Pigment dispersion composition for black matrix and its manufacturing method, photoresist composition for black matrix, and black photoresist film.

Abstract

The pigment dispersion composition for black matrix of the present invention contains carbon black, a pigment dispersant containing basic groups, a pigment dispersing aid containing acidic groups, an alkali-soluble resin, an ion scavenger, and a solvent. The carbon black is acidic carbon black, and the ion scavenger is an inorganic compound with a median diameter of 0.1 to 10 μm, and is present in a concentration of 1 to 15 parts by mass relative to 100 parts by mass of the carbon black. This pigment dispersion composition for black matrix exhibits excellent optical concentration and fine-line adhesion.

Description

Technical field

[0001] The invention relates to a pigment dispersion composition for black matrices and a method of fabrication thereof, a photoresist composition for black matrices, and a black photoresist film. Prior technology

[0002] The photoresistive compositions of pigment dispersion compositions with pigments of black matrix using carbon black, pigment dispersants containing basic groups, pigment dispersion aids containing acidic groups, adhesive resins and solvents, etc., have been required to have higher optical concentration (shielding) or fine line closeness (resolution) (Patent literature 1), In addition, it is known that if the carbon black is cleaned to improve the optical occlusion (literature 2 can improve the concentration of potassium (patent literature). [Previous technical literature] [Patent Literature]

[0003] [Patent Literature 1] Japan Special Bulletin No. 2021-38289 [Patent Literature 2] Bulletin of Japan Special Open No. 2007-316620 Contents of the invention

[0004] [Invent the topic to be solved] []

[0005] However, as mentioned above in the case of cleaning the carbon black, there is the following problem, namely, the need to use a large amount of water, and consequently, the need to perform cumbersome operations such as cleaning, filtration, and drying. In addition, in order to remove potassium ions in the composition, it is generally known that there is a method to pass the composition liquid through a resin tower equipped with ion exchange resin.

[0006] The invention is made in view of the above practical situation, where the purpose is to provide a black matrix pigment-dispersed composition obtaining a photoresist composition for black matrix with excellent optical concentration and fine wire closeness. [Technical means of solving the problem]

[0007] In other words, the present invention relates to a pigment dispersion composition for a black matrix, comprising carbon black, a pigment dispersant containing basic groups, a pigment dispersing aid containing acidic groups, an alkali-soluble resin, an ion scavenger, and a solvent, wherein the carbon black is acidic carbon black, and the ion scavenger is an inorganic compound with a median diameter of 0.1 to 10 μm, and is present in a concentration of 1 to 15 parts by mass relative to 100 parts by mass of the carbon black.

[0008] Furthermore, the present invention relates to a photoresist composition for black matrix, which contains the aforementioned pigment dispersion composition for black matrix, a photopolymerizable compound, and a photopolymerization initiator.

[0009] Furthermore, the present invention relates to a black photoresist film obtained using a black matrix photoresist composition.

[0010] Furthermore, the present invention relates to a method for manufacturing a pigment dispersion composition for a black matrix, which is a method for manufacturing the aforementioned pigment dispersion composition for a black matrix, wherein the aforementioned carbon black is at least dispersed in the presence of the aforementioned ion scavenger. [Effects of the Invention]

[0011] The pigment dispersion composition for black matrix of the present invention contains carbon black, a pigment dispersant containing basic groups, a pigment dispersant aid containing acidic groups, an alkali-soluble resin, an ion scavenger, and a solvent. The carbon black is acidic carbon black, and the ion scavenger is an inorganic compound with a median diameter of 0.1 to 10 μm, and is present in an amount of 1 to 15 parts by mass relative to 100 parts by mass of the carbon black. Because the pigment dispersion composition for black matrix of the present invention can capture substances containing potassium ions or similar ions mixed in during the manufacture of acidic carbon black using the aforementioned ion scavenger, a photoresist composition for black matrix with excellent optical concentration and fine-line adhesion can be obtained even without the need for cleaning operations such as acidic carbon black. Simple Explanation of the Diagram

[0012] none Implementation

[0013] The black matrix pigment dispersion composition of the present invention contains carbon black, a pigment dispersant containing basic groups, a pigment dispersant containing acidic groups, an alkali-soluble resin, an ion scavenger, and a solvent.

[0014] <Carbon Black> The aforementioned carbon black is an acidic carbon black containing acidic groups such as carboxyl groups. As the aforementioned acidic carbon black, known acidic carbon blacks used in pigment dispersion compositions for black matrix can be used. For example, from the viewpoint of improving developability and fine line adhesion, a pH of 5.0 or lower is preferred, more preferably a pH of 1.0 or higher and 3.5 or lower. Furthermore, a DBP oil absorption of 80 ml / 100 g or lower is preferred, more preferably a DBP oil absorption of 70 ml / 100 g or lower, and a particle size of 20-60 nm is preferred. The aforementioned pH can be determined by adding 1 g of carbon black to 20 ml of decarbonated distilled water (pH 7.0), mixing with a magnetic stirrer to prepare an aqueous suspension, and measuring the pH at 25°C using a glass electrode (German Industrial Standard DIN ISO 787 / 9). Furthermore, DBP oil absorption refers to the indirect quantification of the carbon black structure by measuring the pore volume, and is a value obtained according to JIS K6217-4. Additionally, the aforementioned particle size refers to the average primary particle size measured or calculated by microscopic observation. For these values, refer to the catalog values ​​when using commercially available products. The aforementioned carbon black can be used alone or in combination of two or more types.

[0015] Specific examples of acidic carbon blacks mentioned above include: Raven 1080 (pH 2.4, average primary particle size 28 nm, DBP oil absorption 60 ml / 100 g) manufactured by Colombian Chemicals, Raven 1100U (pH 2.9, average primary particle size 32 nm, DBP oil absorption 72 ml / 100 g), NEROX 305 (pH 2.8, average primary particle size 28 nm, DBP oil absorption 58 ml / 100 g), and NEROX 3500 (pH 3.0, average primary particle size 31 nm, DBP oil absorption 43 ml / 100 g); TPK 1104R (pH 3.0, average primary particle size approximately 30 nm, DBP oil absorption 38 ml / 100 g) manufactured by Cabot; and MA14 (pH 2.8, average primary particle size 40 nm, DBP oil absorption 73 ml / 100 g) manufactured by Mitsubishi Chemicals. (g), MA220 (pH 2.9, average primary particle size 55 nm, DBP oil absorption 93 ml / 100 g), etc.

[0016] In the above-mentioned pigment dispersion composition for black matrix, from the viewpoint of improving the opacity when forming a black matrix film, the carbon black is preferably 3% by mass or more, more preferably 10% by mass or more, and from the viewpoint of pigment dispersion, the carbon black is preferably 70% by mass or less, more preferably 50% by mass or less.

[0017] Pigment dispersants containing basic groups The aforementioned pigment dispersant containing a basic group is suitable as long as it can disperse the carbon black. Known pigment dispersants containing basic groups used in pigment dispersion compositions for black matrices can be used, such as anionic surfactants, polyester-based pigment dispersants containing basic groups, acrylic-based pigment dispersants containing basic groups, urethane-based pigment dispersants containing basic groups, and carbodiimide-based pigment dispersants containing basic groups. From the viewpoint of excellent dispersibility, primary, secondary, or tertiary amine groups are particularly preferred as the basic group. The aforementioned pigment dispersants containing basic groups can be used alone or in combination of two or more.

[0018] From the viewpoint of achieving good pigment dispersibility, the aforementioned pigment dispersant containing a basic group is preferably a polymeric pigment dispersant containing a basic group. Examples of such polymeric pigment dispersants containing basic groups include: amine ester-based polymeric pigment dispersants containing basic groups, polyester-based polymeric pigment dispersants containing basic groups, and acrylic-based polymeric pigment dispersants containing basic groups. Among these, amine ester-based polymeric pigment dispersants and acrylic-based polymeric pigment dispersants containing basic groups are preferred. More preferably, the aforementioned amine ester-based polymeric pigment dispersant containing a basic group is an amine ester-based polymeric pigment dispersant having at least one type of chain selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains.

[0019] From the viewpoint of achieving low viscosity in the pigment dispersion composition for black matrix coatings and high carbon black concentration in the coating film, the amine value of the aforementioned pigment dispersant containing basic groups is preferably 5~50 mgKOH / g, and more preferably 5~35 mgKOH / g. Furthermore, the amine value represents the free bases and the total amount of bases, expressed as the number of mg of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of sample.

[0020] The pigment dispersant containing alkaline groups is preferably 1 to 100 parts by weight, and more preferably 2 to 50 parts by weight, relative to 100 parts by weight of carbon black.

[0021] <Pigment dispersing aids containing acidic groups> The aforementioned pigment dispersing aids containing acidic groups are used to further improve pigment dispersibility. Examples include: acetamide black, perylene compounds, pyrrolopyrrole dione compounds, azonaphthol compounds, and dioxane compounds. Acetylene compounds, quinacridone compounds, phthalocyanine compounds and their metal complexes; anthraquinones, naphthalenes, acridinones or triterpenoids Compounds obtained by introducing acidic groups such as carboxyl groups and sulfonic acid groups into pigments (pigment derivatives with acidic groups); or compounds obtained by neutralizing these compounds with organic amines, etc. From the viewpoint of good dispersibility of carbon black, phthalocyanine-based pigment derivatives (those with phthalocyanine skeletons) with sulfonic acid groups are preferred as the aforementioned pigment derivatives with acidic groups. The aforementioned pigment dispersing aids containing acidic groups can be used alone or in combination of two or more.

[0022] The pigment dispersing aid containing acidic groups is preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, relative to 100 parts by weight of carbon black.

[0023] Alkali-soluble resins There are no particular limitations on the alkali-soluble resins mentioned above, as long as they can dissolve in alkaline developing solutions. Preferably, they are resins containing one or more anionic groups such as carboxyl groups, sulfonic acid groups, or phosphonic acid groups (-P(=O)(OH 2)). The alkali-soluble resins mentioned above can be used alone or in combination of two or more.

[0024] From the viewpoint of alkaline developability, the acid value of the above-mentioned alkali-soluble resin is preferably 10 mgKOH / g or more and 300 mgKOH / g or less, and more preferably 20 mgKOH / g or more and 200 mgKOH / g or less.

[0025] From the viewpoint of photoresist film formation, the weight average molecular weight of the aforementioned alkali-soluble resin is preferably 3,000 or more, and more preferably 4,000 or more. From the viewpoint of improving solubility in alkaline developer, the weight average molecular weight of the aforementioned alkali-soluble resin is preferably 100,000 or less, and more preferably 50,000 or less.

[0026] The aforementioned weight-average molecular weight can be determined using gel permeation chromatography (GPC). For example, a Water 2690 (manufactured by Waters Corporation) can be used as the GPC apparatus, with a PLgel, 5 μm, MIXED-D (manufactured by Polymer Laboratories) column, and tetrahydrofuran as the developing solvent. Chromatography can be performed at a column temperature of 25°C, a flow rate of 1 mL / min, an RI detector, a sample injection concentration of 10 mg / mL, and an injection volume of 100 μL to determine the converted weight-average molecular weight of polystyrene.

[0027] Examples of alkali-soluble resins include: alkali-soluble polyimide resins, alkali-soluble polyimide precursors, and alkali-soluble polyphenylene oxide resins. azole resin, alkali-soluble polybenzo[a]pyrene Examples of suitable resins include azole precursors, alkali-soluble cardo resins, alkali-soluble epoxy (meth)acrylate resins, alkali-soluble polysiloxane resins, alkali-soluble phenolic varnish resins, alkali-soluble (meth)acrylate resins, alkali-soluble polyurethane resins, and alkali-soluble polyester resins. From the perspective of coating heat resistance, alkali-soluble cardo resins and alkali-soluble epoxy (meth)acrylate resins are preferred.

[0028] The aforementioned alkali-soluble calo resin refers to an alkali-soluble resin with a calo skeleton. A calo skeleton is a skeleton in which two aromatic groups are connected by single bonds to the quaternary carbon atoms that constitute the cyclic carbon structure. Specific examples of alkali-soluble calo resins include: ADEKA ARKLS WR-301 (manufactured by ADEKA Corporation), OGSOL CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, and CR-TR6 (manufactured by Osaka Gas Chemicals Corporation).

[0029] The aforementioned alkali-soluble epoxy (meth)acrylate resin refers to a resin among the following acid-modified epoxy resins that does not possess the aforementioned caloric skeleton and is equivalent to the aforementioned alkali-soluble resin. The aforementioned acid-modified epoxy resin is obtained by introducing an ethylene unsaturated group through a ring-opening addition reaction between the carboxyl group of an ethylene unsaturated monocarboxylic acid and the epoxy group of the epoxy resin, and further by introducing a carboxyl group through the addition reaction between a polycarboxylic acid (or its anhydride) and at least a portion of the hydroxyl groups generated by the ring-opening of the epoxy group. Among the aforementioned alkali-soluble epoxy (meth)acrylate resins, epoxy resins that serve as the parent raw material are preferably, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having a biphenyl structure, phenolic varnish type epoxy resin, and cresol varnish type epoxy resin. As ethylene unsaturated monocarboxylic acids used to modify the epoxy resin, preferably, for example, acrylic acid and methacrylic acid. Examples of polycarboxylic acids (or their anhydrides) preferably include maleic anhydride, succinic anhydride, and tetrahydrophthalic anhydride. From the viewpoint of improving the tightness of the fine threads, alkali-soluble epoxy (meth)acrylate resins having a biphenyl backbone are preferred. Specific examples of the aforementioned alkali-soluble epoxy (meth)acrylate resins include ZAR-1494H, ZAR-2001H, ZFR-1491H, ZCR-1797H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.). Furthermore, as a preferred example, alkali-soluble epoxy (meth)acrylate resins having a partial structure represented by any of the following structural formulas can be listed.

[0030]

[0031] The alkali-soluble resin is preferably 1 to 70 parts by weight, and more preferably 2 to 40 parts by weight, relative to 100 parts by weight of carbon black.

[0032] <Ion scavenger> The aforementioned ion scavengers are inorganic compounds with a median diameter of 0.1 to 10 μm. The ion scavengers only need to be able to capture at least one of cations and anions; examples include cation scavengers, anion scavengers, and zwitterion scavengers with ion-capturing capabilities. Examples of inorganic compounds include those containing one or more metal atoms selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. Preferably, the inorganic compounds contain one or more metal atoms selected from the group consisting of bismuth, zirconium, magnesium, and aluminum. The aforementioned ion scavengers can be used alone or in combination of two or more. Furthermore, the aforementioned median diameter can be measured using a laser diffraction / scattering particle size distribution measuring device; when using commercially available products, refer to the catalog values.

[0033] The aforementioned ion trapping agent is 1 to 15 parts by mass relative to 100 parts by mass of the aforementioned carbon black. From the viewpoint of improving the tightness of the fine wires, the aforementioned ion trapping agent is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the aforementioned carbon black. Furthermore, from the viewpoint of improving optical density, the aforementioned ion trapping agent is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, relative to 100 parts by mass of the aforementioned carbon black.

[0034] Solvent The solvents described above can be any known solvents used in the pigment dispersion composition of the black matrix. From the viewpoint of being able to stably disperse the pigment and fully dissolve the pigment dispersant containing the basic group or the alkali-soluble resin described above, the solvents are preferably ester solvents, ether solvents, ether-ester solvents, ketone solvents, aromatic hydrocarbon solvents, nitrogen-containing solvents, etc. The solvents described above can be used alone or in combination of two or more.

[0035] Examples of ester-based solvents include: 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, glycolic acid ester, and n-pentyl formate. Examples of ether-based 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, and diethylene glycol methyl ethyl ether. Examples of ether-ester solvents include: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Examples of ketone solvents include: methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone. Examples of aromatic hydrocarbon solvents include: toluene, xylene, and alkylnaphthalene. Examples of nitrogen-containing solvents include: N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0036] In the above-mentioned black matrix pigment dispersion composition, from the viewpoint of processability, the proportion of the solvent is preferably 40% by mass or more, more preferably 50% by mass or more, and from the viewpoint of dispersion stability, the proportion of the solvent is preferably 90% by mass or less, more preferably 80% by mass or less.

[0037] <Epoxy Resin> From the viewpoint of improving the tightness of fine lines, epoxy resin can also be used in the pigment dispersion composition of the aforementioned black matrix. Especially in high-resistivity applications, blended epoxy resin is preferred. The aforementioned epoxy resin is a polyfunctional epoxy resin having two or more epoxy groups. Examples of such epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, triphenol methane type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, epoxy propylene ester type epoxy resin, epoxy propylene ethers of condensates of phenolic compounds (phenol, cresol, alkylphenol, catechol, bisphenol F, bisphenol A, bisphenol S, etc.) and aldehyde compounds (formaldehyde, salicylaldehyde, etc.), epoxy propylene ethers of difunctional phenols, epoxy propylene ethers of difunctional alcohols, epoxy propylene ethers of polyphenols with three or more functions, and their hydrides or halides, etc. The epoxy resin mentioned above can be a multifunctional epoxy resin having alicyclic or aromatic rings. Alternatively, it can be a multifunctional epoxy resin having a dicyclopentadiene skeleton as an alicyclic ring. From the viewpoint of improving the tightness of the fine wires, a multifunctional epoxy resin having aromatic rings is preferred. Specific examples of the aforementioned epoxy resins include: Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 80MF, Epolight 4000, Epolight 3002 (all manufactured by Kyoei Chemical Co., Ltd.); DENACOL EX-212L, DENACOL EX-214L, DENACOL EX-216L, DENACOL EX-850L, DENACOL EX-321L (all manufactured by Nagase Chemical Co., Ltd.); GAN, GOT, NC3000, NC6000, EPPN502H, EPPN-503 (all manufactured by Nippon Kayaku Co., Ltd.); Epikote 828, Epikote 1002, Epikote... 1750, Epikote 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resins); EPICLON EXA-9583, EPICLON N695, HP7200, HP4032 (all manufactured by Dai Nippon Ink & Chemical Co., Ltd.); VG3101 (manufactured by Mitsui Chemicals); TEPIC S, TEPIC G, TEPIC P (manufactured by Nissan Chemical Industries, Ltd.); Epotohto YH-434L (manufactured by Toto Kasei Corporation), etc. Furthermore, from the perspective of reactivity, the above epoxy resins are preferably free of indene or biphenyl structures..

[0038] As an example of the aforementioned epoxy resin, the following are preferred examples: multifunctional epoxy resins having aromatic rings represented by formulas 1 to 7 below.

[0039] (Equation 1) (m is 0~20)

[0040] (Equation 2)

[0041] (Equation 3) (n is 1~20)

[0042] (Equation 4) (R 1~6 are each a saturated hydrocarbon group with 1~6 carbon atoms, and n is 1~20)

[0043] (Equation 5) (n is 1~20)

[0044] (Equation 6) (R 1~2 are each independently hydrogen or saturated hydrocarbon groups with 1~6 carbon atoms, and n is 1~20)

[0045] (Equation 7) (n is 1~20)

[0046] From the viewpoint of resistivity when forming a black matrix, the epoxy resin is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of carbon black contained in the pigment dispersion composition for the black matrix or the photoresist composition for the black matrix. Furthermore, from the viewpoint of blackness based on pigment concentration, the epoxy resin is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of carbon black contained in the pigment dispersion composition for the black matrix or the photoresist composition for the black matrix.

[0047] The aforementioned black matrix pigment dispersion composition may also be further supplemented with leveling agents, resins other than the aforementioned epoxy resin and alkali-soluble resin, antioxidants, defoamers, and other additives as needed. From an odor perspective, it is preferable to avoid the presence of thiol compounds (e.g., thiol compounds with a molecular weight of 1000 or less).

[0048] In the aforementioned pigment dispersion composition for black matrix, the total proportion of the carbon black, the pigment dispersant containing basic groups, the pigment dispersing aid containing acidic groups, the alkali-soluble resin, the ion scavenger, and the solvent is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more. Furthermore, when the aforementioned epoxy resin is incorporated, the total proportion of the carbon black, the pigment dispersant containing basic groups, the pigment dispersing aid containing acidic groups, the alkali-soluble resin, the ion scavenger, the solvent, and the epoxy resin in the aforementioned pigment dispersion composition for black matrix is ​​preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more.

[0049] Regarding the aforementioned pigment dispersion composition for black matrix, it can be prepared by dispersing the above components using a tumbling mill, kneader, high-speed mixer, bead mill, ball mill, sand mill, ultrasonic disperser, high-pressure dispersion device, etc. In particular, from the viewpoint of efficiently capturing ionic substances contained in the aforementioned carbon black to improve optical concentration and fine-line adhesion, it is preferable to at least disperse the aforementioned carbon black in the presence of the aforementioned ion-capturing agent.

[0050] <Black Matrix using photoresist composition> The photoresist composition for black matrix of the present invention contains the above-mentioned pigment dispersion composition for black matrix, a photopolymerizable compound, and a photopolymerization initiator. Furthermore, in the solid composition of the above-mentioned photoresist composition for black matrix, the proportion of carbon black is preferably 30% by mass or more and 80% by mass or less.

[0051] <Photopolymerizable compounds> The aforementioned photopolymerizable compounds can be any known photopolymerizable compounds used in the photoresist composition of black matrices, such as monomers and oligomers having photopolymerizable unsaturated bonds. These photopolymerizable compounds can be used alone or in combination of two or more.

[0052] Monomers possessing one photopolymerizable unsaturated bond can be exemplified by: methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and other alkyl methacrylates or alkyl acrylates; benzyl methacrylate, benzyl acrylate, and other aralkyl methacrylates or aralkyl acrylates; butoxyethyl methacrylate, butoxyethyl acrylate, and other alkoxyalkyl methacrylates or alkoxyalkyl acrylates; methacrylic acid-N,N- Dimethylaminoethyl ester, N,N-dimethylaminoethyl acrylate, and other aminoalkyl methacrylates or aminoalkyl acrylates; diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and other polyalkylene glycol monoalkyl ethers in the form of methacrylates or acrylates; hexaethylene glycol monophenyl ether and other polyalkylene glycol monoaryl ethers in the form of methacrylates or acrylates; isoborneol methacrylate or isoborneol acrylate; glyceryl methacrylate or glyceryl acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, etc.

[0053] Monomers possessing two or more photopolymerizable unsaturated bonds include, for example: bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, glyceryl dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl tetramethacrylate, and dinepentyl tetramethacrylate. Esters, dinepentylenetetroxide hexamethacrylate, dinepentylenetetroxide pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glyceryl diacrylate, neopentylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, neopentylenetetroxide triacrylate, neopentylenetetroxide tetraacrylate, dinepentylenetetroxide hexaacrylate, dinepentylenetetroxide pentaacrylate, etc.

[0054] Oligomers with photopolymerizable unsaturated bonds can be exemplified by oligomers obtained by appropriately polymerizing the aforementioned monomers.

[0055] In the solid composition of the above-mentioned black matrix photoresist composition, the photopolymerizable compound is preferably 2-20% by mass, more preferably 4-15% by mass.

[0056] The aforementioned photopolymerization initiators can be well-known photopolymerization initiators used in black matrix photoresist compositions, such as: benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, ethylene glycol diacetate, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl benzoate, 9-oxosulfuron 2-Chloro-9-oxosulfur 1-Hydroxycyclohexylphenyl ketone, tributylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, tri- These include photopolymerization initiators such as oxime esters and other similar initiators. These photopolymerization initiators can be used alone or in combination of two or more.

[0057] In the solid composition of the above-mentioned black matrix photoresist composition, the above-mentioned photopolymerization initiator is preferably 0.1~15% by mass, more preferably 1~10% by mass.

[0058] From the viewpoint of developing alkaline developer properties, the aforementioned alkali-soluble resin can be further added to the above-mentioned photoresist composition for black matrix. Furthermore, the total amount of the alkali-soluble resin in the solids component of the above-mentioned photoresist composition for black matrix is ​​preferably 10% by mass or more and 50% by mass or less. Furthermore, from the viewpoint of improving coatability, the aforementioned solvent can be further added to the above-mentioned photoresist composition for black matrix. The total proportion of the aforementioned solvent in the above-mentioned photoresist composition for black matrix is ​​preferably 50% by mass or more, and more preferably 70% by mass or more.

[0059] In the above-mentioned black matrix photoresist composition, additives such as leveling agents, antioxidants, and defoamers can also be added as needed.

[0060] Regarding the aforementioned photoresist composition for black matrix, it can be prepared by simply using a stirring device or the like to stir and mix the aforementioned pigment dispersion composition for black matrix, photopolymerizable compound, and photopolymerization initiator.

[0061] <Black photoresist film> The black photoresist film of the present invention is obtained using the aforementioned black matrix photoresist composition. The surface resistivity of the aforementioned black photoresist film is preferably 5.0 × 10⁹ Ω / □ or higher, more preferably 1.0 × 10¹⁰ Ω / □ or higher, and even more preferably 1.0 × 10¹¹ Ω / □ or higher. Particularly in high-resistivity applications, the surface resistivity is preferably 1.0 × 10¹² Ω / □ or higher, and more preferably 1.0 × 10¹³ Ω / □ or higher. [Example]

[0062] The present invention will be described below by way of examples, but the present invention is not limited to these examples.

[0063] <Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-6> <Preparation of Pigment Dispersions for Black Matrix> The various raw materials shown in Tables 1 and 2 were mixed in such a way as the blending composition (mass %) shown in Tables 1 and 2, and then milled using a bead mill to prepare the black matrix pigment dispersion composition of each embodiment and comparative example.

[0064] [Table 1] Example Comparative example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-1 1-2 1-3 carbon black NEROX305 24.0 24.0 24.0 24.0 24.0 24.0 24.0 25.0 21.0 24.8 TPK1104R Ion scavengers IXEPLAS B1 1.0 IXE-100 1.0 4.0 0.2 IXE-500 1.0 IXE-550 1.0 IXE-600 1.0 IXE-700F IXE-770F 1.0 IXE-6136 1.0 Pigment dispersants containing alkaline groups DB167 (52% solids) 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 Pigment dispersing aids containing acidic groups SS5000S 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 BYK2100 Alkali-soluble resins ZCR-1569H (solid content 69%) 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 Epoxy resin EPPN-503 solvent PGMEA 62.8 62.8 62.8 62.8 62.8 62.8 62.8 62.8 62.8 62.8 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

[0065] [Table 2] Example Comparative example 1-8 1-9 1-10 1-11 1-4 1-5 1-6 carbon black NEROX305 TPK1104R 24.0 24.0 24.0 24.0 25.0 21.0 24.8 Ion scavengers IXEPLAS B1 IXE-100 1.0 4.0 0.2 IXE-500 IXE-550 1.0 IXE-600 IXE-700F 1.0 IXE-770F IXE-6136 1.0 Pigment dispersants containing basic groups DB167 (52% solids) 7.3 7.3 7.3 7.3 7.3 7.3 7.3 Pigment dispersing aids containing acidic groups SS5000S BYK2100 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Alkali-soluble resins ZCR-1569H (solid content 69%) 4.3 4.3 4.3 4.3 4.3 4.3 4.3 Epoxy resin EPPN-503 2.5 2.5 2.5 2.5 2.5 2.5 2.5 solvent PGMEA 59.8 59.8 59.8 59.8 59.8 59.8 59.8 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

[0066] In Tables 1 and 2, NEROX 305 indicates acidic carbon black (oil absorption 58 ml / 100 g, pH 2.8, average primary particle size 28 nm, manufactured by Orion Engineered Carbons). TPK1104R indicates acidic carbon black (oil absorption: 38 ml / 100 g, pH 3.0, average primary particle size approximately 30 nm, manufactured by Cabot). IXEPLAS B1 indicates a zirconium / bismuth based zirconium ion trap (median diameter 0.4 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-100 indicates a cation scavenger (zirconium-based, median diameter 1 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-500 indicates anion scavenger (bismuth-based, median diameter 1.5 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-550 indicates an anion scavenger (bismuth-based, median diameter 1.5 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-600 indicates a zwitterion (antimony / bismuth based, median diameter 1 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-700F indicates an anion scavenger (aluminum / magnesium based, median diameter 1.5 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-770F indicates anion scavenger (aluminum / magnesium based, median diameter 6 μm, manufactured by Toa Synthetic Co., Ltd.); IXE-6136 indicates a zirconium / bismuth based zirconium ion trap (median diameter 2.1 μm, manufactured by Toa Synthetic Co., Ltd.); DB167 indicates a polyurethane polymeric dispersant containing amine groups and having polyester chains (manufactured by BYK-Chemie, amine value of solids content 25 mgKOH / g, solids content 52% by mass); SS5000S indicates a phthalocyanine pigment derivative with a sulfonic acid group (manufactured by Lubrizol). BYK2100 indicates a phthalocyanine pigment derivative with sulfonic acid groups (manufactured by BYK-Chemie). ZCR-1569H indicates an alkali-soluble epoxy (meth)acrylate resin with a biphenyl backbone (69% solids content, manufactured by Nippon Kayaku Co., Ltd.); EPPN-503 indicates a trihydroxyphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.); PGMEA stands for propylene glycol monomethyl ether acetate.

[0067] <Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-6> <Preparation of Photoresist Compositions for Black Matrix> Using a high-speed mixer, the various raw materials shown in Tables 3 and 4 were mixed in such a way as the blending composition (mass %) shown in Tables 3 and 4, and then filtered using a filter with a pore size of 0.5 μm to prepare the photoresist composition for black matrix of each embodiment and comparative example.

[0068] Furthermore, using the black matrix photoresist composition obtained above, each item was evaluated according to the following evaluation method. The results are shown in Tables 3 and 4.

[0069] Evaluation of the optical density (OD value) of photoresist patterns Using a spin coater, the aforementioned black matrix photoresist compositions were coated onto a glass substrate (Corning 1737) with a film thickness of 1 μm. After pre-baking at 100°C for 3 minutes, the substrate was exposed using a high-pressure mercury lamp and then baked at 230°C for 30 minutes to obtain a photoresist film consisting only of solid portions. The optical density (OD value) of each solid portion of the obtained photoresist film was measured using a Macbeth density meter (TD-931, trade name, manufactured by Macbeth Corporation). An OD value of 4.0 or higher was considered acceptable.

[0070] Evaluation of the fine-line adhesion of black photoresist film (A) and (B) Using a spin coater, the aforementioned black matrix photoresist compositions were coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm, and pre-baked at 100°C for 3 minutes. Next, a photomask with line patterns spaced 1 μm apart and linewidths ranging from 1 μm to 20 μm was exposed using a high-pressure mercury lamp at a UV cumulative intensity of 100 mJ / cm². Then, development was performed at 23°C in a 0.05% potassium hydroxide aqueous solution at a spray development pressure of 1 kgf / cm², starting from the time when the developed pattern first appeared (development point). In the evaluation of fine line adhesion (A), development was stopped when the time was 1.3 times the development point; in the evaluation of fine line adhesion (B), development was stopped 30 seconds after the development point. Finally, a spray wash was performed at a pressure of 1 kgf / cm². The size (μm) of the smallest line pattern remaining on the glass substrate was evaluated. In the evaluation of fine line adhesion (A), a development time of 50 ± 25 seconds and a minimum line pattern size of 10 μm or less are considered acceptable. Furthermore, in the evaluation of fine line adhesion (B), a development time of 20 ± 10 seconds and a minimum line pattern size of 8 μm or less are considered acceptable.

[0071] <Determination of Surface Resistivity of Black Photoresist Film> Using a spin coater, the aforementioned black matrix photoresist compositions were coated onto a glass substrate (EAGLE XG) with a film thickness of 1 μm. After pre-baking at 100°C for 3 minutes, the substrate was exposed using a high-pressure mercury lamp (UV cumulative light intensity 80 mJ / cm²), and then baked at 230°C for 60 minutes to create a black photoresist pattern (black matrix) consisting only of solid portions. The surface resistivity of each black photoresist pattern was measured using a micro-galvanometer R8340 (main body) and a shielding box R12702A (optional) (both manufactured by ADVANCE).

[0072] [Table 3] Example Comparative example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-1 2-2 2-3 Black matrix uses pigment dispersion components Example 1-1 51 Examples 1-2 51 Examples 1-3 51 Examples 1-4 51 Examples 1-5 51 Examples 1-6 51 Examples 1-7 51 Comparative Example 1-1 51 Comparative Examples 1-2 51 Comparative Examples 1-3 51 Photopolymerization initiator OXE02 1 1 1 1 1 1 1 1 1 1 Photopolymers DPHA 2 2 2 2 2 2 2 2 2 2 Alkali-soluble resins WR-301 (solid content 44%) 4 4 4 4 4 4 4 4 4 4 solvent PGMEA 42 42 42 42 42 42 42 42 42 42 total 100 100 100 100 100 100 100 100 100 100 Evaluation results OD value 4.0 4.0 4.1 4.0 4.0 4.0 4.0 4.1 3.8 4.1 BP (seconds) 50 50 52 54 53 69 51 52 42 51 Fine-line adhesion (A) (μm) 7 5 8 10 7 8 6 13 4 11

[0073] [Table 4] Example Comparative example 2-8 2-9 2-10 2-11 2-4 2-5 2-6 Black matrix uses pigment dispersion components Examples 1-8 51 Examples 1-9 51 Examples 1-10 51 Examples 1-11 51 Comparative Examples 1-4 51 Comparative Examples 1-5 51 Comparative Examples 1-6 51 Photopolymerization initiator OXE02 1 1 1 1 1 1 1 Photopolymers DPHA 2 2 2 2 2 2 2 Alkali-soluble resins WR-301 (solid content 44%) 4 4 4 4 4 4 4 solvent PGMEA 42 42 42 42 42 42 42 total 100 100 100 100 100 100 100 Evaluation results OD value 4.0 4.3 4.0 4.0 4.1 3.8 4.1 BP (seconds) 19 20 27 20 20 16 19 Fine-line adhesion (B)(μm) 5 5 8 6 10 6 9 Surface resistivity (Ω / □) 7.5×10 13 2.5×10 13 5.3×10¹⁴ 3.7×10¹³ 1.5×10 13 8.0×10 13 2.7×10 13

[0074] In Tables 3 and 4, DPHA represents dinepentylenetetroxide hexaacrylate; OXE02 indicates the oxime ester-based photopolymerization initiator 'IRGACURE OXE02' (manufactured by BASF Japan). WR-301 indicates alkali-soluble carbomer resin 'ADEKA ARKLS WR-301' (44% solids, manufactured by ADEKA Corporation); PGMEA stands for propylene glycol monomethyl ether acetate.

[0075] none

Claims

1. A pigment dispersion composition for black matrix, characterized in that it contains carbon black, a pigment dispersant containing basic groups, a pigment dispersing aid containing acidic groups, an alkali-soluble resin, an ion scavenger, and a solvent, wherein the carbon black is acidic carbon black, and the ion scavenger is an inorganic compound with a median diameter of 0.1 to 10 μm, and is present in a concentration of 1 to 15 parts by mass relative to 100 parts by mass of the carbon black.

2. As in request item 1, the black matrix is ​​composed of pigment dispersions, wherein, The DBP oil absorption of the carbon black mentioned above is less than 80 ml / 100 g.

3. As in request item 1 or 2, the black matrix is ​​composed of a pigment dispersion, wherein, The amine value of the above-mentioned pigment dispersants containing basic groups is 5 to 50 mgKOH / g.

4. As in claim 1 or 2, the black matrix is ​​composed of pigment dispersions, wherein, The aforementioned alkali-soluble resin is alkali-soluble cardo resin and / or alkali-soluble epoxy (meth)acrylate resin.

5. A photoresist composition for black matrix, characterized in that it contains a pigment dispersion composition for black matrix according to any one of claims 1 to 4, a photopolymerizable compound, and a photopolymerization initiator.

6. A black photoresist film, characterized in that it is obtained using the black matrix photoresist composition of claim 5.

7. A method for manufacturing a black matrix pigment dispersion composition according to any one of claims 1 to 4, characterized in that: the carbon black is at least dispersed in the presence of the aforementioned ion scavenger.