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

Abstract

The present invention relates to a pigment dispersion composition for a black matrix and a pigment dispersion photoresist composition for a black matrix. The pigment dispersion composition for a black matrix comprises carbon black and / or lactam black, a pigment dispersant containing a basic group, an alkali-soluble resin, and a solvent. Furthermore, the composition further comprises one or more inorganic compounds selected from the group consisting of barium titanate, aluminum oxide, and aluminum hydroxide, wherein the inorganic compound is present in an amount of 30 parts by mass or less per 100 parts by mass of the carbon black and / or lactam black. The pigment dispersion composition for a black matrix exhibits excellent dispersion stability and can provide a pigment dispersion photoresist composition for a black matrix with good developer reusability.

Description

Technical Field

[0001] The present invention relates to a pigment dispersion composition for a black matrix and a pigment dispersion photoresist composition for a black matrix. Background Art

[0002] Currently, there are known pigment dispersion compositions for black matrices comprising carbon black and / or lactam black, a pigment dispersant containing a basic group, an alkali-soluble resin, and a solvent, and pigment dispersion photoresist compositions for black matrices comprising the pigment dispersion composition for black matrices, a photopolymerizable compound, and a photopolymerization initiator (Patent Documents 1-6).

[0003] [Prior art literature]

[0004] [Patent Document]

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-102346

[0006] Patent Document 2: International Publication No. 2015 / 056688

[0007] Patent Document 3: Japanese Patent Application Laid-Open No. 2016-79245

[0008] Patent Document 4: Japanese Patent Application Publication No. 2019-81831

[0009] Patent Document 5: Japanese Patent Application Publication No. 2019-81857

[0010] Patent Document 6: Japanese Patent Application Publication No. 2019-82533 Summary of the Invention

[0011] [Technical Problems that the Present Invention Aims to Solve]

[0012] When forming a black matrix pattern using the pigment-dispersed photoresist composition for black matrix as described above, the pigment-dispersed photoresist composition for black matrix is ​​usually applied to a substrate to form a photoresist film, and then ultraviolet light is passed through a photomask having a desired pattern for exposure. After the photoresist film in the exposed portion is hardened, a developer is used to remove the photoresist film in the unexposed portion.

[0013] On the other hand, in terms of improving productivity, the market demands that the developer have reusability, and the pigment dispersion composition for black matrix described in the above patent documents still has room for improvement in this property.

[0014] Furthermore, generally, a pigment dispersion photoresist composition for a black matrix is ​​prepared by mixing a pigment dispersion composition for a black matrix, a photopolymerizable compound, a photopolymerization initiator, etc. before coating, and therefore the pigment dispersion composition for a black matrix needs to have dispersion stability during storage.

[0015] The present invention has been made in view of the above-mentioned actual situation, and its object is to provide a pigment dispersion photoresist composition for black matrix with good developer reusability and a pigment dispersion composition for black matrix with excellent dispersion stability.

[0016] [Technical means to solve technical problems]

[0017] The present invention relates to a pigment dispersion composition for a black matrix, comprising carbon black and / or lactam black, a pigment dispersant containing a basic group, an alkali-soluble resin, and a solvent, and further comprising one or more inorganic compounds selected from the group consisting of barium titanate, aluminum oxide, and aluminum hydroxide, wherein the amount of the inorganic compound is 30 parts by mass or less relative to 100 parts by mass of the carbon black and / or lactam black.

[0018] Furthermore, the present invention relates to a pigment-dispersed photoresist composition for a black matrix, comprising the pigment-dispersed photoresist composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator.

[0019] [Technical Effects of the Invention]

[0020] The detailed mechanism of action of the pigment dispersion composition for black matrices of the present invention is not yet clear, but can be presumed as follows. However, the present invention is not limited to this mechanism of action.

[0021] The pigment dispersion composition for a black matrix of the present invention includes carbon black and / or lactam black, a pigment dispersant containing a basic group, an alkali-soluble resin, and a solvent, and further includes one or more inorganic compounds selected from the group consisting of barium titanate, aluminum oxide, and aluminum hydroxide, relative to 100 parts by mass of the carbon black and / or lactam black, and the inorganic compound is 30 parts by mass or less. In the pigment dispersion composition for a black matrix of the present invention, the inorganic compound is below a certain amount relative to the carbon black and / or lactam black, so the dispersion stability is excellent. In addition, due to the inclusion of the inorganic compound, it is not easily affected by the developer for reuse, and therefore a pigment dispersion photoresist composition for a black matrix with good developer reusability can be obtained. In addition, the reusability of the developer is evaluated using the used developer according to the developability and adhesion of the resist pattern described in the above-mentioned patent document 1, etc. DETAILED DESCRIPTION

[0022] The pigment dispersion composition for black matrix of the present invention comprises carbon black and / or lactam black, a basic group-containing pigment dispersant, an alkali-soluble resin and a solvent, and further comprises one or more inorganic compounds selected from the group consisting of barium titanate, aluminum oxide and aluminum hydroxide.

[0023] Inorganic compounds

[0024] The inorganic compound is one or more selected from the group consisting of barium titanate, aluminum oxide, and aluminum hydroxide. The inorganic compound can be used alone or in combination of two or more.

[0025] To achieve a pigment-dispersed photoresist composition for black matrices with good developer reusability, the average primary particle size of the inorganic compound is preferably 20 nm or greater, more preferably 30 nm or greater. To prevent precipitation of the inorganic compound in the pigment-dispersed composition or photoresist composition, the average primary particle size is preferably 2000 nm or less, more preferably 1700 nm or less. Typically, the average primary particle size is the arithmetic mean particle size obtained by electron microscopic observation, but for commercially available products, reference should be made to catalog values.

[0026] The amount of the inorganic compound is 30 parts by mass or less relative to 100 parts by mass of the carbon black and / or lactam black. In terms of obtaining a pigment-dispersed photoresist composition for a black matrix having good developer reusability, the amount of the inorganic compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the carbon black and / or lactam black. Furthermore, in terms of obtaining a pigment-dispersed photoresist composition for a black matrix having good developer reusability and improving dispersion stability, the amount of the inorganic compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0027] Carbon black and / or lactam black

[0028] The carbon black can be any known carbon black used in pigment dispersion compositions for black matrices, such as neutral carbon black and acidic carbon black. The average primary particle size of the carbon black is preferably approximately 20 to 60 nm. Examples of the lactam black include compounds having the following structures. These carbon blacks and / or lactam blacks can be used alone or in combination of two or more.

[0029] [Compound 1]

[0030] The pH of the neutral carbon black is preferably in the range of 8 to 10. Examples of commercially available neutral carbon black include Printex25 (average primary particle size of 56 nm, pH of 9.5), Printex35 (average primary particle size of 31 nm, pH of 9.5), and Printex65 (average primary particle size of 21 nm, pH of 9.5) manufactured by Orion Engineered Carbons Co., Ltd.; and MA#20 (average primary particle size of 40 nm, pH of 8.0), MA#40 (average primary particle size of 40 nm, pH of 8.0), and MA#30 (average primary particle size of 30 nm, pH of 8.0) manufactured by Mitsubishi Chemical Corporation.

[0031] The pH of the acidic carbon black is preferably in the range of 2 to 4. Examples of commercially available acidic carbon black include Raven 1080 (average primary particle size of 28 nm, pH of 2.4) and Raven 1100 (average primary particle size of 32 nm, pH of 2.9) manufactured by Columbia Chemical, MA-8 (average primary particle size of 24 nm, pH of 3.0), MA-100 (average primary particle size of 22 nm, pH of 3.5), and MA#70 (average primary particle size of 24 nm, pH of 3.0) manufactured by Mitsubishi Chemical Corporation, and Special Black 250 (average primary particle size of 56 nm, pH of 3.0), Special Black 350 (average primary particle size of 31 nm, pH of 3.0), and Special Black 700 (average primary particle size of 24 nm, pH of 3.0) manufactured by Orion Engineered Carbons Co., Ltd. NEROX 550 (average primary particle size: 25 nm, pH: 4), NEROX 2500 (average primary particle size: 56 nm, pH: 3.0), NEROX 3500 (average primary particle size: 31 nm, pH: 3.0), etc.

[0032] In addition, pH is generally measured as follows: 1 g of carbon black is added to 20 mL of decarbonated distilled water (pH 7.0), mixed with a magnetic stirrer to prepare an aqueous suspension, and measured at 25°C using a glass electrode (German Industrial Product Standard DIN ISO 787 / 9). In addition, in general, the average primary particle size is the value of the arithmetic mean particle size obtained by electron microscopic observation. However, the pH and average primary particle size of the commercially available carbon black mentioned above are catalog values.

[0033] In the pigment dispersion composition for a black matrix, the carbon black and / or lactam black is preferably 3% by mass or more, more preferably 10% by mass or more, in terms of improving light-shielding properties when a black matrix is ​​formed, and is preferably 70% by mass or less, more preferably 50% by mass or less, in terms of pigment dispersion.

[0034] Pigment dispersants containing basic groups

[0035] The pigment dispersant containing a basic group can be any of the known pigment dispersants containing a basic group used in the pigment dispersion composition for the black matrix as long as it can disperse the carbon black and / or lactam black. Examples of the pigment dispersant containing a basic group include anionic surfactants, polyester pigment dispersants containing a basic group, acrylic pigment dispersants containing a basic group, urethane pigment dispersants containing a basic group, and carbodiimide pigment dispersants containing a basic group. As the above-mentioned basic group, in particular, with respect to excellent dispersibility, it is preferably a primary amino group, a secondary amino group, or a tertiary amino group. The pigment dispersant containing a basic group can be used alone or in combination of two or more.

[0036] In terms of achieving good pigment dispersibility, the basic group-containing pigment dispersant is preferably a polymeric basic group-containing pigment dispersant. Examples of the polymeric basic group-containing pigment dispersant include: basic group-containing urethane polymeric pigment dispersants, basic group-containing polyester polymeric pigment dispersants, basic group-containing acrylic polymeric pigment dispersants, etc. Among them, the basic group-containing urethane polymeric pigment dispersants and basic group-containing acrylic polymeric pigment dispersants are preferred. The basic group-containing urethane polymeric pigment dispersant is more preferably a basic group-containing urethane polymeric pigment dispersant having at least one selected from the group consisting of a polyester chain, a polyether chain, and a polycarbonate chain.

[0037] The amount of the basic group-containing pigment dispersant is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, relative to 100 parts by mass of the carbon black and / or lactam black.

[0038] Alkali-soluble resin

[0039] The alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline developer, and is preferably a resin containing one or more anionic groups such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group (-P(=O)(OH2)). The alkali-soluble resin can be used alone or in combination of two or more.

[0040] In terms of alkali developability, the acid value of the 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.

[0041] In terms of photoresist film formation, the weight average molecular weight of the alkali-soluble resin is preferably 5000 or more, more preferably 10000 or more. In terms of improving solubility in alkaline developer, the weight average molecular weight of the alkali-soluble resin is preferably 100000 or less, more preferably 50000 or less.

[0042] The weight-average molecular weight can be measured by gel permeation chromatography (GPC). For example, using a Water 2690 (manufactured by Waters Corporation) as the GPC apparatus, a PLgel 5μ MIXED-D (manufactured by Polymer Laboratories) as the column, tetrahydrofuran as the developing solvent, 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, the weight-average molecular weight in terms of polystyrene can be obtained.

[0043] Examples of the alkali-soluble resin include acrylic copolymer resins, maleic copolymer resins, polyester resins obtained by polycondensation, and polyurethane resins. Of these, acrylic copolymer resins are preferred in terms of developability, molecular design range, and cost.

[0044] The amount of the alkali-soluble resin is preferably 20 to 90 parts by mass, more preferably 40 to 80 parts by mass, relative to 100 parts by mass of the carbon black and / or lactam black.

[0045] solvent

[0046] The solvent may be a known solvent used in a pigment dispersion composition for a black matrix. From the perspective of being able to stably disperse the pigment and fully dissolve the basic group-containing pigment dispersant and the alkali-soluble resin, the solvent is preferably an ester solvent, an ether solvent, an ether-ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, a nitrogen-containing solvent, or the like. These solvents may be used alone or in combination of two or more.

[0047] Examples of the ester solvents include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, butyl 3-methyl-3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, glycolate, and n-amyl formate. Examples of the ether 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 the 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 the ketone solvents include methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone. Examples of the aromatic hydrocarbon solvents include toluene, xylene, and alkylnaphthalene. Examples of the nitrogen-containing solvents include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0048] In the pigment dispersion composition for a black matrix, the proportion of the solvent is preferably 40% by mass or more, more preferably 50% by mass or more, in terms of process efficiency, and is preferably 90% by mass or less, more preferably 80% by mass or less, in terms of dispersion stability.

[0049] Pigment dispersing additives with acidic groups

[0050] For the purpose of further improving the dispersibility of pigment, the pigment dispersion composition for black matrix can also contain a pigment dispersing aid with an acidic group. The pigment dispersing aid with an acidic group can be enumerated as follows: in pigments such as lactam black, perylene compounds, diketopyrrolopyrrole compounds, azonaphthol compounds, dioxazine compounds, quinacridone compounds, phthalocyanine compounds and their metal complexes, anthraquinone, naphthalene, acridone or triazine, compounds (pigment derivatives with acidic groups) such as carboxyl and sulfonic groups are connected, and compounds formed by neutralizing them with organic amines etc. As the pigment derivative with an acidic group, in terms of good carbon black dispersibility, it is preferably a phthalocyanine pigment derivative with a sulfonic group. The pigment derivative can be used alone or in combination of two or more.

[0051] The amount of the pigment dispersing aid having an acidic group is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the carbon black and / or lactam black.

[0052] In the pigment dispersion composition for a black matrix, the total proportion of the carbon black, the pigment dispersant containing a basic group, the alkali-soluble resin, the solvent, and the inorganic compound is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. In addition, when a pigment dispersing aid having an acidic group is used, in the pigment dispersion composition for a black matrix, the total proportion of the carbon black, the pigment dispersant containing a basic group, the alkali-soluble resin, the solvent, the inorganic compound, and the pigment dispersing aid having an acidic group is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more.

[0053] The pigment dispersion composition for the black matrix is ​​prepared by dispersing the above components using a roll mill, a kneader, a high-speed stirrer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure disperser, or the like.

[0054] Pigment-dispersed photoresist composition for black matrix

[0055] The pigment-dispersed photoresist composition for a black matrix of the present invention comprises the pigment-dispersed composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator. Furthermore, the proportion of the carbon black and / or lactam black in the solid content of the pigment-dispersed photoresist composition for a black matrix is ​​preferably 30% by mass or more and 80% by mass or less. Furthermore, the proportion of the inorganic compound in the solid content of the pigment-dispersed photoresist composition for a black matrix is ​​preferably 1% by mass or more and 10% by mass or less, more preferably 1.3% by mass or more and 8% by mass or less.

[0056] Photopolymerizable compounds

[0057] The photopolymerizable compound may be a known photopolymerizable compound used in a pigment-dispersed resist composition for a black matrix, and examples thereof include monomers and oligomers having a photopolymerizable unsaturated bond. The photopolymerizable compound may be used alone or in combination of two or more.

[0058] Examples of the monomer having one photopolymerizable unsaturated bond include: alkyl methacrylates or alkyl acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aryl methacrylates or aryl acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or alkoxyalkyl acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; N,N-dimethacrylate; Aminoalkyl methacrylates or aminoalkyl acrylates such as methylaminoethyl ester and N,N-dimethylaminoethyl acrylate; methacrylates or acrylates of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; methacrylates or acrylates of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether; isobornyl methacrylate or isobornyl acrylate; glyceryl methacrylate or glyceryl acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, etc.

[0059] Examples of the monomer having two or more photopolymerizable unsaturated bonds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol tetramethacrylate. Ester, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, 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, etc.

[0060] Examples of the oligomer having a photopolymerizable unsaturated bond include oligomers obtained by appropriately polymerizing the above-mentioned monomers.

[0061] The photopolymerizable compound preferably accounts for 2 to 20% by mass, and more preferably 4 to 15% by mass, of the solid content of the pigment-dispersed photoresist composition for black matrix.

[0062] The photopolymerization initiator may be a known photopolymerization initiator used in a pigment-dispersed photoresist composition for a black matrix, and examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzil, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzil dimethyl ketal, α-hydroxyisobutylbenzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl 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, triazine-based photopolymerization initiators, and oxime ester-based photopolymerization initiators. The photopolymerization initiators may be used alone or in combination of two or more.

[0063] The photopolymerization initiator preferably accounts for 0.1 to 15% by mass, and more preferably 1 to 10% by mass, of the solid content of the pigment-dispersed photoresist composition for black matrix.

[0064] In terms of the developability of the alkaline developer, the pigment-dispersed photoresist composition for the black matrix may additionally contain the alkali-soluble resin. In addition, in the solid content of the pigment-dispersed photoresist composition for the black matrix, the total proportion of the alkali-soluble resin is preferably 10% by mass or more and 50% by mass or less. In addition, in terms of improving the coating properties, the pigment-dispersed photoresist composition for the black matrix may additionally contain the solvent. In the pigment-dispersed photoresist composition for the black matrix, the total proportion of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more.

[0065] Additives such as a leveling agent, an antioxidant, and a defoaming agent may be further added to the pigment-dispersed photoresist composition for a black matrix as needed.

[0066] The pigment-dispersed photoresist composition for a black matrix is ​​prepared by stirring and mixing the pigment-dispersed composition for a black matrix, a photopolymerizable compound, a photopolymerization initiator and other components using a stirring device or the like.

[0067] [Example]

[0068] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

[0069] Preparation Examples 1 to 8, Comparative Preparation Examples 1 to 3

[0070] Preparation of pigment dispersion composition for black matrix

[0071] The various raw materials shown in Table 1 were mixed to have the formulation composition (mass %) shown in Table 1, and then milled using a bead mill to prepare a pigment dispersion composition for a black matrix of each Preparation Example and Comparative Preparation Example.

[0072] Evaluation of dispersion stability

[0073] Each of the pigment dispersion compositions for black matrices was placed in a glass bottle, the bottle cap was tightened, and the state after storage at room temperature for 7 days was evaluated according to the following evaluation criteria. A was used as the passing standard. The results are shown in Table 1.

[0074] A: No increase in thickness or precipitation was observed.

[0075] B: Thickening or precipitation is observed to such an extent that it recovers after gentle shaking.

[0076] C: Thickening or precipitation to such an extent that the sample does not recover even after vigorous shaking is observed.

[0077] Examples 1 to 8, Comparative Examples 1 to 3

[0078] Preparation of pigment-dispersed photoresist composition for black matrix

[0079] The various raw materials shown in Table 2 were mixed in a high-speed mixer in the formulation composition (mass %) shown in Table 2, and then filtered through a filter with a pore size of 0.5 μm to prepare pigment dispersion photoresist compositions for black matrices of various examples and comparative examples.

[0080] Evaluation of reusability (1): Evaluation of the adhesion of the resist pattern using the treated developer

[0081] The above-mentioned various pigment dispersion photoresist compositions for black matrix were coated on a glass substrate (Corning 1737) with a thickness of 1 μm by a spin coater and pre-baked at 100°C for 3 minutes. Subsequently, a photomask with a line pattern of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm was used to coat the black matrix with a high-pressure mercury lamp at 400 mJ / cm 2 The UV cumulative light dose was exposed to produce a photoresist film including the exposed part (cured part). Then, a 0.05% potassium hydroxide aqueous solution (developer) was used at 23°C and 0.5 kgf / cm 2 The spray pressure condition is 3.0kgf / cm2, and the development is carried out for 20 seconds from the time when the development pattern begins to appear (development point), and then at 3.0kgf / cm2 2Then, the photoresist film including the exposed part (hardened part) was prepared again by the same operation as above. The photoresist film including the exposed part (hardened part) prepared again and the recovered developer were used to prepare the photoresist film at 23°C and 0.5 kgf / cm 2 The spray pressure condition is 3.0kgf / cm2, and the development is carried out for 20 seconds from the time when the development pattern begins to appear (development point), and then at 3.0kgf / cm2 2 The substrate was sprayed with water at a pressure of . The size of the smallest pattern remaining on the substrate was measured, and the reusability was evaluated according to the following evaluation criteria. A was considered the passing standard. The results are shown in Table 2.

[0082] A: The minimum remaining pattern sizes are 2μm, 5μm, and 8μm.

[0083] B: The minimum remaining pattern size is 10 μm and 15 μm.

[0084] C: The minimum remaining pattern size is 20 μm and 30 μm.

[0085] Evaluation of Recyclability (2): Evaluation of the Developability of the Resist Pattern Using the Treated Developer

[0086] The following evaluation criteria were used to evaluate the time (development point) at which the developed pattern began to appear during development using the recovered developer in the "Evaluation of Adhesion of Resist Patterns Using Treated Developers" described above. A or B was considered acceptable. The results are shown in Table 2.

[0087] A: It can be completely removed within 30 seconds.

[0088] B: Can be completely removed within more than 30 seconds and within 60 seconds.

[0089] C: It cannot be completely removed even after 60 seconds.

[0090] Furthermore, the obtained pigment-dispersed photoresist composition for black matrix was evaluated for various items according to the following evaluation methods. The results are shown in Table 2.

[0091] Evaluation of optical density (OD value) of resist pattern

[0092] Each of the pigment-dispersed photoresist compositions for black matrices was applied to a glass substrate (Corning 1737) using a spin coater to a thickness of 1 μm. The film was pre-baked at 100°C for 3 minutes, exposed to light using a high-pressure mercury lamp, and baked at 230°C for 30 minutes to obtain a photoresist film consisting solely of solid portions. The optical density (OD) of each solid portion of the photoresist film was measured using a MacBeth densitometer (trade name D-200II, manufactured by MacBeth).

[0093] Evaluation of developability of resist pattern

[0094] The various pigment dispersion photoresist compositions for black matrix were coated on a glass substrate (Corning 1737) with a thickness of 1 μm by a spin coater and pre-baked at 100°C for 3 minutes. Subsequently, a photomask with a line pattern of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm was used to coat the black matrix with a high-pressure mercury lamp at 400 mJ / cm 2 The UV cumulative light exposure is carried out to produce a photoresist film. A high pressure mercury lamp is used at 400mJ / cm 2 Then, a 0.05% potassium hydroxide aqueous solution (developer) was used at 23°C and 0.5 kgf / cm 2 The time when the development pattern begins to appear (development point) was evaluated according to the following evaluation criteria under the condition of the spray pressure of .

[0095] A: It can be completely removed within 30 seconds.

[0096] B: Can be completely removed within more than 30 seconds and within 60 seconds.

[0097] C: It cannot be completely removed even after 60 seconds.

[0098] Evaluation of the adhesiveness of the resist pattern

[0099] The various pigment dispersion photoresist compositions for black matrix were coated on a glass substrate (Corning 1737) with a thickness of 1 μm by a spin coater and pre-baked at 100°C for 3 minutes. Subsequently, a photomask with a pattern of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm was used to coat the black matrix with a high-pressure mercury lamp at 400 mJ / cm 2 Then, a 0.05% potassium hydroxide aqueous solution (developer) was used at 23°C and 0.5 kgf / cm 2 The spray pressure condition is 3.0kgf / cm2, and the development is carried out for 20 seconds from the time when the development pattern begins to appear (development point), and the development is carried out at 3.0kgf / cm2. 2 The minimum size of the pattern remaining on the substrate was evaluated according to the following evaluation criteria.

[0100] A: The minimum remaining pattern sizes are 2μm, 5μm, and 8μm.

[0101] B: The minimum remaining pattern size is 10 μm and 15 μm.

[0102] C: The minimum remaining pattern size is 20 μm and 30 μm.

[0103] Evaluation of seal strength

[0104] The various pigment-dispersed photoresist compositions for black matrices are applied to a glass substrate (Corning1737) with a thickness of 1 μm by a spin coater, pre-baked at 100 ° C for 3 minutes, exposed by a high-pressure mercury lamp, and baked at 230 ° C for 30 minutes to obtain a photoresist film formed only by a solid portion. Aluminum pins with a diameter of 5 mm are attached to the obtained substrate and a glass substrate (Corning1737) not coated with a photoresist composition by a certain amount of sealant. Subsequently, the glass substrate with aluminum pins is baked at 150 ° C for 1 hour to prepare a test piece. In addition, the obtained test piece is subjected to a tensile test, the strength at the time of peeling is read, and divided by the coating area of ​​the sealant to obtain the strength per unit area (sealing strength). According to the sealing strength of each composition, the relative value when the sealing strength of the glass not coated with the photoresist composition is set to 100 is calculated, and evaluated according to the following evaluation criteria.

[0105] A: The relative value is above 80.

[0106] B: The relative value is above 60 and below 80.

[0107] C: The relative value does not reach 60.

[0108] Table 1

[0109]

[0110] Table 2

[0111]

[0112] In Tables 1 and 2, Raven 1080 represents carbon black (average primary particle size of 28 nm, pH of 2.4, manufactured by Columbia Chemical Company);

[0113] Iragaphor Black S 0100 CF represents lactam black (manufactured by BASF);

[0114] Aluminum hydroxide was represented by "C301N" (average primary particle size: 1500 nm, manufactured by Sumitomo Chemical Co., Ltd.);

[0115] Alumina (a) represents "AKP-53" (average primary particle size of 180 nm, manufactured by Sumitomo Chemical Co., Ltd.);

[0116] Alumina (b) represents "AA-03" (average primary particle size of 440 nm, manufactured by Sumitomo Chemical Co., Ltd.);

[0117] Barium titanate (a) was BTC-4FA (average primary particle size: 200 nm, manufactured by Nippon Chemical Industry Co., Ltd.);

[0118] Barium titanate (b) represents “BTC-4FB” (average primary particle size of 300 nm, manufactured by Nippon Chemical Industry Co., Ltd.);

[0119] Barium titanate (c) represents "KZM-50" (average primary particle size of 50 nm, manufactured by Nippon Chemical Industry Co., Ltd.);

[0120] Barium sulfate was represented by "BF-40" (average primary particle size: 10 nm, manufactured by Sakai Chemical Industry Co., Ltd.);

[0121] Solsperse5000 represents a phthalocyanine pigment derivative having a sulfonic acid group (manufactured by Lubrizol Corporation);

[0122] BYK-167 represents an amino-containing polyurethane-type polymer dispersant having a polyester chain (manufactured by BYK-Chemie, solid content: 52% by mass);

[0123] BYK-LPN-22329 represents an amino group-containing acrylic polymer pigment dispersant (manufactured by BYK-Chemie, solid content 58%);

[0124] BzMA / MAA represents BzMA (benzyl methacrylate) / MAA (methacrylic acid) copolymer (acid value of 100 mgKOH / g, weight-average molecular weight of 30,000);

[0125] PGMEA stands for propylene glycol monomethyl ether acetate.

[0126] In Table 2 , DPHA represents dipentaerythritol hexaacrylate;

[0127] Irgacure OXE02 represents an oxime ester photopolymerization initiator (manufactured by BASF Corporation);

[0128] MEGAFAC F555 represents an oligomer containing a fluorine-containing group-hydrophilic group-lipophilic group (manufactured by DIC Corporation, solid content: 30% by mass).

Claims

1. A pigment dispersion composition for a black matrix, comprising carbon black and / or lactam black, a pigment dispersant containing a basic group, an alkali-soluble resin, and a solvent, wherein: further comprising one or more inorganic compounds selected from the group consisting of barium titanate, aluminum oxide, and aluminum hydroxide, The inorganic compound is an inorganic particle having an average primary particle size of 20 nm to 2000 nm. The inorganic compound is contained in an amount of 30 parts by mass or less relative to 100 parts by mass of the carbon black and / or lactam black. 2 . A pigment-dispersed photoresist composition for a black matrix, comprising the pigment-dispersed composition for a black matrix according to claim 1 , a photopolymerizable compound, and a photopolymerization initiator.

3. The pigment-dispersed photoresist composition for a black matrix according to claim 2, wherein: In the solid content of the pigment-dispersed photoresist composition for a black matrix, the ratio of the inorganic compound is 1% by mass or more and 10% by mass or less.

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