JP2024006903A - Pigment dispersion composition for black matrix, pigment dispersion resist composition for black matrix, and black resist film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersion composition for a black matrix from which a pigment dispersion resist composition for a black matrix that is excellent in thin line adhesion and surface roughness resistance can be obtained.

SOLUTION: A pigment dispersion composition for a black matrix contains carbon black, an inorganic compound, a basic group-containing pigment dispersion agent, an acidic group-containing pigment dispersion aid, an alkali-soluble resin and a solvent, wherein the inorganic compound is one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, barium sulfate, barium titanate, boron nitride and an ion scavenger, the alkali-soluble resin is an alkali-soluble cardo resin, and 1-10 pts.mass of the inorganic compound is contained with respect to 100 pts.mass of the carbon black.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

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

Conventionally, a pigment dispersion composition for a black matrix containing carbon black, an inorganic compound, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersion aid, an alkali-soluble resin, and a solvent; Pigment-dispersed resist compositions for black matrices containing a photopolymerizable compound and a photopolymerization initiator are known (Patent Documents 1 and 2).

Japanese Patent Application Publication No. 2021-173876 Japanese Patent Application Publication No. 2021-038289

To form a black matrix pattern using the pigment-dispersed resist composition for a black matrix as described above, the pigment-dispersed resist composition for a black matrix is usually coated on a substrate to form a resist film, and then the desired coating is applied. After exposing the resist film to ultraviolet rays through a mask having a pattern of , the resist film in the exposed areas is cured, and then the resist film in the unexposed areas is removed with a developer. Therefore, a pigment-dispersed resist composition for a black matrix is usually required to have fine line adhesion (resolution) as in Patent Documents 1-2.

On the other hand, in recent years, in order to improve manufacturing yield rates, there has been a demand for performance that can withstand harsher developing conditions in the exposed area. In particular, under such development conditions, there was a problem that the surface of the exposed area became rough. In areas where the surface is rough, the film thickness is thinner than in areas where the surface is rough, and the light-shielding properties of the black matrix are impaired, resulting in poor black reproduction.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a pigment dispersion composition for a black matrix from which a pigment dispersion resist composition for a black matrix having excellent fine line adhesion and surface roughness resistance can be obtained. do.

That is, the present invention provides a pigment dispersion composition for a black matrix containing carbon black, an inorganic compound, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersion aid, an alkali-soluble resin, and a solvent, wherein the inorganic compound is one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, barium sulfate, barium titanate, boron nitride, and an ion scavenger, the alkali-soluble resin is an alkali-soluble cardo resin, and the inorganic The compound is used in a pigment dispersion composition for a black matrix in an amount of 1 to 10 parts by mass based on 100 parts by mass of the carbon black.

The present invention also relates to a pigment-dispersed resist composition for a black matrix, which includes the pigment-dispersed composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator.

The present invention also relates to a black resist film formed from the pigment-dispersed resist composition for black matrix.

The mechanism of effect of the pigment dispersion composition for black matrix of the present invention is estimated as follows. However, the invention is not limited to this mechanism of action.

The pigment dispersion composition for a black matrix of the present invention is a pigment dispersion composition for a black matrix containing carbon black, an inorganic compound, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersion aid, an alkali-soluble resin, and a solvent. The inorganic compound is one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, barium sulfate, barium titanate, boron nitride, and an ion scavenger, and the alkali-soluble resin is an alkali-soluble cardinal. The inorganic compound is a resin in an amount of 1 to 10 parts by mass based on 100 parts by mass of the carbon black. The pigment dispersion composition for a black matrix of the present invention differs from the above-mentioned Patent Documents 1-2 in that a part of carbon black is replaced with the above-mentioned inorganic compound, and further, an alkali-soluble cardo resin is used as the alkali-soluble resin. As a result, sensitivity during UV exposure is improved while maintaining good pigment dispersibility, so surface roughness of the coating film can be improved while maintaining break point (BP) and fine line adhesion.

Furthermore, when the content of the alkali-soluble cardo resin is 10 parts by mass or less based on 100 parts by mass of the carbon black, the pigment dispersion composition for a black matrix of the present invention has particularly excellent fine line adhesion, and is also alkali-soluble. Since the amount of dissolved components is reduced, it also has excellent resistance to the phenomenon (water unevenness) in which the black color of the coating film becomes dark and light after alkaline development.

The pigment dispersion composition for a black matrix of the present invention is a pigment dispersion composition for a black matrix containing carbon black, an inorganic compound, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersion aid, an alkali-soluble resin, and a solvent. The inorganic compound is one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, barium sulfate, barium titanate, boron nitride, and an ion scavenger, and the alkali-soluble resin is an alkali-soluble cardinal. The inorganic compound is a resin in an amount of 1 to 10 parts by mass based on 100 parts by mass of the carbon black.

<Carbon black>
As the carbon black, any known carbon black used in a pigment dispersion composition for a black matrix can be used, and examples thereof include neutral carbon black, acidic carbon black, and the like. Further, the carbon black preferably has an average primary particle diameter of about 20 to 60 nm. The carbon black may be used alone or in combination of two or more.

The neutral carbon black preferably has a pH in the range of 8 to 10. Commercial products of the neutral carbon black include, for example, Printex 25 (average primary particle diameter 56 nm, pH 9.5) and Printex 35 (average primary particle diameter 31 nm, pH 9.5) manufactured by Orion Engineered Carbons. ), Printex 65 (average primary particle diameter 21 nm, pH 9.5), MA #20 (average primary particle diameter 50 nm, pH 7.5) manufactured by Mitsubishi Chemical Corporation, MA #30 (average primary particle diameter 30 nm, pH 8.0) ), MA#40 (average primary particle diameter 40 nm, pH 8.0), and the like.

The acidic carbon black preferably has a pH in the range of 2 to 4. Commercially available acidic carbon blacks include Raven 1080 (average primary particle size 28 nm, pH 2.4) manufactured by Columbia Chemicals, Raven 1100 (average primary particle size 32 nm, pH 2.9), and MA-8 (manufactured by Mitsubishi Chemical Corporation). (average primary particle diameter 24 nm, pH 3.0), MA-100 (average primary particle diameter 22 nm, pH 3.5), MA#70 (average primary particle diameter 24 nm, pH 3.0), manufactured by Orion Engineered Carbons. Special Black 250 (average primary particle diameter 56 nm, pH 3.0), Special Black 350 (average primary particle diameter 31 nm, pH 3.0), Special Black 550 (average primary particle diameter 25 nm, pH 4.0), NEROX 2500 (average primary particle diameter (diameter 56 nm, pH 3.0), NEROX3500 (average primary particle diameter 31 nm, pH 3.0), and the like.

Note that the pH is usually determined by adding 1 g of carbon black to 20 mL of distilled water (pH 7.0) from which carbonic acid has been removed, mixing with a magnetic stirrer to prepare an aqueous suspension, and using a glass electrode to adjust the pH to 25 mL. Measured in °C (German Industrial Standard DIN ISO 787/9). Moreover, the average primary particle diameter is usually the value of the arithmetic mean diameter observed by electron microscopy. However, the pH and average primary particle diameter of the above commercially available carbon black are catalog values.

In the solid content of the pigment dispersion composition for black matrix, the carbon black is preferably 60% by mass or more, and preferably 65% by mass or more, from the viewpoint of improving the light-shielding property when forming a black matrix. More preferably, from the viewpoint of pigment dispersion, it is preferably 85% by mass or less, and more preferably 90% by mass or less.

<Inorganic compounds>
The inorganic compound is one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, barium sulfate, barium titanate, boron nitride, and ion scavengers. The median diameter of the aluminum hydroxide, aluminum oxide, barium sulfate, and boron nitride is preferably 5 nm or more, more preferably 10 nm or more from the viewpoint of preventing reagglomeration, and the median diameter is preferably 5 nm or more, more preferably 10 nm or more. From the viewpoint of preventing sedimentation of inorganic compounds in the resist composition, the particle diameter is preferably 3,000 nm or less, more preferably 2,500 nm or less. The average primary particle diameter of the barium titanate is preferably 10 nm or more, more preferably 50 nm or more, from the viewpoint of preventing reagglomeration, and is suitable for use as an inorganic compound in pigment dispersion compositions and resist compositions. From the viewpoint of preventing sedimentation, the particle diameter is preferably 2,500 nm or less, more preferably 2,000 nm or less. The ion trapping agent may be anything that can trap at least one of cations and anions, and includes cation trapping agents, anion trapping agents, and amphoteric ion trapping agents that have ion trapping ability. The ion trapping agent preferably has a median diameter of 0.1 to 10 μm, and contains, for example, one or more metal atoms selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. Examples include ion scavengers. Among these, ion scavengers containing one or more metal atoms selected from the group consisting of bismuth, zirconium, magnesium, and aluminum are preferred. Note that the median diameter is a value that can be measured using a laser diffraction/scattering particle size distribution measurement device, and the average primary particle diameter is the arithmetic mean diameter value observed by electron microscopy. In this case, refer to the catalog value. Among these, aluminum hydroxide and aluminum oxide are preferred from the viewpoint of excellent improvement in surface roughness of the coating film while maintaining break point (BP) and fine line adhesion.

Examples of aluminum hydroxide include C301N (median diameter 1.5 μm), C302A (median diameter 2.4 μm) manufactured by Sumitomo Chemical Co., Higilite H-42M (median diameter 1.0 μm) manufactured by Showa Denko Co., Ltd. Examples include Light H-43M (median diameter 0.75 μm), B1403 (median diameter 2 μm) manufactured by Nippon Light Metal Co., Ltd., and BF013 (median diameter 1 μm).

Examples of aluminum oxide include AKP-15 (median diameter 0.60 μm), AKP-20 (median diameter 0.42 μm), AKP-30 (median diameter 0.26 μm), and AKP-50 (median diameter 0.26 μm) manufactured by Sumitomo Chemical Co., Ltd. diameter 0.20 μm), AKP-53 (median diameter 0.17 μm), AKP-3000 (median diameter 0.67 μm), AA-03 (median diameter 0.40 μm), AA-04 (median diameter 0.47 μm), Examples include AA-05 (median diameter 0.58 μm), AA-07 (median diameter 0.88 μm), AA-1.5 (median diameter 1.7 μm), and AA-2 (median diameter 2.2 μm).

As barium sulfate, precipitated barium sulfate is preferable, such as BARIFINE BF-40 (median diameter 0.01 μm), BARIFINE BF-20 (median diameter 0.03 μm), and BARIFINE BF-10 (median diameter 0.03 μm) manufactured by Sakai Chemical Industry Co., Ltd. diameter 0.06 μm), BARIFINE BF-1L (median diameter 0.1 μm), BARIFINE BF-1 (median diameter 0.05 μm), Takehara Chemical Industry Co., Ltd. P-30 (median diameter 1 μm), TS-2 (median diameter TS-3 (median diameter 0.6 μm), SC-201 (median diameter 0.3 μm), and HC-A (median diameter 0.1 μm).

Examples of barium titanate include Pulceram AKBT-S (average primary particle size 0.15 μm), Pulceram AKBT-M (average primary particle size 0.3 μm), and Pulceram AKBT-L (average primary particle size) manufactured by Nihon Kagaku Kogyo Co., Ltd. diameter 0.6 μm), Pulceram BT-UP-2 (average primary particle diameter 2 μm), BTC-4FA (average primary particle diameter 200 nm), BTC-4FB (average primary particle diameter 300 nm), KZM-50 (average primary particle diameter 50 nm), etc.

Examples of boron nitride include Denka Boron Nitride XGP (median diameter 30 μm), SGP (median diameter 18 μm), MGP (median diameter 10 μm), GP (median diameter 7 μm), HGP (median diameter 5 μm), SP-2 (median diameter 4 μm), SP-3 (median diameter 4 μm), SGPS (median diameter 12 μm), Showa Denko Showa N UHP-S2 (median diameter 0.7 μm), UHP-1K (median diameter 8 μm), UHP-2 (median diameter 11 μm), UHP-G1H (median diameter 33 μm), etc.

Examples of the ion trapping agent include IXEPLAS B1 (both ion trapping agent, zirconium/bismuth type, median diameter 0.4 μm) manufactured by Toagosei Co., Ltd., IXE-100 (cation trapping agent, zirconium type, median diameter 1 μm), IXE-500 (anion scavenger, bismuth type, median diameter 1.5 μm), IXE-550 (anion scavenger, bismuth type, median diameter 1.5 μm), IXE-600 (both ion scavenger, antimony/bismuth) system, median diameter 1 μm), IXE-700F (anion scavenger, aluminum/magnesium based, median diameter 1.5 μm), IXE-770F (anion scavenger, aluminum/magnesium based, median diameter 6 μm), IXE-6136 (Amphoteric ion scavenger, zirconium/bismuth type, median diameter 2.1 μm), etc.

The amount of the inorganic compound is 1 to 10 parts by weight based on 100 parts by weight of the carbon black. From the viewpoint of fine line adhesion and surface roughness, the amount of the inorganic compound is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the carbon black. From the viewpoint of stability of the composition and blackness of the black matrix, the amount is preferably 9 parts by mass or less, more preferably 8 parts by mass or less.

<Basic group-containing pigment dispersant>
The basic group-containing pigment dispersant only needs to be able to disperse the carbon black, and any known basic group-containing pigment dispersant used in pigment dispersion compositions for black matrices can be used, such as anionic surfactants, Examples include basic group-containing polyester pigment dispersants, basic group-containing acrylic pigment dispersants, basic group-containing urethane pigment dispersants, and basic group-containing carbodiimide pigment dispersants. As the basic group, a primary, secondary or tertiary amino group is particularly preferred from the viewpoint of excellent dispersibility. The basic group-containing pigment dispersants can be used alone or in combination of two or more.

The basic group-containing pigment dispersant is preferably a polymer type basic group-containing pigment dispersant, since good pigment dispersibility can be obtained. Examples of the polymeric basic group-containing pigment dispersants include basic group-containing urethane polymer pigment dispersants, basic group-containing polyester polymer pigment dispersants, and basic group-containing acrylic polymer pigments. Examples include dispersants and the like. Among these, a basic group-containing urethane polymer pigment dispersant and a basic group-containing acrylic polymer pigment dispersant are preferred. The basic group-containing urethane polymer pigment dispersant is more preferably a basic group-containing urethane polymer pigment dispersant having at least one selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains. .

The basic group-containing pigment dispersant has an amine value of 5 to 50 mg KOH / g, and more preferably the amine value is 5 to 35 mgKOH/g. Note that the amine value indicates the total amount of free base and base, and is expressed in mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize 1 g of sample.

The amount of the basic group-containing pigment dispersant is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of the carbon black.

<Acidic group-containing pigment dispersion aid>
The acidic group-containing pigment dispersion aid is used for the purpose of further improving the dispersibility of pigments, and includes, for example, lactam black, perylene compounds, diketopyrrolopyrrole compounds, azonaphthol compounds, dioxazine compounds, and quinacridone compounds. Compounds, phthalocyanine compounds and their metal complexes, compounds in which acidic groups such as carboxyl groups and sulfonic acid groups are introduced into dyes such as anthraquinone, naphthalene, acridone, or triazine (dye derivatives having acidic groups); Examples include compounds neutralized with organic amines and the like. As the dye derivative having an acidic group, a phthalocyanine-based dye derivative (having a phthalocyanine skeleton) having a sulfonic acid group is preferable from the viewpoint of good dispersibility of carbon black. The acidic group-containing pigment dispersion aids can be used alone or in combination of two or more.

The amount of the acidic group-containing pigment dispersion aid is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the carbon black.

<Alkali-soluble resin>
The alkali-soluble resin is an alkali-soluble cardo resin. The alkali-soluble cardo resin is not particularly limited as long as it can be dissolved in an alkaline developer, but resins containing one or more anionic groups such as carboxyl groups, sulfonic acid groups, and phosphonic acid groups may be used. preferable. The alkali-soluble resins can be used alone or in combination of two or more.

The alkali-soluble cardo resin refers to an alkali-soluble resin that has a cardo skeleton, and the cardo skeleton is a carbon atom in which two aromatic groups are bonded to a quaternary carbon atom, which is a ring carbon atom constituting a cyclic structure. A connected skeleton. Specific examples of alkali-soluble cardo resins include ADEKA ARKLS WR-301 (manufactured by ADEKA), OGZOL CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 (the above, (manufactured by Osaka Gas Chemical Co., Ltd.).

From the viewpoint of alkali developability, the acid value of the alkali-soluble cardo 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.

The amount of the alkali-soluble resin is preferably 2 parts by mass or more and 45 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the carbon black.

<Solvent>
As the solvent, a known solvent used in a pigment dispersion composition for a black matrix can be used. From the viewpoint of stably dispersing the pigment and sufficiently dissolving the basic group-containing pigment dispersant and the alkali-soluble resin, the solvent may be an ester solvent, an ether solvent, an ether ester solvent, or a ketone solvent. Preferred are solvents, aromatic hydrocarbon solvents, nitrogen-containing solvents, and the like. The above solvents can be used alone or in combination of two or more.

Examples of the ester solvent include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, and methyl 3-methoxypropionate. , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetate, n-amyl formate, and the like. Examples of the ether solvent 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, and propylene glycol monoethyl ether. , propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and the like. Examples of the ether ester solvent include 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 the like. Examples of the ketone solvent include methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone. Examples of the aromatic hydrocarbon solvent include toluene, xylene, alkylnaphthalene, and the like. Examples of the nitrogen-containing solvent include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

The proportion of the solvent in the black matrix pigment dispersion composition is preferably 40% by mass or more, more preferably 50% by mass or more from the viewpoint of processability, and from the viewpoint of dispersion stability. Therefore, it is preferably 90% by mass or less, more preferably 80% by mass or less.

If necessary, additives such as a leveling agent, a resin other than the alkali-soluble cardo resin, an antioxidant, and an antifoaming agent may be added to the pigment dispersion composition for a black matrix.

In the black matrix pigment dispersion composition, the total proportion of the carbon black, the inorganic compound, the basic group-containing pigment dispersant, the acidic group-containing pigment dispersion aid, the alkali-soluble resin, and the solvent is: It is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 95% by mass or more.

The pigment dispersion composition for a black matrix may be prepared by dispersing the above-mentioned components using a roll mill, kneader, high-speed stirrer, bead mill, ball mill, sand mill, ultrasonic dispersion machine, high-pressure dispersion device, etc.

<Pigment dispersion resist composition for black matrix>
The pigment dispersion resist composition for a black matrix of the present invention includes the pigment dispersion composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator. Note that the proportion of the carbon black is preferably 30% by mass or more and 80% by mass or less in the solid content of the pigment-dispersed resist composition for black matrix. In addition, the proportion of the inorganic compound is determined from the viewpoint of combining fine line adhesion and surface roughness resistance, stability of the pigment dispersion composition, and blackness of the black matrix in the solid content of the pigment dispersion resist composition for black matrix. It is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 0.2% by mass or more and 8.0% by mass or less.

<Photopolymerizable compound>
As the photopolymerizable compound, a known photopolymerizable compound used in a pigment-dispersed resist composition for a black matrix can be used, and examples thereof include monomers and oligomers having a photopolymerizable unsaturated bond. The photopolymerizable compounds can be used alone or in combination of two or more.

Examples of monomers having one photopolymerizable unsaturated bond include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; benzyl methacrylate, benzyl acrylate, etc. aralkyl methacrylates or acrylates; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate, butoxyethyl acrylate; aminoalkyl methacrylates or acrylates such as N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate; diethylene glycol monoethyl ether , methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoalkyl ethers such as triethylene glycol monobutyl ether and dipropylene glycol monomethyl ether; methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether Examples include ester; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate.

Examples of monomers having two or more photopolymerizable unsaturated bonds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, and neopentyl. Glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipenta Erythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol 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, and the like.

Examples of the oligomer having a photopolymerizable unsaturated bond include those obtained by suitably polymerizing the above monomers.

The amount of the photopolymerizable compound is preferably 2 to 20% by mass, more preferably 4 to 15% by mass, based on the solid content of the pigment-dispersed resist composition for black matrix.

The photopolymerization initiator may be a known photopolymerization initiator used in a pigment-dispersed resist composition for a black matrix, such as benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4- Methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl Phenylketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4 -dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and the like. The photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the solid content of the pigment-dispersed resist composition for black matrix.

The pigment-dispersed resist composition for black matrix may further contain the above-mentioned alkali-soluble resin from the viewpoint of developability with an alkaline developer. Further, the total amount of the alkali-soluble resin is preferably 4% by mass or more and 20% by mass or less in the solid content of the pigment-dispersed resist composition for black matrix. Moreover, the above-mentioned solvent may be further added to the pigment-dispersed resist composition for black matrix from the viewpoint of improving coating properties. The total proportion of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more in the pigment-dispersed resist composition for black matrix.

If necessary, additives such as a surface modifier, a leveling agent, an antioxidant, and an antifoaming agent may be added to the pigment-dispersed resist composition for a black matrix. However, from the viewpoint of odor, it is preferable not to include a thiol compound.

The pigment dispersion resist composition for a black matrix can be prepared by stirring and mixing the components such as the pigment dispersion composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator using a stirring device or the like. good.

<Black resist film>
The black resist film of the present invention can be obtained by a known method using the black matrix resist composition.

The method for forming the black matrix of the present invention is not particularly limited. For example, the resist composition for a black matrix of the present invention is applied onto a transparent substrate, dried to form a coating film, and then a photo film is coated on the coating film. A black matrix can be formed by placing a mask and performing image exposure through the photomask, development, and if necessary photocuring.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

<Preparation Examples 1 to 13, Comparative Preparation Examples 1 to 4>
<Preparation of pigment dispersion composition for black matrix>
The various raw materials shown in Table 1 or 2 are mixed to have the composition (mass%) shown in Table 1 or 2, and then kneaded in a bead mill to form the pigment dispersion composition for black matrix of each preparation example and comparative preparation example. I prepared something.

<Examples 1 to 13, Comparative Examples 1 to 4>
<Preparation of pigment-dispersed resist composition for black matrix>
The various raw materials shown in Table 3 or 4 were mixed using a high-speed stirrer so that the composition (mass%) shown in Table 3 or 4 was obtained, and then filtered through a filter with a pore size of 0.5 μm. A pigment-dispersed resist composition for a black matrix was prepared as a comparative example.

Using the pigment-dispersed resist composition for black matrix obtained above, each item was evaluated according to the following evaluation method. The results are shown in Table 2.

<Fine line adhesion>
Each of the above pigment-dispersed resist compositions for a black matrix was applied onto a glass substrate (EAGLE XG) using a spin coater to a film thickness of 2 μm, and prebaked at 100° C. for 3 minutes. Next, using a photomask having a line pattern with a line width of 1 μm to 20 μm and an interval of 1 μm, exposure was performed using a high-pressure mercury lamp at an integrated UV light amount of 100 mJ/cm ² . Thereafter, development was started from the time (break point) at which a developed pattern began to appear in a 0.04% potassium hydroxide aqueous solution at 23°C under a shower development pressure of 1 kgf/ ^cm2 . Development was terminated when the time was 1.3 times and 1.5 times the point, and finally, spray water washing at 1 kgf/cm ² pressure was performed. The size (μm) of the smallest line pattern remaining on the glass substrate after washing with water was evaluated. At 1.3 times the break point, the minimum line pattern size (μm) is 13 μm or less as an acceptance criterion, preferably 6 μm or less, and at 1.5 times the break point. The acceptance criterion is that the minimum line pattern size (μm) is 22 μm or less, and preferably 9 μm or less.

<Surface roughness resistance>
Development was completed at 1.3 times the break point, and the surface of the glass substrate, which was spray washed with water, was observed with an optical microscope (1000 times magnification) and evaluated based on the following criteria. The acceptance criteria is 〇 or △, and 〇 is preferred.
○: There is no surface roughness on the entire surface of the coating film.
Δ: Surface roughness is observed in a part of the coating film.
×: Surface roughness is observed on the entire surface of the coating film.

<Uneven water>
Each pigment-dispersed resist composition for black matrix was applied onto a glass substrate (EAGLE XG) using a spin coater to a film thickness of 1.5 μm, and prebaked at 100° C. for 3 minutes. Next, exposure was performed using a high-pressure mercury lamp at an integrated UV light amount of 40 mJ/cm ² . Thereafter, development was performed at 23°C in a 0.04% potassium hydroxide aqueous solution at a shower development pressure of 1 kgf/cm ² at 1.1 times the break point, and finally, spray washing was performed at 1 kgf/cm ² pressure. Ta. The surface of the glass substrate after washing with water was observed and evaluated based on the following criteria. The acceptance criteria is 〇 or △, and 〇 is preferred.
○: There is no unevenness on the entire surface of the coating film.
Δ: Unevenness is observed in a part of the coating film.
×: Unevenness is observed over the entire surface of the coating film.

In Table 1-4, Raven 1080 is carbon black (average primary particle size 28 nm, pH 2.4, manufactured by Columbia Chemicals);
C301N is aluminum hydroxide (median diameter 1.5 μm, manufactured by Sumitomo Chemical Co., Ltd.);
C302A is aluminum hydroxide (median diameter 2.4 μm, manufactured by Sumitomo Chemical Co., Ltd.);
AKP-053 is aluminum oxide (median diameter 0.17 μm, manufactured by Sumitomo Chemical Co., Ltd.);
BF40 is precipitated barium sulfate “BARIFINE BF-40” (median diameter 0.01 μm, manufactured by Sakai Chemical Industry Co., Ltd.);
BTC-4FA is barium titanate (average primary particle size 200 nm, manufactured by Nihon Kagaku Kogyo Co., Ltd.);
IXE-500 is an anion scavenger (bismuth type, median diameter 1.5 μm, manufactured by Toagosei Co., Ltd.);
IXE-100 is a cation scavenger (zirconium-based, median diameter 1 μm, manufactured by Toagosei Co., Ltd.);
SP-2 is boron nitride (Denka boron nitride SP-2, median diameter 4 μm, manufactured by Denka Corporation);
SP-3 is boron nitride (Denka boron nitride SP-3, median diameter 4 μm, manufactured by Denka Corporation);
DB167 is an amino group-containing polyurethane polymer dispersant having a polyester chain (manufactured by Bikkemie, solid content amine value 25 mgKOH/g, solid content 52% by mass);
SS5000S is a phthalocyanine dye derivative having a sulfonic acid group (manufactured by Lubrizol);
SS12000S is a phthalocyanine dye derivative having a sulfonic acid group (manufactured by Lubrizol);
The cardo-based resin is an alkali-soluble cardo resin "ADEKA ARKLS WR-301" (acid value 100 mgKOH/g, Mw 6,000, solid content 44%, manufactured by ADEKA);
Acrylic resin 1 is an alkali-soluble acrylic resin “Follet ZAH-110” (acid value 100 mgKOH/g, Mw 1,0000, solid content 35%, manufactured by Soken Chemical Co., Ltd.);
Acrylic resin 2 is an alkali-soluble acrylic resin “Follet ZAH-510” (acid value 100 mgKOH/g, Mw 5,0000, solid content 35%, manufactured by Soken Chemical Co., Ltd.);
DPHA is dipentaerythritol hexaacrylate;
IRGACURE OXE02 is an oxime ester photopolymerization initiator "IRGACURE OXE02" (manufactured by BASF Japan);
MF-554 is "Megafac F-554" (fluorine-containing group/lipophilic group-containing oligomer, solid content 100%, manufactured by DIC Corporation);
PGMEA stands for propylene glycol monomethyl ether acetate;

In Table 4, Comparative Example 2 is rated as not rated, indicating that no fine lines remain after development. In addition, the evaluation of Comparative Example 3 as not acceptable indicates that dissolution did not start even after exposure to the developer for 180 seconds or more. Furthermore, "-" in Tables 3 and 4 indicates that no evaluation was performed.

Claims (3)

A pigment dispersion composition for a black matrix comprising carbon black, an inorganic compound, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersion aid, an alkali-soluble resin, and a solvent,
The inorganic compound is one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, barium sulfate, barium titanate, boron nitride, and an ion scavenger,
The alkali-soluble resin is an alkali-soluble cardo resin,
A pigment dispersion composition for a black matrix, wherein the inorganic compound is present in an amount of 1 to 10 parts by mass based on 100 parts by mass of the carbon black. A pigment-dispersed resist 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. A black resist film formed from the pigment-dispersed resist composition for black matrix according to claim 2.