invention also relates to a black matrix formed by the aforementioned black matrix using a resist composition.

[0029] Invention Effects

[0030] Based on the present invention, a pigment dispersion composition for forming a black matrix with high surface resistivity can be provided. Detailed Implementation

[0031] <Pigment Dispersion Composition for Black Matrix>

[0032] The black matrix pigment dispersion composition of the present invention comprises a black colorant, a sulfonated copper phthalocyanine, and an amine compound, wherein the amine compound is at least one selected from the following compounds (A) and (B):

[0033] (A) Amine compounds having a second-order or higher carbon atom within three atoms after the nitrogen atom of the amino group;

[0034] (B) Amine compounds in which an amino group is attached to one or more aromatic rings via a hydrocarbon group having 3 or fewer carbon atoms.

[0035] (Black colorant)

[0036] The black matrix pigment dispersion composition of the present invention contains a black colorant.

[0037] The aforementioned black colorant preferably contains carbon black, and more preferably, the aforementioned carbon black is acidic carbon black.

[0038] As the carbon black, the average primary particle size is preferably 20-60 nm, and more preferably neutral carbon black and / or acidic carbon black with an average primary particle size of 20-60 nm.

[0039] When the primary particle size of the black colorant is less than 20 nm or greater than 60 nm, it sometimes lacks sufficient light-blocking properties and has poor storage stability.

[0040] In addition, the average primary particle size is the arithmetic mean particle size value obtained by electron microscopy.

[0041] From the viewpoint of appropriately imparting a surface resistivity value, it is preferable that the black colorant contains only acidic carbon black.

[0042] On the other hand, when neutral carbon black and acid carbon black are used together, the neutral carbon black is preferably 85% by mass or less, more preferably 75% by mass or less, relative to the total mass of neutral carbon black and acid carbon black.

[0043] When the content of neutral carbon black in carbon black is greater than 85% by mass, the sealing strength may sometimes decrease.

[0044] The acidic carbon black and neutral carbon black are described below.

[0045] Carbon black can be broadly classified into acidic carbon black and neutral carbon black based on its surface structure. Acidic carbon black refers to carbonaceous materials that are already oxidized or artificially oxidized, and exhibit acidity when boiled with distilled water. On the other hand, neutral carbon black is known to exhibit a neutral or higher pH when boiled with distilled water.

[0046] As the neutral carbon black, the pH is preferably in the range of 8.0 to 10.0. Specifically, examples include: PRINTEX 25 (average primary particle size of 56 nm, pH 9.5), PRINTEX 35 (average primary particle size of 31 nm, pH 9.5), and PRINTEX 65 (average primary particle size of 21 nm, pH 9.5) manufactured by Orion Engineered Carbons; and MA#20 (average primary particle size of 40 nm, pH 8.0), MA#40 (average primary particle size of 40 nm, pH 8.0), and MA#30 (average primary particle size of 30 nm, pH 8.0) manufactured by Mitsubishi Chemical Corporation.

[0047] As for the acidic carbon black, the pH is preferably in the range of 2.0 to 4.0, and a specific example is Raven 10 manufactured by Columbia Chemical Company. 8 Raven 1100 (average primary particle size 28nm, pH 2.4), Raven 1100 (average primary particle size 32nm, pH 2.9); MA-8 (average primary particle size 24nm, pH 3.0) and MA-100 (average primary particle size 22nm, pH 3.5) manufactured by Mitsubishi Chemical Corporation; SpecialBlack 250 (average primary particle size 56nm, pH 3.0), SpecialBlack 350 (average primary particle size 31nm, pH 3.0), SpecialBlack 550 (average primary particle size 25nm, pH 4.0), and NEROX 305 (average primary particle size approximately 28nm, pH approximately 2.8) manufactured by Orion Engineering Carbon Co., Ltd., etc.

[0048] As the black colorant, SpecialBlack250 or NEROX305 are preferred from the viewpoint of appropriately imparting pigment dispersibility or surface resistivity.

[0049] Alternatively, the pH can be determined as follows: 1g of carbon black is added to 20ml of decarbonated distilled water (pH 7.0), mixed with a magnetic stirrer to prepare an aqueous suspension, and the pH is measured using a glass electrode at 25°C (German industrial standard DIN ISO 787 / 9).

[0050] The content of the black colorant, as a mass fraction relative to the total solid components of the black matrix pigment dispersion composition of the present invention, is preferably 3 to 70% by mass, more preferably 10 to 50% by mass.

[0051] When the content of the black colorant is less than 3% by mass, the opacity when forming a black matrix sometimes becomes low; when the content exceeds 70% by mass, pigment dispersion sometimes becomes difficult.

[0052] (Sulfonated form of copper phthalocyanine)

[0053] The black matrix pigment dispersion composition of the present invention contains a sulfonate of copper phthalocyanine.

[0054] The sulfonated copper phthalocyanine, during the micronization or dispersion process of the black colorant, has a portion of its basic skeleton adsorbed onto the pigment surface. By increasing the affinity between the sulfonic acid groups and the organic solvent or pigment dispersant, it has the effect of improving the micronization of the black colorant during dispersion or the dispersion stability after dispersion.

[0055] As for the copper phthalocyanine sulfonate, there is no particular limitation as long as it has a copper phthalocyanine skeleton. For example, it can have known substituents such as alkyl or halogen atoms on the copper phthalocyanine skeleton, but from the viewpoint of easily introducing sulfonic acid groups, it is preferred to have a structure without substituents.

[0056] The sulfonated form of copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in its molecule.

[0057] Thus, by having 0.5 to 3 sulfonic acid groups in the molecule, a composition for black matrix can be formed that can obtain a coating with excellent surface resistivity.

[0058] For the sulfonated form of copper phthalocyanine, it is more preferable to have 0.5 to 1.5 sulfonic acid groups in the molecule, and even more preferably to have 0.7 to 1.5 sulfonic acid groups.

[0059] In addition, the number of sulfonic acid groups in the molecule can be determined based on the ratio of sulfur atoms to copper atoms obtained from elemental analysis.

[0060] As the sulfonated form of copper phthalocyanine, commercially available products can be used, such as the desodiumed form of Solsperse 12000 (both manufactured by The Lubrizol Corporation of Japan) or VALIFAST BLUE 1605.

[0061] The content of the copper phthalocyanine sulfonate is preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the above-mentioned black colorant.

[0062] (amine compounds)

[0063] The pigment dispersion composition for black matrix of the present invention contains an amine compound.

[0064] The amine compound is selected from at least one of the following compounds (A) and (B):

[0065] (A) Amine compounds having a second-order or higher carbon atom within three atoms after the nitrogen atom of the amino group;

[0066] (B) Amine compounds in which an amino group is attached to one or more aromatic rings via a hydrocarbon group having 3 or fewer carbon atoms.

[0067] By including such an amine compound, the electron pairs of (A) and (B) on the nitrogen atom are buried by the bulky substituents, resulting in a milder ionicity during the neutralization of the amine compound with the sulfonic acid. Therefore, it is believed that the electrophoresis caused by this ionicity can be suppressed. Furthermore, the steric hindrance caused by the bulky substituents inhibits the approach between pigment particles.

[0068] However, the present invention may not be limited to the above-described mechanism.

[0069] The amine compound having a second-order or higher carbon atom within three atoms after the nitrogen atom of the aforementioned amino group is preferably an amine compound having a second-order or higher carbon atom within three atoms after the nitrogen atom of all the amino groups present in the amine compound. Specifically, examples include 1,1,3,3-tetramethylbutylamine, diisopropylamine, triisopropylamine, diisobutylamine, triisobutylamine, diisopentylamine, triisopentylamine, tri(2-ethylhexyl)amine, etc.

[0070] In addition, the term "within 3 atoms starting from the nitrogen atom of the amino group" means counting by setting the atom adjacent to the nitrogen atom of the amino group as 1, the atom adjacent to the nitrogen atom as 2, and the atom adjacent to the atom adjacent to the atom adjacent to the nitrogen atom as 3.

[0071] Examples of amine compounds in which the amino group is linked to one or more aromatic rings via a hydrocarbon group having 3 or fewer carbon atoms include 3-phenylpropanamine, 2-phenylpropanamine, 1-phenylpropanamine, 2-phenylethylamine, 1-phenylethylamine, phenylmethylamine, and triphenylmethylamine.

[0072] From the viewpoint of appropriately increasing the surface resistivity, the amine compound is preferably selected from at least one of 3-phenylpropylamine, 1,1,3,3-tetramethylbutylamine and triisobutylamine.

[0073] Relative to 100 parts by mass of the sulfonated copper phthalocyanine described above, the amine compound is preferably 5 to 100 parts by mass, more preferably 20 to 60 parts by mass.

[0074] (Organic solvents)

[0075] The pigment dispersion composition for black matrix of the present invention preferably contains an organic solvent.

[0076] As the organic solvent, organic solvents conventionally used in the field of liquid crystal black matrix resists are preferred.

[0077] The organic solvent, specifically, is at atmospheric pressure (1.013 × 10⁻⁶). 2 Organic solvents with boiling points of 100–250 °C at kPa include esters, ethers, ether esters, ketones, aromatic hydrocarbons, and nitrogen-containing organic solvents.

[0078] If a large amount of organic solvent with a boiling point exceeding 250°C is present, the organic solvent will not evaporate sufficiently and will remain in the dried coating film when the coating film formed by coating the black matrix pigment dispersion composition of the present invention is pre-baked, and sometimes the heat resistance of the dried coating film will decrease.

[0079] In addition, if a large amount of organic solvent with a boiling point of less than 100°C is present, it is difficult to coat the coating evenly without deviation, and sometimes a coating with excellent surface smoothness cannot be obtained.

[0080] Specifically, 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, and other 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, and other ether-ester organic solvents; methyl isobutyl ketone, cyclohexanone, 2- Ketone organic solvents such as heptanone and δ-butyrolactone; ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxylate, ethyl hydroxyacetate, 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 mixtures of two or more.

[0081] From the viewpoints of solubility, dispersibility, and coatability, the preferred organic solvents are diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and n-pentyl formate, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being more preferred.

[0082] (Pigment dispersant)

[0083] The pigment dispersion composition for black matrix of the present invention preferably contains a pigment dispersant.

[0084] As the aforementioned pigment dispersant, it is a pigment dispersant containing alkaline groups, and can be anionic surfactants, polyester pigment dispersants containing alkaline groups, acrylic pigment dispersants containing alkaline groups, polyurethane pigment dispersants containing alkaline groups, carbodiimide pigment dispersants containing alkaline groups, and polymeric pigment dispersants containing acidic groups, etc.

[0085] These pigment dispersants containing basic groups can be used alone, or in combination of two or more. From the viewpoint of achieving good pigment dispersibility, polymeric pigment dispersants containing basic groups are preferred.

[0086] Specific examples of the aforementioned polymeric pigment dispersants containing alkaline groups can be given as follows:

[0087] (1) A reaction product of the amino and / or imino groups of a polyamine compound (e.g., polyallylamine, polyvinylamine, polyethylene polyimine, etc., poly(lower) alkyleneamines) with at least one selected from the group consisting of polyesters, polyamides and polyesteramides having free carboxyl groups (Japanese Patent Application Publication No. 2001-59906).

[0088] (2) Reactions of low molecular weight amine compounds such as poly(low) alkylene imides and methyliminodipropylamine with polyesters having free carboxyl groups (Japanese Patent Application Publication No. 54-37082, Japanese Patent Application Publication No. 01-311177);

[0089] (3) A reaction product formed by sequentially reacting alcohols such as methoxy polyethylene glycol, polyesters such as caprolactone polyester with one hydroxyl group, compounds with 2 to 3 isocyanate reactive functional groups, aliphatic or heterocyclic hydrocarbon compounds with isocyanate reactive functional groups and tertiary amino groups with the isocyanate groups of polyisocyanate compounds (Japanese Patent Application Publication No. 02-612).

[0090] (4) Compounds obtained by reacting polyisocyanate compounds and hydrocarbon compounds having amino groups with polymers of acrylates having alcoholic hydroxyl groups;

[0091] (5) Reactions formed by the addition of polyether chains to low molecular weight amine compounds;

[0092] (6) A reaction product formed by reacting an amino group compound with an isocyanate group (Japanese Patent Application Publication No. 04-210220);

[0093] (7) The reaction products obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having a secondary amine group with a polyepoxide compound (Japanese Patent Application Publication No. 09-87537).

[0094] (8) The reaction product of a polycarbonate compound having a functional group at a single end capable of reacting with an amino group and a polyamine compound (Japanese Patent Application Publication No. 09-194585);

[0095] (9) A copolymer of at least one of the following methacrylates or acrylates selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octadecyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octadecyl acrylate, benzyl acrylate, etc., with at least one of the following polymerizable monomers containing basic groups selected from acrylamide, methacrylamide, N-hydroxymethylamide, vinylimidazole, vinylpyridine, monomers having an amino group and a polycaprolactone backbone, and at least one of the following polymerizable monomers selected from styrene, styrene derivatives, and other polymerizable monomers (Japanese Patent Application Publication No. 01-164429);

[0096] (10) Carbodiimide pigment dispersants containing basic groups (International Publication No. WO04 / 000950);

[0097] (11) A block copolymer composed of blocks having basic groups such as tertiary amino groups and quaternary ammonium bases and blocks without functional groups (see Japanese Patent Application Publication No. 2005-55814).

[0098] (12) A pigment dispersant obtained by Michael addition reaction of polycarbonate compound with polyallylamine (Japanese Patent Application Publication No. 09-194585);

[0099] (13) Carbodiimide compounds having at least one polybutadiene chain and a basic nitrogen-containing group respectively (Japanese Patent Application Publication No. 2006-257243);

[0100] (14) Carbodiimide compounds having at least one side chain with an amide group and a basic nitrogen-containing group in the molecule (Japanese Patent Application Publication No. 2006-176657);

[0101] (15) A polyurethane compound having structural units having ethylene oxide chains and propylene oxide chains and having amino groups that have been quaternized by a quaternizing agent (Japanese Patent Application Publication No. 2009-175613).

[0102] (16) A compound obtained by reacting the isocyanate group of an isocyanate compound having an isocyanate 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, wherein the amount of the carbazole ring and the azobenzene skeleton in the molecule of the compound is 15 to 85% relative to the total amount of the carbazole ring and the carbamate bond and the urea bond generated by the reaction of the isocyanate group and the active hydrogen group (Japanese Patent Application 2009-220836).

[0103] (17) A graft copolymer in which polyether or polyester side chains are introduced into an acrylate polymer containing amino groups.

[0104] Among the aforementioned polymeric pigment dispersants containing basic groups, polyurethane pigment dispersants, polyester pigment dispersants, and acrylic pigment dispersants containing basic groups are more preferred; amino-containing polyurethane pigment dispersants, polyester pigment dispersants, and acrylic pigment dispersants are even more preferred. Among the aforementioned polymeric pigment dispersants containing basic groups, polymeric pigment dispersants having at least one basic group (amino) selected from polyester chains, polyether chains, and polycarbonate chains are particularly preferred.

[0105] The content of the pigment dispersant is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, relative to 100 parts by weight of the black colorant.

[0106] (Adhesive resin)

[0107] The pigment dispersion composition for black matrix of the present invention preferably contains a binder resin.

[0108] Examples of adhesive resins include thermosetting resins, thermoplastic resins, photopolymerizable compounds, and alkali-soluble resins. They can be used alone or in combination of two or more.

[0109] Examples of the aforementioned thermosetting or thermoplastic resins include: butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resins, phenolic resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclic rubber, epoxy resins, cellulose resins, polybutadiene, polyimide resins, benzoguanamine resins, melamine resins, urea-formaldehyde resins (urea resins), etc.

[0110] Examples of photopolymerizable compounds include monomers having one or more photopolymerizable unsaturated bonds within their molecules, and oligomers having photopolymerizable unsaturated bonds.

[0111] As monomers with a single photopolymerizable unsaturated bond within the molecule, the following can be used: methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., alkyl methacrylates or acrylates; benzyl methacrylate, benzyl acrylate, etc., aralkyl methacrylates or acrylates; butoxyethyl methacrylate, butoxyethyl acrylate, etc., alkoxyalkyl methacrylates or acrylates; N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, etc., aminoalkyl methacrylates or acrylates; diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc., polyalkylene glycol monoalkyl ethers, methacrylates or acrylates; hexaethylene glycol monophenyl ether, etc., polyalkylene glycol monoaryl ethers, methacrylates or acrylates; isobornyl methacrylate or acrylates; glyceryl methacrylate or acrylates; 2-hydroxyethyl methacrylate or acrylates, etc.

[0112] As monomers having two or more photopolymerizable unsaturated bonds within the aforementioned molecules, the following can be used: 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, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol tetramethacrylate, etc. Hexamethacrylate, pentaerythritol pentamethacrylate, epoxy methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, epoxy acrylate, etc.

[0113] As the oligomers with photopolymerizable unsaturated bonds mentioned above, oligomers obtained by appropriately polymerizing the above monomers can be used.

[0114] The above-mentioned adhesive resins can be used alone or in combination of two or more.

[0115] From the viewpoint of heat resistance and developability, epoxy acrylate resin is preferred as the adhesive resin.

[0116] The alkali-soluble resins mentioned above will be described later.

[0117] The content of the above-mentioned adhesive resin is preferably 3 to 50% by mass relative to the total solid components of the black matrix pigment dispersion composition of the present invention.

[0118] (Method for manufacturing a pigment dispersion composition for a black matrix)

[0119] As a method for manufacturing the pigment dispersion composition for black matrix of the present invention, it can be obtained by adding the above-mentioned components and mixing and grinding them.

[0120] There are no particular limitations on the method for performing the above-mentioned ink grinding process. For example, a bead mill, readymill, ultrasonic homogenizer, high-pressure homogenizer, paint shaker, ball mill, roller mill, sand mill, sand grinder, Dyno-Mill, DISPERMAT, SC mill, or Nanomiizer can be used to perform the ink grinding process using known methods.

[0121] <Resistant Composition for Black Matrix>

[0122] The present invention also relates to a resist composition for black matrix obtained from the pigment dispersion composition for black matrix of the present invention.

[0123] (Black matrix pigment dispersion composition)

[0124] The resist composition for black matrix of the present invention contains the above-described pigment dispersion composition for black matrix of the present invention.

[0125] As the content of the above-mentioned pigment dispersion composition for black matrix, based on the total mass of the black matrix resist composition of the present invention, it is preferably 30 to 80% by mass, more preferably 40 to 75% by mass.

[0126] (Photopolymerization initiator)

[0127] The resist composition for black matrix of the present invention preferably contains a photopolymerization initiator.

[0128] As for the aforementioned photopolymerization initiators, there are no particular limitations as long as they are polymerization initiators that 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-acetyloxime) ethyl ketone, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, and benzoin methyl ether. Photopolymerization initiators such as benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenyl ketone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenyl ketone, tert-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, etc., are all benzophenones, thioxanthones, anthraquinones, triazines, etc.

[0129] The photopolymerization initiator can be used alone or in combination of two or more.

[0130] The content of the aforementioned photopolymerization initiator, as a mass fraction relative to the total solid components of the black matrix resist composition of the present invention, is preferably 1 to 20% by mass.

[0131] (Photopolymerizable compounds)

[0132] The resist composition for black matrix of the present invention preferably contains a photopolymerizable compound.

[0133] As the aforementioned photopolymerizable compounds, those compounds described for the aforementioned pigment dispersion compositions for black matrix can be appropriately selected and used.

[0134] The content of the aforementioned photopolymerizable compound, as a mass fraction relative to the total solid components of the black matrix resist composition of the present invention, is preferably 0.1 to 50% by mass.

[0135] (Alkali-soluble resin)

[0136] The resist composition for black matrix of the present invention preferably contains an alkali-soluble resin.

[0137] As the aforementioned alkali-soluble resin, it is preferable to have a resin that acts as a binder for the aforementioned black colorant and is soluble in the developing solution (especially an alkaline developing solution) used in the developing process during the manufacture of the black matrix.

[0138] The aforementioned alkali-soluble resin can be a block copolymer. By using a block copolymer, the pigment dispersion ability is improved compared to other copolymers, and it can impart solubility for PGMEA or alkaline developing solutions.

[0139] In this block copolymer, it is preferably a block copolymer having blocks composed of vinyl unsaturated monomers having one or more carboxyl groups and blocks composed of other copolymerizable vinyl unsaturated monomers.

[0140] There are no particular limitations on the block copolymers mentioned above, and commonly used block copolymers can be used. Specifically, examples include copolymers between carboxyl-containing vinyl unsaturated monomers such as acrylic acid and methacrylic acid, and at least one vinyl unsaturated monomer selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glyceryl monoacrylate, glyceryl methacrylate, N-phenylmaleimide, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

[0141] However, it is preferable not to use N-vinylpyrrolidone or sulfur-containing monomers.

[0142] The block copolymers described above can be block resins synthesized by living radical polymerization or anionic polymerization.

[0143] A portion of the block copolymers mentioned above may be composed of random copolymers.

[0144] As the aforementioned alkali-soluble resin, alkali-soluble Cardo resin can be used.

[0145] Examples of the aforementioned alkali-soluble Cardo resins include epoxy (meth)acrylate adducts having a fluorene skeleton, which are addition products of fluorene epoxy (meth)acrylate derivatives with dicarboxylic anhydrides and / or tetracarboxylic dianhydrides.

[0146] In addition, the alkali-soluble resin may also have photopolymerizable functional groups.

[0147] From the viewpoint of developing properties, the acid value of the alkali-soluble resin is preferably 5 to 300 mg KOH / g, more preferably 5 to 250 mg KOH / g, even more preferably 10 to 200 mg KOH / g, and particularly preferably 60 to 150 mg KOH / g.

[0148] Furthermore, in this specification, the acid value mentioned above is a theoretical acid value, which is a value obtained by calculation based on the ethylene unsaturated monomers with carboxyl groups and their content.

[0149] From the viewpoint of developing properties and solubility in organic solvents, the weight-average molecular weight of the above-mentioned alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000.

[0150] Furthermore, in this invention, the aforementioned weight-average molecular weight is the weight-average molecular weight of polystyrene converted from GPC.

[0151] In this specification, the Water2690 (manufactured by Waters Corporation) was used as the apparatus for determining the weight-average molecular weight, and the PLgel 5μm MIXED-D (manufactured by Agilent Technologies Corporation) was used as the column.

[0152] The content of the alkali-soluble resin is preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight, relative to 100 parts by weight of the black colorant.

[0153] At this time, if the content of the above-mentioned alkali-soluble resin is less than 1 part by mass, the development characteristics may be reduced; if the content of the above-mentioned alkali-soluble resin exceeds 200 parts by mass, the concentration of the above-mentioned black colorant is relatively reduced, so it is sometimes difficult to achieve the target color concentration as a film.

[0154] As the aforementioned alkali-soluble resin, it is preferable that it does not contain any of the primary, secondary, and tertiary amine groups, and more preferably that it does not contain quaternary ammonium groups. Furthermore, it is even more preferable that it does not have basic groups.

[0155] In addition, without compromising the effects of the present invention, alkali-soluble resins having structures other than block copolymers may also be mixed.

[0156] (Organic solvents)

[0157] As the organic solvents described above, those organic solvents already described for the pigment dispersion composition for the black matrix can be appropriately selected and used.

[0158] The content of the aforementioned organic solvent, based on the total mass of the black matrix resist composition of the present invention, is preferably 1 to 40% by mass, more preferably 5 to 35% by mass.

[0159] (Other additives)

[0160] The resist composition for black matrix of the present invention may use various additives such as heat-resistant polymerizers (heat polymerization inhibitors), ultraviolet absorbers, and antioxidants as needed.

[0161] (Method for manufacturing a resist composition for black matrix)

[0162] As a method for manufacturing the resist composition for black matrix of the present invention, it can be manufactured, for example, by adding the remaining materials after preparing the pigment dispersion composition for black matrix of the present invention and mixing it using a stirring device or the like.

[0163] There are no particular limitations on the above-mentioned mixing method; known methods such as ultrasonic dispersers, high-pressure emulsifiers, bead mills, triple roll mills, sand mills, and kneaders can be used.

[0164] Alternatively, the mixture can be filtered using a filter after stirring and mixing.

[0165] In addition, when preparing the resist composition for black matrix of the present invention, the above-described black colorant, epoxy resin, oxazine compound, etc., described in the pigment dispersion composition for black matrix of the present invention may be added as needed.

[0166] <Black Matrix>

[0167] The black matrix of the present invention is formed by using a photoresist composition.

[0168] There are no particular limitations on the method for forming the black matrix of the present invention. For example, the black matrix can be formed by coating a transparent substrate with the photoresist composition for the black matrix of the present invention, drying it to form a coating film, placing a photomask on the coating film, exposing and developing an image through the photomask, and photocuring as needed.

[0169] For the coating, drying, exposure, and development methods of the resist composition for black matrix of the present invention, known methods may be appropriately selected.

[0170] In addition, as the aforementioned transparent substrate, known transparent substrates such as glass substrates and plastic substrates can be appropriately selected.

[0171] The thickness of the coating film, measured by the film thickness after drying, is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm.

[0172] By setting the thickness to the above range, the specified pattern can be developed appropriately and the specified optical density can be appropriately assigned.

[0173] The black matrix of this invention is coated onto a glass substrate (EAGLE XG) using a spin coater to achieve a film thickness of 1 μm, pre-baked at 100°C for 3 minutes, and then exposed to a high-pressure mercury lamp (UV cumulative light intensity 80 mJ / cm²). 2Then, a post-baking process is performed at 230°C for 60 minutes. The preferred surface resistivity for preparing a black resist pattern formed only by the solid areas is 2.0 × 10⁻⁶. 9 Ω / □ or higher, more preferably 5.0 × 10 9 Ω / □ or higher, more preferably 9.0 × 10⁻⁶ 9 Ω / □ and above.

[0174] If the above surface resistance value is set to 2.0 × 10 9 A value of Ω / □ or higher can effectively prevent short circuits or current leakage.

[0175] In addition, the above surface resistance value can be measured using a "micro-ammeter R8340" as the main body and a "shielded box R12702A" as the option (both manufactured by ADVANCE Co., Ltd.).

[0176] Since the pigment dispersion composition for black matrix, the resist composition for black matrix, and the black matrix of the present invention have the above-mentioned characteristics, they can be preferably used as black matrices for image display devices or touch panels, etc.

[0177] Example

[0178] The present invention will now be illustrated with specific examples; however, the invention is not limited to these examples as long as it does not depart from its spirit and scope of application. It should be noted that, unless otherwise specified, in these examples, "parts" and "%" respectively represent "parts by mass" and "% by mass".

[0179] The various materials used in the following embodiments and comparative examples are described below.

[0180] <Black dye>

[0181] Carbon black (trade name "NEROX 305", average primary particle size of about 28nm, pH of about 2.8, manufactured by Orion Engineered Carbons)

[0182] <Pigment Dispersant>

[0183] DISPERBYK-167 (solid content 52 g / L, manufactured by BYK-Chemie)

[0184] <Amine compounds>

[0185] 3-Phenylephrine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0186] 1,1,3,3-Tetramethylbutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0187] Triisobutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0188] <Adhesive Resins>

[0189] ZCR-1569H (Epoxy acrylate resin, 70% solids by mass, manufactured by Nippon Kayaku Co., Ltd.)

[0190] <Organic Solvents>

[0191] PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[0192] <Photopolymerization Initiator>

[0193] OXE 02 (trade name "Irgacure OXE02", 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime) ethyl ketone, manufactured by BASF)

[0194] <Photopolymerizable compounds>

[0195] DPHA (Dipentaerythritol Hexaacrylate)

[0196] <Alkali-soluble resins>

[0197] WR-301 (product name is "WR-301", Cardo resin, acid value is 100mgKOH / g, solid content is 45% by mass, manufactured by ADEKA)

[0198] <Preparation of the Dispersion Composition>

[0199] (Dispersion Composition 1)

[0200] Solsperse 12000 (a sulfonated form of copper phthalocyanine (containing about 0.9 sulfonic acid groups per molecule), manufactured by The Lubrizol Corporation, Japan) was mixed with 3-phenylpropylamine at a mass ratio of 25:8 to obtain dispersion composition 1.

[0201] (Dispersion Composition 2)

[0202] Solsperse12000 (a sulfonated form of copper phthalocyanine (containing about 0.9 sulfonic acid groups per molecule), manufactured by The Lubrizol Corporation, Japan) was mixed with 1,1,3,3-tetramethylbutylamine at a mass ratio of 10:3 to obtain dispersion composition 2.

[0203] (Dispersion Composition 3)

[0204] Solsperse 12000 (a sulfonated form of copper phthalocyanine (containing about 0.9 sulfonic acid groups per molecule), manufactured by The Lubrizol Corporation, Japan) and triisobutylamine were mixed at a mass ratio of 25:11 to obtain dispersion composition 3.

[0205] <Dispersion Materials>

[0206] Solsperse 12000 (a sulfonated form of copper phthalocyanine (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by The Lubrizol Corporation, Japan)

[0207] Solsperse 5000 (a quaternary ammonium salt of copper phthalocyanine sulfonate (containing approximately 0.9 sulfonic acid groups per molecule), manufactured by The Lubrizol Corporation, Japan)

[0208] VALIFAST BLUE 1605 (VB 1605, sodium neutralization of copper phthalocyanine sulfonate, manufactured by ORIENT Chemical Industry Co., Ltd.)

[0209] <Preparation of Pigment Dispersion Compositions for Black Matrix>

[0210] The materials were mixed to form the composition shown in Table 1, and then kneaded in a bead mill for 24 hours to prepare a pigment dispersion composition for black matrix.

[0211] [Table 1]

[0212]

[0213] <Preparation of the Resist Composition for Black Matrix>

[0214] Using a high-speed mixer, the above-mentioned black matrix pigment dispersion composition and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator and organic solvent) were uniformly mixed in the manner shown in Table 2, and then filtered through a filter with a pore size of 3 μm to obtain the black matrix resist compositions of the examples and comparative examples.

[0215] <Evaluation Experiment>

[0216] (Surface resistivity)

[0217] The black matrix compositions of the examples and comparative examples were coated onto a glass substrate (EAGLE XG) using a spin coater with a pigment-dispersed resist composition to achieve a film thickness of 1 μm. After pre-baking at 100°C for 3 minutes, the films were exposed to a high-pressure mercury lamp (UV cumulative light intensity of 80 mJ / cm²). 2 Then, bake at 230°C for 60 minutes to prepare a black resist pattern (black matrix) formed only by the solid part.

[0218] The surface resistivity of each prepared black resist pattern was measured using a micro-ammeter R8340 (with an optional shielded box R12702A) (both manufactured by ADVANCE Co., Ltd.). The results are shown in Table 2.

[0219] [Table 2]

[0220]

[0221] In examples using a pigment dispersion composition for a black matrix comprising a black colorant, a copper phthalocyanine sulfonate, and a specific amine compound, it was confirmed that a black matrix with a high surface resistivity could be formed.

[0222] Industrial applicability

[0223] Based on the present invention, a pigment dispersion composition for forming a black matrix with high surface resistivity can be provided.

Claims

1. A pigment dispersion composition for a black matrix, wherein, The black matrix pigment dispersion composition comprises a black colorant, a sulfonated copper phthalocyanine, and an amine compound. The sulfonated phthalocyanine copper does not contain compounds represented by the following structural formula: ； The amine compound is selected from at least one of the following compounds (A) and (B): (A) 1,1,3,3-Tetramethylbutylamine, diisopropylamine, triisopropylamine, diisobutylamine, triisobutylamine, diisoamylamine, triisoamylamine, tri(2-ethylhexyl)amine; (B) 3-Phenylamidine, 2-Phenylamidine, 1-Phenylamidine, 2-Phenylethylamine, 1-Phenylethylamine, phenylmethylamine, triphenylmethylamine.

2. The pigment dispersion composition for black matrix as described in claim 1, wherein, The sulfonated form of copper phthalocyanine has 0.5 to 3 sulfonic acid groups in its molecule.

3. The pigment dispersion composition for black matrix as described in claim 2, wherein, The sulfonated form of copper phthalocyanine has 0.5 to 1.5 sulfonic acid groups in its molecule.

4. The pigment dispersion composition for black matrix as described in claim 1 or 2, wherein, The black colorant contains carbon black.

5. The pigment dispersion composition for black matrix as described in claim 4, wherein, The carbon black is acidic carbon black.

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

7. A black matrix formed by using a resist composition according to claim 6.

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