KR20230091013A - Black matrix pigment dispersion composition and manufacturing method thereof, black matrix resist composition, and black resist film - Google Patents

Abstract

The present invention relates to a pigment dispersion composition for a black matrix including carbon black, a pigment dispersant including a basic group, a pigment dispersant including an acidic group, an alkali-soluble resin, an ion trapping agent, and a solvent, wherein the carbon black is acidic carbon black and the ion trapping agent is an inorganic compound with a median diameter of 0.1 to 10 μm and is included in 1 to 15 parts by mass based on 100 parts by mass of the carbon black. The pigment dispersion composition for a black matrix has excellent optical density and fine line adhesion.

Description

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

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

Conventionally, a resist composition using a pigment dispersion composition for a black matrix containing carbon black, a pigment dispersant containing a basic group, a pigment dispersion aid containing an acidic group, a binder resin and a solvent has high optical density (light blocking property) and fine wire adhesion (resolution). This is demanded (Patent Document 1), and it is known that the optical density (light-shielding property) and the like can be improved by further washing the carbon black to reduce potassium ions (Patent Document 2).

[Patent Document 1] Japanese Unexamined Patent Publication No. 2021-38289 [Patent Document 2] Japanese Unexamined Patent Publication No. 2007-316620

However, in the case of washing carbon black as described above, there is a problem in that a large amount of water needs to be used and complicated operations such as washing, filtration, and drying are required. In addition, in order to remove potassium ions in the composition, a method of generally passing the composition through a resin tower equipped with an ion exchange resin is also known, but since a large amount of ion exchange resin is used, high costs are incurred in procurement and disposal of the ion exchange resin. There was a problem requiring

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a pigment dispersion composition for a black matrix from which a resist composition for a black matrix excellent in optical density and fine wire adhesion can be obtained.

That is, the present invention contains carbon black, a pigment dispersant containing a basic group, a pigment dispersing aid containing an acidic group, an alkali-soluble resin, an ion scavenger, and a solvent, wherein the carbon black is acidic carbon black, and the ion scavenger is a median It is an inorganic compound with a diameter of 0.1 to 10 µm, and relates to a pigment dispersion composition for a black matrix, which is 1 to 15 parts by mass based on 100 parts by mass of the carbon black.

Further, the present invention relates to a resist composition for a black matrix containing the pigment dispersion composition for a black matrix, a photopolymerizable compound, and a photopolymerization initiator.

Moreover, this invention relates to the black resist film obtained using the resist composition for black matrices.

Further, the present invention relates to a method for producing the pigment dispersion composition for a black matrix, wherein at least the carbon black is subjected to a dispersion treatment in the presence of the ion trapping agent.

The pigment dispersion composition for a black matrix of the present invention contains carbon black, a basic group-containing pigment dispersant, an acidic group-containing pigment dispersing aid, an alkali-soluble resin, an ion trapping agent, and a solvent, wherein the carbon black is acidic carbon black, The ion trapping agent is an inorganic compound having a median diameter of 0.1 to 10 µm, and is 1 to 15 parts by mass based on 100 parts by mass of the carbon black. Since the pigment dispersion composition for a black matrix of the present invention can capture substances containing ions such as potassium ions, which are mixed in the production of acidic carbon black by the ion trapping agent, operations such as washing the acidic carbon black are not required. A resist composition for a black matrix excellent in optical density and thin line adhesion without the need for a black matrix can be obtained.

The pigment dispersion composition for a black matrix of the present invention contains carbon black, a pigment dispersant containing a basic group, a pigment dispersing aid containing an acidic group, an alkali-soluble resin, an ion trapping agent, and a solvent.

<Carbon Black>

The said carbon black is acidic carbon black which has acidic groups, such as a carboxyl group. As the acidic carbon black, known acidic carbon blacks used in pigment dispersion compositions for black matrices can be used. For example, from the viewpoint of improving developability and fine wire adhesion, the pH is preferably 5.0 or less, and the pH is 1.0 or more. It is more preferably 3.5 or less, and the DBP oil absorption amount is preferably 80 ml/100 g or less, more preferably the DBP oil absorption amount is 70 ml/100 g or less, and the particle size is preferably 20 to 60 nm. In addition, the pH can be measured by adding 1 g of carbon black to 20 ml of distilled water (pH 7.0) excluding carbonic acid, 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). In addition, DBP oil absorption amount indirectly quantifies the structure of carbon black by measuring void volume, and is a numerical value measured based on JIS K 6217-4. In addition, the said particle diameter means the average primary particle diameter measured or computed by microscopic observation. For these values, in the case of commercial products, refer to the catalog values. These carbon blacks may be used alone or in combination of two or more.

Specific examples of the acidic carbon black include Raven 1080 (pH 2.4, average primary particle size 28 nm, DBP oil absorption 60 ml/100 g) and Raven 1100U (pH 2.9, average primary particle size 32 nm, DBP oil absorption 72 ml/100 g) manufactured by Columbia Chemicals. , NEROX305 (pH2.8, average primary particle size 28 nm, DBP oil absorption 58 ml / 100 g), NEROX3500 (pH3.0, average primary particle size 31 nm, DBP oil absorption 43 ml / 100 g) TPK1104R (pH 3.0, Average primary particle size about 30 nm, DBP oil absorption 38ml/100g), MA14 (pH2.8, average primary particle size 40nm, DBP oil absorption 73ml/100g) manufactured by Mitsubishi Chemical, MA220 (pH 2.9, average primary particle size 55nm, DBP oil absorption 93ml/100g) and the like.

The carbon black is preferably 3% by mass or more, more preferably 10% by mass or more, and 70% by mass from the viewpoint of pigment dispersion, from the viewpoint of enhancing the light-shielding property when a black matrix film is formed in the pigment dispersion composition for a black matrix. It is preferable that it is below, and it is more preferable that it is 50 mass % or less.

<Basic group-containing pigment dispersant>

The basic group-containing pigment dispersant only needs to be capable of dispersing the carbon black, and known basic group-containing pigment dispersants used in pigment dispersion compositions for black matrices can be used, such as anionic surfactants and basic group-containing polycarbonates. Ester-type pigment dispersants, basic group-containing acrylic pigment dispersants, basic group-containing urethane-type pigment dispersants, basic group-containing carbodiimide-type pigment dispersants, and the like are exemplified. As the basic group, a primary, secondary or tertiary amino group is particularly preferred from the standpoint of excellent dispersibility. The said basic group containing pigment dispersant can be used individually or in combination of 2 or more types.

The pigment dispersant containing a basic group is preferably a polymeric type pigment dispersant containing a basic group from the viewpoint of obtaining good pigment dispersibility. Examples of the polymer type pigment dispersant containing a basic group include a basic group-containing urethane polymer pigment dispersant, a basic group-containing polyester polymer pigment dispersant, and a basic group-containing acrylic polymer pigment dispersant. Among these, a basic group-containing urethane-based polymer pigment dispersant and a basic group-containing acrylic polymer pigment dispersant are preferable. The basic group-containing urethane-based polymer pigment dispersant is more preferably a basic group-containing urethane-based polymer pigment dispersant having at least one selected from the group consisting of a polyester chain, a polyether chain, and a polycarbonate chain.

The basic group-containing pigment dispersant preferably has an amine value of 5 to 50 mgKOH/g, and an amine value of 5 to 35 mgKOH/g from the viewpoint of being able to lower the viscosity of the pigment dispersion composition for a black matrix and to increase the concentration of carbon black in the coating film. It is more preferable that it is g. In addition, the amine value indicates the total amount of free base and base, and is expressed as the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize 1 g of the sample.

It is preferable that it is 1-100 mass parts, and it is more preferable that it is 2-50 mass parts with respect to 100 mass parts of the said carbon black of the said basic group containing pigment dispersant.

<Acidic group-containing pigment dispersing aid>

The acidic group-containing pigment dispersing aid is used for the purpose of further improving the dispersibility of the pigment, for example, lactam black, perylene-based compound, diketopyrrolopyrrole-based compound, azonaphthol-based compound, dioxazine-based compound, quinacridone-based compound , phthalocyanine-based compounds and their metal complexes, compounds in which an acidic group such as a carboxyl group or a sulfonic acid group is introduced into a pigment such as anthraquinone, naphthalene, acridone, or triazine (pigment derivative having an acidic group), these as organic amines, etc. A neutralized compound is mentioned. As the pigment derivative having an acidic group, a phthalocyanine-based (having a phthalocyanine skeleton) pigment derivative having a sulfonic acid group is preferable from the viewpoint of good dispersibility of carbon black. The acidic group-containing pigment dispersing aid may be used alone or in combination of two or more.

It is preferable that it is 0.1-20 mass parts, and it is more preferable that it is 1-10 mass parts with respect to 100 mass parts of said carbon blacks of the said acidic group containing pigment dispersing aid.

<Alkali-soluble resin>

The alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline developer, but one or more of anionic groups such as carboxyl group, sulfonic acid group, and phosphonic acid group (-P(=O)(OH ₂ )) are used. Resin containing is preferable. The alkali-soluble resin may be used alone or in combination of two or more.

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, from the viewpoint of alkali developability.

It is preferable that it is 3,000 or more, and, as for the weight average molecular weight of the said alkali-soluble resin, it is more preferable that it is 4,000 or more from a viewpoint of formation property of a resist film. It is preferable that it is 100,000 or less, and, as for the weight average molecular weight of the said alkali-soluble resin, it is more preferable that it is 50,000 or less from a viewpoint of improving solubility to alkali developing solution.

The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. As an example, using Water2690 (manufactured by Waters) as a GPC device, PLgel, 5 μm, MIXED-D (manufactured by Polymer Laboratories) as a column, tetrahydrofuran as a developing solvent, column temperature 25 ° C., flow rate 1 milliliter / min, Chromatography is performed under the conditions of an RI detector, a sample injection concentration of 10 milligrams/milliliter, and an injection amount of 100 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.

Examples of the alkali-soluble resin include alkali-soluble polyimide resin, alkali-soluble polyimide precursor, alkali-soluble polybenzoxazole resin, alkali-soluble polybenzoxazole precursor, alkali-soluble cardo resin, alkali-soluble epoxy (meth)acrylic acid. rate resins, alkali-soluble polysiloxane resins, alkali-soluble novolak resins, alkali-soluble (meth)acrylic resins, alkali-soluble polyurethane resins, alkali-soluble polyester resins and the like. Among these, alkali-soluble cardo resin and alkali-soluble epoxy (meth)acrylate resin are preferable from a viewpoint of the heat resistance of a coating film.

The alkali-soluble cardo resin refers to an alkali-soluble resin having a cardo skeleton, and the cardo skeleton refers to a skeleton in which two aromatic groups are connected by a single bond to a quaternary carbon atom, which is a ring carbon atom constituting a cyclic structure. As a specific example of alkali-soluble cardo resin, ADEKA ARKLS WR-301 (made by ADEKA), Ogsol CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 (above, manufactured by Osaka Gas Chemical Co., Ltd.).

The alkali-soluble epoxy (meth) acrylate resin refers to the introduction of an ethylenically unsaturated group by ring-opening addition of a carboxyl group of an ethylenically unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, and further to at least a part of the hydroxyl groups generated by ring-opening of the epoxy group Among the acid-modified epoxy resins obtained by introducing a carboxyl group by adding a polybasic carboxylic acid (or its anhydride), it does not have the cardo skeleton and corresponds to the alkali-soluble resin. Examples of the epoxy resin serving as a base material in the alkali-soluble epoxy (meth)acrylate resin include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, epoxy resins having a biphenyl structure, phenol novolak-type epoxy resins, Cresol novolak-type epoxy resins are preferably used. As an ethylenically unsaturated monocarboxylic acid used in order to modify|denature an epoxy resin, acrylic acid and methacrylic acid are mentioned preferably, for example. As polybasic carboxylic acid (or its anhydride), maleic acid anhydride, succinic acid anhydride, and tetrahydrophthalic anhydride are mentioned preferably, for example. Among these, an alkali-soluble epoxy (meth)acrylate resin having a biphenyl skeleton is preferable from the viewpoint of improving the thin wire adhesion. Specific examples of the alkali-soluble epoxy (meth)acrylate resin include ZAR-1494H, ZAR-2001H, ZFR-1491H, ZCR-1797H, ZCR-1569H, and ZCR-1798H (above, manufactured by Nippon Kayaku Co., Ltd.). can Moreover, as a preferable specific example, the alkali-soluble epoxy (meth)acrylate resin which has a partial structure represented by any one of the following structural formulas is mentioned.

[Formula 1]

It is preferable that it is 1-70 mass parts, and, as for the said alkali-soluble resin, it is more preferable that it is 2-40 mass parts with respect to 100 mass parts of said carbon black.

<Ion capture agent>

The ion trapping agent is an inorganic compound having a median diameter of 0.1 to 10 μm. The ion trapping agent may be any one capable of trapping at least one of cations and anions, and examples thereof include cation trapping agents, anion trapping agents, and both ion trapping agents having ion trapping ability. Examples of the inorganic compound include inorganic compounds containing at least one metal atom selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, magnesium, and aluminum. Among these, an inorganic compound containing at least one metal atom selected from the group consisting of bismuth, zirconium, magnesium, and aluminum is preferable. The said ion trapping agent can be used individually or in combination of 2 or more types. In addition, the median diameter can be measured using a laser diffraction/scattering type particle size distribution measuring device, and in the case of a commercial product, reference is made to the catalog value.

The ion trapping agent is 1 to 15 parts by mass based on 100 parts by mass of the carbon black. The ion trapping agent is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and 10 parts by mass or less from the viewpoint of improving the optical density, with respect to 100 parts by mass of the carbon black. It is preferable, and it is more preferable that it is 8 mass parts or less.

<Solvent>

As the solvent, a known solvent used in a pigment dispersion composition for a black matrix may be used. The solvent stably disperses the pigment and is an ester solvent, an ether solvent, an ether ester solvent, a ketone solvent, or an aromatic hydrocarbon solvent from the viewpoint of sufficiently dissolving the basic group-containing pigment dispersant or the alkali-soluble resin. , nitrogen-containing solvents, etc. are preferable. These 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, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid ester, n-amyl formate, etc. are mentioned. Examples of the ether-based 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, and propylene glycol. monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and 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, and propylene glycol monoethyl ether acetate. Examples of the ketone solvent include methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone. Examples of the aromatic hydrocarbon-based solvent include toluene, xylene, and alkyl naphthalene. Examples of the nitrogen-containing solvent include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

The ratio of the solvent is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 90% by mass or less from the viewpoint of processability, and 80% by mass in the pigment dispersion composition for a black matrix. It is more preferable that it is % or less.

<Epoxy resin>

You may use an epoxy resin for the said pigment dispersion composition for black matrices from a viewpoint of improving thin wire adhesiveness. In particular, in high-resistance applications, it is preferable to blend an epoxy resin. The epoxy resin is a multifunctional epoxy resin having two or more epoxy groups. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, trisphenolmethane type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain type epoxy resin, Glycidyl ester type epoxy resin, glycidyl condensate of phenolic compounds (phenol, cresol, alkylphenol, catechol, bisphenol F, bisphenol A, bisphenol S, etc.) and aldehyde compounds (formaldehyde, salicylaldehyde, etc.) Ether compounds, glycidyl ether products of bifunctional phenols, glycidyl ether products of bifunctional alcohols, glycidyl ether products of trifunctional or higher functional polyphenols, and hydrogenated products or halides thereof. The epoxy resin may be a polyfunctional epoxy resin having an alicyclic ring or an aromatic ring, or may be a multifunctional epoxy resin having an alicyclic dicyclopentadiene backbone. Resin is preferred. Specific examples of the epoxy resin include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, and Epolite 3002 ( Manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L, Denacol EX-321L (above, manufactured by Nagase ChemteX Co., Ltd.), GAN, GOT , NC3000, NC6000, EPPN502H, EPPN-503 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, E4275 (above, Japan Epoxy Resin company), Epicron EXA-9583, Epicron N695, HP7200, HP4032 (above, manufactured by Dainippon Inkki Chemical Industries, Ltd.), VG3101 (manufactured by Mitsui Chemicals, Inc.), Tepic S, Tepic G, Tepic P (above, manufactured by Nissan Chemical Industries, Ltd.) ), Potot YH-434L (manufactured by Doto Kasei Co., Ltd.), and the like. Moreover, it is preferable from points, such as reactivity, that the said epoxy resin does not have an indan structure or a biphenyl structure.

As said epoxy resin, the polyfunctional epoxy resin which has an aromatic ring represented by the following formulas 1-7 is mentioned preferably, for example.

[Formula 2]

(Equation 1)

(m is 0 to 20)

[Formula 3]

(Equation 2)

[Formula 4]

(Equation 3)

(n is 1 to 20)

[Formula 5]

(Equation 4)

(R ₁ to R ₆ are each independently a saturated hydrocarbon group having 1 to 6 carbon atoms, and n is 1 to 20)

[Formula 6]

(Equation 5)

(n is 1 to 20)

[Formula 7]

(Equation 6)

(R ¹ to R ² are each independently a saturated hydrocarbon group having 1 to 6 carbon atoms, and n is 1 to 20)

[Formula 8]

(Equation 7)

(n is 1 to 20)

The epoxy resin is preferably 1 part by mass or more, and preferably 2 parts by mass or more, from the viewpoint of resistance value as a black matrix with respect to 100 parts by mass of carbon black contained in the pigment dispersion composition for a black matrix or a resist composition for a black matrix described later. More preferably, it is more preferably 5 parts by mass or more, and from the viewpoint of blackness by pigment concentration, it 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.

You may further add additives, such as a leveling agent, resin other than the said epoxy resin and the said alkali-soluble resin, antioxidant, and an antifoamer, to the said pigment dispersion composition for black matrices as needed. However, it is preferable not to contain a thiol compound (for example, a thiol compound having a molecular weight of 1000 or less) from the viewpoint of odor.

In the pigment dispersion composition for a black matrix, the total ratio of the carbon black, the basic group-containing pigment dispersant, the acidic group-containing pigment dispersant aid, the alkali-soluble resin, the ion trapping agent, and the solvent is 75% by mass or more. It is preferable, and it is more preferable that it is 85 mass % or more, and it is still more preferable that it is 95 mass % or more. In the case of blending the epoxy resin, in the black matrix pigment dispersion composition, the carbon black, the basic group-containing pigment dispersant, the acidic group-containing pigment dispersing aid, the alkali-soluble resin, the ion trapping agent, and the solvent and the ratio of the total of the epoxy resin is preferably 75% by mass or more, more preferably 85% by mass or more, and still more preferably 95% by mass or more.

The pigment dispersion composition for the black matrix may be 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 dispersion device, or the like. In particular, from the viewpoint of efficiently trapping substances containing ions contained in the carbon black and improving optical density and fine wire adhesion, it is preferable to carry out a dispersion treatment of at least the carbon black in the presence of the ion trapping agent.

<Resist composition for black matrix>

The 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. In addition, it is preferable that the ratio of the said carbon black is 30 mass % or more and 80 mass % or less with respect to the solid content of the said resist composition for black matrixes.

<Photopolymerizable compound>

As the photopolymerizable compound, known photopolymerizable compounds used in resist compositions for black matrices may be used, and examples thereof include monomers and oligomers having photopolymerizable unsaturated bonds. The photopolymerizable compound may be used alone or in combination of two or more.

Examples of the monomer having one photopolymerizable unsaturated bond include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. acrylates or acrylates; aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; aminoalkyl methacrylates or acrylates such as N.N-dimethylaminoethyl methacrylate and N.N-dimethylaminoethyl acrylate; methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, 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; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate; and the like.

Examples of the monomer having two or more photopolymerizable unsaturated bonds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, and diethylene glycol dimethacrylate. , glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimeta acrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate Rate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaeryth A ritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. are mentioned.

As an oligomer which has a photopolymerizable unsaturated bond, what was obtained by suitably polymerizing the said monomer is mentioned, for example.

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

As the photopolymerization initiator, known photopolymerization initiators used in resist compositions for black matrices may be used, and examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy- 4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoinmethyl ether, benzoin isobutyl ether, benzyldimethylketal, α-hydroxyisobutylphenone, thioxanthone, 2 -Chlorothioxanthone, 1-hydroxycyclohexylphenylketone, 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, and oxime ester-based photopolymerization initiators. The photopolymerization initiator may be used alone or in combination of two or more.

It is preferable that it is 0.1-15 mass %, and, as for the said photoinitiator, it is more preferable that it is 1-10 mass % in the solid content of the said black matrix resist composition.

The alkali-soluble resin may be further added to the resist composition for a black matrix from the viewpoint of developability with an alkali developer. In addition, it is preferable that the total amount of the alkali-soluble resin is 10% by mass or more and 50% by mass or less based on the solid content of the resist composition for a black matrix. In addition, the said solvent may be further added to the said resist composition for black matrices from a viewpoint of improving paintability. It is preferable that it is 50 mass % or more, and, as for the ratio of the sum total of the said solvent, in the said black matrix resist composition, it is more preferable that it is 70 mass % or more.

You may further add additives, such as a leveling agent, antioxidant, and an antifoamer, to the said resist composition for black matrices as needed.

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

<Black Resist Film>

The black resist film of the present invention is obtained using the above resist composition for a black matrix. The black resist film preferably has a surface resistance value of 5.0×10 ⁹ Ω/□ or more, more preferably 1.0×10 ¹⁰ Ω/□ or more, and still more preferably 1.0×10 ¹¹ Ω/□ or more. In particular, for high-resistance applications, the surface resistance value is preferably 1.0×10 ¹² Ω/□ or more, and more preferably 1.0×10 ¹³ Ω/□ or more.

[Example]

The present invention will be described below by examples and the like, but the present invention is not limited to these.

<Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-6>

<Preparation of Pigment Dispersion Composition for Black Matrix>

After mixing the various raw materials shown in Tables 1 and 2 so as to have the compounding composition (% by mass) shown in Tables 1 and 2, they were tenderized with a bead mill to prepare black matrix pigment dispersion compositions of Examples and Comparative Examples.

In Tables 1 and 2, NEROX305 is acidic carbon black (oil absorption 58 ml/100 g, pH 2.8, average primary particle size 28 nm, manufactured by Orion Engineered Carbons);

TPK1104R is acidic carbon black (oil absorption: 38 ml/100 g, pH 3.0, average primary particle diameter of about 30 nm, manufactured by Cabot Co.);

IXEPLAS B1 is a cation scavenger (zirconium/bismuth type, median diameter 0.4 μm, manufactured by Toa Synthetic Industries Co., Ltd.);

IXE-100 is a cation scavenger (zirconium-based, median diameter of 1 μm, manufactured by Toa Synthetic Co., Ltd.);

IXE-500 is an anion scavenger (bismuth type, median diameter 1.5 μm, manufactured by Toa Synthetic Industries Co., Ltd.);

IXE-550 is an anion scavenger (bismuth type, median diameter 1.5 μm, manufactured by Toa Synthetic Industries Co., Ltd.);

IXE-600 is a cation scavenger (antimony/bismuth type, median diameter of 1 μm, manufactured by Toa Synthetic Industries Co., Ltd.);

IXE-700F is an anion scavenger (aluminum/magnesium type, median diameter 1.5 μm, manufactured by Toa Synthesis Co., Ltd.);

IXE-770F is an anion scavenger (aluminum/magnesium type, median diameter of 6 μm, manufactured by Toa Synthetic Technology Co., Ltd.);

IXE-6136 is a cation scavenger (zirconium/bismuth type, median diameter 2.1 μm, manufactured by Toa Synthetic Industries Co., Ltd.);

DB167 is an amino group-containing polyurethane-based polymer dispersant having a polyester chain (manufactured by Big Chemie Co., Ltd., amine value of 25 mgKOH/g in solid content, solid content of 52% by mass);

SS5000S is a phthalocyanine-based pigment derivative having a sulfonic acid group (manufactured by Lubrizol);

BYK2100 is a phthalocyanine-based pigment derivative having a sulfonic acid group (manufactured by Big Chemistry);

ZCR-1569H is an alkali-soluble epoxy (meth)acrylate resin having a biphenyl backbone (solid content: 69%, manufactured by Nippon Kayaku Co., Ltd.);

EPPN-503 is a trishydroxyphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.);

PGMEA stands for propylene glycol monomethyl ether acetate;

<Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-6>

<Preparation of resist composition for black matrix>

Various raw materials shown in Tables 3 and 4 were mixed using a high-speed stirrer so as to have the compounding composition (% by mass) shown in Tables 3 and 4, and then filtered through a filter with a pore diameter of 0.5 μm, and each Example and Comparative Example A resist composition for a black matrix was prepared.

In addition, each item was evaluated according to the following evaluation method using the resist composition for black matrices obtained above. The results are shown in Table 3 and Table 4.

<Evaluation of optical density (OD value) of resist pattern>

Each of the above black matrix resist compositions was coated on a glass substrate (Corning 1737) to a film thickness of 1 μm by a spin coater, prebaked at 100° C. for 3 minutes, then exposed with a high-pressure mercury lamp, and further at 230° C. for 30 minutes Post-baking was performed to obtain a resist film formed of only the front portion (solid portion). The optical density (OD value) of the resulting resist film on each front surface was measured with a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth). An optical density (OD value) of 4.0 or more was used as the acceptance criterion.

<Evaluation of thin wire adhesion (A) and (B) of black resist film>

Each of the above black matrix resist compositions was coated on a glass substrate (EAGL XG) with a spin coater to a film thickness of 1 μm, and prebaked at 100° C. for 3 minutes. Subsequently, a photomask having a line pattern at intervals of 1 μm for a line width of 1 μm to 20 μm was used, and exposure was performed with a cumulative UV light amount of 100 mJ/cm 2 using a high-pressure mercury lamp. Thereafter, development was started from the time at which the development pattern began to appear (break point) at 23°C and a shower development pressure of 1 kgf/cm in a 0.05% potassium hydroxide aqueous solution. Development was terminated at the time of , and development was terminated at 30 seconds after the break point in the evaluation of thin wire adhesion (B). Thereafter, spray washing was performed at a pressure of 1 kgf/cm 2 . The size (μm) of the minimum line pattern remaining on the glass substrate was evaluated. The evaluation of thin wire adhesion (A) was based on a break point of 50 ± 25 seconds and a minimum line pattern size of 10 µm or less. In the evaluation of thin wire adhesion (B), a break point of 20±10 seconds and a minimum line pattern size of 8 μm or less were used as acceptance criteria.

<Measurement of Surface Resistance of Black Resist Film>

Each of the above black matrix resist compositions was coated on a glass substrate (EAGL XG) with a spin coater to a film thickness of 1 μm, prebaked at 100° C. for 3 minutes, and then exposed with a high pressure mercury lamp (UV light intensity) 80 mJ/ cm 2 ), and post-baking at 230° C. for 60 minutes was further performed to produce a black resist pattern (black matrix) formed only on the front portion. The surface resistance value of each produced black resist pattern was measured with main body: microcurrent meter R8340, option: shield box R12702A (both manufactured by Advance Co.).

In Tables 3 and 4, DPHA is dipentaerythritol hexaacrylate;

OXE02 is an oxime ester photopolymerization initiator "IRGACURE OXE02" (manufactured by BASF Japan);

WR-301 is an alkali-soluble cardo resin "ADEKA ARKLS WR-301" (44% solid content, manufactured by ADEKA Corporation);

PGMEA stands for propylene glycol monomethyl ether acetate;

Claims (7)

containing carbon black, a pigment dispersant containing a basic group, a pigment dispersing aid containing an acidic group, an alkali-soluble resin, an ion trapping agent, and a solvent;
The carbon black is an acidic carbon black,
The ion trapping agent is an inorganic compound having a median diameter of 0.1 to 10 µm, and is 1 to 15 parts by mass based on 100 parts by mass of the carbon black. The pigment dispersion composition for a black matrix, characterized in that: The pigment dispersion composition for a black matrix according to claim 1, wherein the carbon black has a DBP oil absorption of 80 ml/100 g or less. The pigment dispersion composition for a black matrix according to claim 1 or 2, wherein the basic group-containing pigment dispersant has an amine value of 5 to 50 mgKOH/g. The pigment dispersion composition for a black matrix according to claim 1 or 2, wherein the alkali-soluble resin is an alkali-soluble cardo resin and/or an alkali-soluble epoxy (meth)acrylate resin. A resist composition for a black matrix characterized by containing the pigment dispersion composition for a black matrix according to claim 1 or 2, a photopolymerizable compound, and a photopolymerization initiator. A black resist film obtained using the resist composition for a black matrix according to claim 5. A method for producing a resist composition for a black matrix according to claim 1 or 2, wherein at least the carbon black is subjected to a dispersion treatment in the presence of the ion trapping agent.