JP2022098114A - Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix - Google Patents

Abstract

Kind Code: A1 A pigment dispersion composition for a black matrix is provided, which can maintain a surface resistance value even after post-baking and can form a black matrix having excellent heat flow properties. A black coloring agent, a sulfonated product of copper phthalocyanine, and an amine compound are included, the amine compound is an imidazole compound and/or a triazole compound, and the content of the amine compound is the black coloring agent. A black matrix pigment dispersion composition containing 0.1 to 1.5 parts by mass per 100 parts by mass of the agent. [Selection figure] None

Description

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

In an image display device using a liquid crystal or plasma, a light-shielding film (on the outside light side of the TFT, etc. Black matrix) is provided.
Then, in the liquid crystal display device, the leakage light mainly from the backlight is prevented from being reflected on the screen, and in the plasma display device, the bleeding mainly due to the turbidity of each color light is prevented from being reflected on the screen, and the display characteristics (contrast and color purity) are improved. Helping to improve.

For example, in a color filter used to convert white light of a backlight of a liquid crystal display device into colored light, red, green, and blue are usually formed on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed. It is manufactured by a method of sequentially forming pixels having different hues in a pattern such as a stripe shape or a mosaic shape.

Also, in the touch panel that combines the image display device and the position input device, a color filter with a black matrix formed as a light-shielding film is also used. It was generally done to form on the side. However, as the demand for weight reduction of the touch panel increases, the development of a technique for simultaneously forming a light-shielding film and a touch sensor on the same side of the cover glass is progressing so that the weight can be further reduced.

As a method for forming such a black matrix, for example, a photolithography method (pigment method) using a pigment is used.
In such a pigment method, a sulfonic acid derivative of copper phthalocyanine may be used in order to enhance the dispersibility of the pigment.

For example, in Patent Document 1, a carbon black having an oil absorption amount in the range of 10 to 150 ml / 100 g and a pH in the range of more than 9, a basic group-containing urethane polymer pigment dispersant having a polyester chain, and an acid group-containing pigment derivative. Disclosed as a pigment dispersion composition for a black matrix, which comprises a phthalocyanine derivative having a sulfonic acid group dispersed in a solvent.

In the black matrix, it is desired that the surface resistance value can be maintained even after post-baking in order to prevent short circuit and current leakage.
Further, in the black matrix, it is possible to prevent the pattern from being missing by forming a forward taper shape by performing heat flow (heat flow) at the time of post-baking. Therefore, it is desired that the black matrix has appropriate heat flow characteristics.
However, in Patent Document 1, the surface resistance value and the heat flow characteristic have not been sufficiently studied, and there is room for further improvement.

International Publication No. 2008/066100

Therefore, an object of the present invention is to provide a pigment dispersion composition for a black matrix, which can maintain a surface resistance value even after post-baking and can form a black matrix having excellent heat flow characteristics. do.

The present inventors have added a specific amount of a specific amine compound in a pigment dispersion composition for a black matrix containing a black colorant and a sulfonated copper phthalocyanine to further add a specific amount of a specific amine compound to a surface resistance value even after post-baking. It has been found that a pigment dispersion composition for a black matrix capable of forming a black matrix having excellent heat flow characteristics can be obtained, and the present invention has been completed.

That is, the present invention contains a black colorant, a sulfonated copper phthalocyanine, and an amine compound. The amine compound is an imidazole-based compound and / or a triazole-based compound, and the content of the amine compound is the above. It is a pigment dispersion composition for a black matrix containing 0.1 to 1.5 parts by mass with respect to 100 parts by mass of a black colorant.
The black colorant is preferably carbon black, more preferably acidic carbon black.
The imidazole-based compound is preferably an alkyl imidazole, more preferably the alkyl imidazole has an alkyl group having 8 to 16 carbon atoms, and the alkyl imidazole is a monoalkyl imidazole having 8 carbon atoms. It is more preferably having ~ 16 linear alkyl groups, and particularly preferably 2-undecylimidazole.
The triazole-based compound preferably has a benzotriazole skeleton, and more preferably benzotriazole.
Further, the sulfonated copper phthalocyanine preferably has 0.5 to 3 sulfonic acid groups in the molecule.
The present invention is also a black matrix resist composition obtained from the above black matrix pigment dispersion composition.
The present invention is also a black matrix formed from the above-mentioned resist composition for black matrix.

According to the present invention, it is possible to provide a pigment dispersion composition for a black matrix that can maintain a surface resistance value even after post-baking and can form a black matrix having excellent heat flow characteristics. ..

<Pigment dispersion composition for black matrix>
A pigment dispersion composition for a black matrix containing the black colorant of the present invention, a sulfonated copper phthalocyanine, and an amine compound, wherein the amine compound is an imidazole-based compound and / or a triazole-based compound.

(Black colorant)
The pigment dispersion composition for a black matrix of the present invention contains a black colorant.
The black colorant preferably contains carbon black, and more preferably the carbon black is acidic carbon black.
As the carbon black, an average primary particle diameter of 20 to 60 nm is preferable, and a neutral carbon black having an average primary particle diameter of 20 to 60 nm and / or an acidic carbon black having an average primary particle diameter of 20 to 60 nm are more preferable.
If the primary particle size of the black colorant is smaller than 20 nm or larger than 60 nm, it may not have sufficient light-shielding properties or may be inferior in storage stability.
The average primary particle diameter is the value of the arithmetic mean diameter observed by electron microscopy.

The black colorant preferably contains only acidic carbon black from the viewpoint of preferably imparting a surface resistance value.
On the other hand, when the neutral carbon black and the acidic carbon black are used in combination, it is preferable that the neutral carbon black is 85% by mass or less with respect to the total mass of the neutral carbon black and the acidic carbon black. It is more preferable that the neutral carbon black is 75% by mass or less.
If the content of the neutral carbon black of the carbon black is more than 85% by mass, the sealing strength may decrease.

The above-mentioned acidic carbon black and neutral carbon black will be described.
Carbon black can be roughly classified into acidic carbon black and neutral carbon black depending on the surface structure. Acidic carbon black is a carbonaceous substance that has been originally or artificially oxidized, and exhibits acidity when mixed with distilled water and boiled. On the other hand, neutral carbon black is known to exhibit a neutral or higher pH when mixed and boiled with distilled water.

The neutral carbon black preferably has a pH in the range of 8.0 to 10.0, specifically, Printex 25 manufactured by Orion Engineered Carbons (average primary particle diameter 56 nm, pH 9.5). , Printex 35 (average primary particle diameter 31 nm, pH 9.5), Printex 65 (average primary particle diameter 21 nm, pH 9.5), MA # 20 manufactured by Mitsubishi Chemical Co., Ltd. (average primary particle diameter 40 nm, pH 8.0). , MA # 40 (average primary particle diameter 40 nm, pH 8.0), MA # 30 (average primary particle diameter 30 nm, pH 8.0) and the like.

The acidic carbon black preferably has a pH in the range of 2.0 to 4.0, specifically, Raven 1080 (average primary particle diameter 28 nm, pH 2.4) and Raven 1100 (average primary particle diameter) manufactured by Columbia Chemicals. 32 nm, pH 2.9), MA-8 (average primary particle diameter 24 nm, pH 3.0) manufactured by Mitsubishi Chemical Co., Ltd., MA-100 (average primary particle diameter 22 nm, pH 3.5), manufactured by Orion Engineered Carbons Co., Ltd. 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), NEROX305 (average primary particle diameter) Particle diameter of about 28 nm, pH of about 2.8) and the like can be mentioned.

The black colorant is preferably Special Black 250 or NEROX 305 from the viewpoint of preferably imparting pigment dispersibility and surface resistance value.

The pH is 25 ° C. using a glass electrode after adding 1 g of carbon black to 20 ml of distilled water (pH 7.0) from which carbon dioxide has been removed and mixing with a magnetic stirrer to prepare an aqueous suspension. It can be measured with (German Industrial Standard DIN ISO 787/9).

The content of the black colorant is preferably 3 to 70% by mass, more preferably 10 to 50% by mass, as a mass fraction of the pigment dispersion composition for black matrix of the present invention with respect to the total solid content.
If the content of the black colorant is less than 3% by mass, the light-shielding property when the black matrix is formed may be low, and if it exceeds 70% by mass, it may be difficult to disperse the pigment.

(Sulfonized copper phthalocyanine)
The pigment dispersion composition for black matrix of the present invention contains a sulfonated copper phthalocyanine.
In the sulfonated copper phthalocyanine, the basic skeleton is adsorbed on the pigment surface in the steps of atomizing and dispersing the black colorant, and the sulfonic acid group enhances the affinity with the organic solvent and the pigment dispersant. It has the effect of improving the fineness of the black colorant during dispersion and the dispersion stability after dispersion.

The copper phthalocyanine in the sulfonated copper phthalocyanine is not particularly limited as long as it has a structure having a copper phthalocyanine skeleton, and for example, the copper phthalocyanine skeleton may have a known substituent such as an alkyl group or a halogen atom. However, from the viewpoint of easiness of introducing a sulfonic acid group, a structure having no substituent is preferable.

The copper phthalocyanine sulfonate preferably has 0.5 to 3 sulfonic acid groups in the molecule.
As described above, by having 0.5 to 3 sulfonic acid groups in the molecule, it is possible to obtain a composition for a black matrix capable of obtaining a coating film having an excellent surface resistance value.
The sulfonated copper phthalocyanine preferably has 0.5 to 1.5 sulfonic acid groups in the molecule, and more preferably 0.7 to 1.5.
The number of sulfonic acid groups contained in the molecule can be calculated based on the ratio of sulfur atoms to copper atoms by elemental analysis.

As the sulfonated copper phthalocyanine, a commercially available product may be used, and examples thereof include a desodium product of Solsperth 12000 (manufactured by Japan Lubrizol Co., Ltd.) and VALUESTAB BLUE 1605 (manufactured by Orient Chemical Industry Co., Ltd.).

The content of the sulfonated copper phthalocyanine is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the black colorant.

(Amine compound)
The pigment dispersion composition for a black matrix of the present invention contains an amine compound.
The amine compound is an imidazole-based compound and / or a triazole-based compound.
Since such an amine compound has low basicity, it is a salt formed by neutralization with a sulfonic acid or a carboxylic acid (for example, the above-mentioned sulfonated acid carbon black or copper phthalocyanine, or the alkali-soluble resin or binder resin described later). It is considered that the surface resistance value is excellent because the ionicity of the black matrix is low and therefore the formed black matrix is difficult to energize. Further, since the amine compound has low basicity, the ionicity of the salt formed by neutralization with sulfonic acid or carboxylic acid is low, and therefore the ionic cross-linking in the resist coating film is weak, so that the resist coating film has a low ionicity. It is considered to be flexible and have excellent heat flowability.
However, the present invention does not have to be construed as being limited to the above mechanism.

Examples of the imidazole-based compound include imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2- (1-naphthyl) imidazole, 2- (1-naphthyl) -4-methylimidazole, 2- (2- (2-). Naftyl) imidazole, 2- (2-naphthyl) -4-methylimidazole, 4-phenylimidazole, 2-methyl-4-phenylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propyl imidazole, 2-isopropyl imidazole , 2-Butyl imidazole, 2-tert-butyl imidazole, 2-pentyl imidazole, 2-hexyl imidazole, 2-heptyl imidazole, 2- (1-ethylpentyl) imidazole, 2-octyl imidazole, 2-nonyl imidazole, 2- Decylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2-tetradecylimidazole, 2-pentadecylimidazole, 2-hexadecylimidazole, 2-heptadecylimidazole, 2- (1-heptyldecyl) ) Imidazole, 2-ethyl-4-methylimidazole, 2-undecyl-4-methylimidazole, 2-heptadecyl-4-methylimidazole, 4-methylimidazole, 4-isopropylimidazole, 4-octylimidazole, 2,4,5 Examples thereof include -trimethylimidazole, 4,5-dimethyl-2-octylimidazole, 2-undecyl-4-methyl-5-bromoimidazole, 4,5-dichloro-2-ethylimidazole and the like.
Among them, an alkyl imidazole is preferable from the viewpoint of preferably imparting a surface resistance value and a heat flow characteristic, and the alkyl imidazole is more preferably having an alkyl group having 8 to 16 carbon atoms, and the alkyl imidazole is more preferable. Is a monoalkylimidazole, more preferably having a linear alkyl group having 8 to 16 carbon atoms, and particularly preferably 2-undecylimidazole.

Examples of the triazole-based compound include 1,2,3-triazole, 1,2,4-triazole, 3-mercaptotriazole, 3-amino-5-mercaptotriazole, benzotriazole, and 2- (2'-hydroxy-5'. -Methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3,5-di-t-butyl-phenyl) benzotriazole, 2- [2'-hydroxy-3,5-bis (α, α-dimethyl) Benzyl) phenyl] benzotriazole, 2- (2'-hydroxy-3,5-di-t-amylphenyl] benzotriazole, 2- (2'-hydroxy-3,5-di-isoamyl-phenyl) benzotriazole, 2- [2'-Hydroxy-3,5-bis- (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole and the like can be mentioned. Will be.

Among them, from the viewpoint of preferably imparting a surface resistance value and heat flow characteristics, it is preferable to have a benzotriazole skeleton, and benzotriazole is more preferable.

The above amine compounds can be used alone or in admixture of two or more.

The content of the amine compound is 0.1 to 1.5 parts by mass, preferably 0.3 to 1.4 parts by mass, and 0.5 to 1 part by mass with respect to 100 parts by mass of the black colorant. It is more preferably 3 parts by mass.
When the content of the amine compound is less than 0.1 part by mass with respect to 100 parts by mass of the black colorant, or when it exceeds 1.5 parts by mass, the surface resistance value and the heat flow characteristics are lowered. ..

(Organic solvent)
The pigment dispersion composition for black matrix of the present invention preferably contains an organic solvent.
As the organic solvent, an organic solvent conventionally used in the field of liquid crystal black matrix resist can be preferably used.

Specific examples of the organic solvent include an ester-based organic solvent, an ether-based organic solvent, an ether ester-based organic solvent, and a ketone-based organic solvent having a boiling point of 100 to 250 ° C. at normal pressure (1.013 × 10 ² kPa). , Aromatic hydrocarbon-based organic solvent, nitrogen-containing organic solvent, etc.
When a large amount of the organic solvent having a boiling point of more than 250 ° C. is contained, the coating film formed by applying the black matrix resist composition obtained from the black matrix pigment dispersion composition of the present invention is prebaked. In addition, the organic solvent may not evaporate sufficiently and may remain in the dry coating film, reducing the heat resistance of the dry coating film.
Further, if a large amount of the organic solvent having a boiling point of less than 100 ° C. is contained, it becomes difficult to apply the organic solvent evenly and uniformly, and a coating film having excellent surface smoothness may not be obtained.

Specific examples of the organic 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 mono. Ether-based organic solvents such as ethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Ethylene ester organic solvents such as propylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2 -Ethyl hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Ester-based organic solvents such as ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl acrylate; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol and butanol; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethyl Examples thereof include nitrogen-containing organic solvents such as acetamide. These can be used alone or in admixture of two or more.

Among the above organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate are used in terms of solubility, dispersibility, coatability, etc. , Cyclohexanone, 2-Heptanone, Ethyl 2-hydroxypropionate, 3-Methyl-3-methoxybutylpropionate, Ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, n-amyl acrylate and the like are preferable, and propylene glycol. More preferably, it is monomethyl ether or propylene glycol monomethyl ether acetate.

(Pigment dispersant)
The pigment dispersion composition for black matrix of the present invention preferably contains a pigment dispersant.
The pigment dispersant includes a basic group-containing pigment dispersant, an anionic surfactant, a basic group-containing polyester pigment dispersant, a basic group-containing acrylic pigment dispersant, and a basic group-containing urethane pigment. Dispersants, basic group-containing carbodiimide pigment dispersants, acidic group-containing polymer pigment dispersants and the like can be used.
These basic group-containing pigment dispersants may be used alone or in combination of two or more. Of these, a basic group-containing polymer pigment dispersant is preferable because good pigment dispersibility can be obtained.

Specific examples of the basic group-containing polymer pigment dispersant include
(1) From polyesters, polyamides and polyesteramides having an amino group and / or an imino group of a polyamine compound (for example, poly (lower alkyleneamine) such as polyallylamine, polyvinylamine, polyethylenepolyimine) and a free carboxyl group. (Japanese Patent Laid-Open No. 2001-59906), a reaction product with at least one selected from the above group.
(2) A reaction product of a low molecular weight amino compound such as poly (lower) alkyleneimine or methyliminobispropylamine and a polyester having a free carboxyl group (Japanese Patent Laid-Open No. 54-37082, Japanese Patent Laid-Open No. 01-31177). Issue),
(3) Alcohols such as methoxypolyisocyanate glycol and polyesters having one hydroxyl group such as caprolactone polyester in the isocyanate group of the polyisocyanate compound, compounds having 2 to 3 isocyanate group reactive functional groups, and isocyanate group reactivity. A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a functional group and a tertiary amino group (Japanese Patent Laid-Open No. 02-612).
(4) A compound obtained by reacting a polyisocyanate compound with a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group.
(5) A reaction product obtained by adding a polyether chain to a small molecule amino compound,
(6) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group (Japanese Patent Laid-Open No. 04-210220).
(7) A reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group (Japanese Patent Laid-Open No. 09-87537).
(8) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound (Japanese Patent Laid-Open No. 09-194585).
(9) Selected from methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, and benzyl acrylate, or acrylic acid esters. At least one of the basic group-containing polymerization monomers such as acrylamide, methacrylicamide, N-methylolamide, vinyl imidazole, vinylpyridine, a monomer having an amino group and a polycaprolactone skeleton, and a styrene, a styrene derivative, Copolymer with at least one of other polymerizable monomers (Japanese Patent Laid-Open No. 01-164429),
(10) Basic group-containing carbodiimide-based pigment dispersant (International Publication WO04 / 00950),
(11) A block copolymer composed of a block having a basic group such as a tertiary amino group and a quaternary ammonium salt machine and a block having no functional group (see the description in JP-A-2005-55514).
(12) A pigment dispersant obtained by carrying out a Michael addition reaction of a polycarbonate compound with polyallylamine (Japanese Patent Laid-Open No. 09-194585).
(13) A carbodiimide-based compound having at least one polybutadiene chain and at least one basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-257243).
(14) A carbodiimide-based compound having at least one side chain having an amide group in the molecule and at least one basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-176657).
(15) A polyurethane compound having an ethylene oxide chain and a structural unit having a propylene oxide chain and having an amino group quaternized by a quaternizing agent (Japanese Patent Laid-Open No. 2009-175613).
(16) Obtained by reacting the isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with the active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton. Carbazole ring with respect to the total of the isocyanate group derived from the isocyanate compound having an isocyanurate ring in the molecule of the compound, and the urethane bond and urea bond generated by the reaction of the isocyanate group and the active hydrogen group. And a compound in which the number of azobenzene skeletons is 15 to 85% (Japanese Patent Application No. 2009-220836).
(17) Examples thereof include a graft copolymer in which a polyether or a polyester side chain is introduced into an acrylate polymer having an amino group.

Among the above basic group-containing polymer pigment dispersants, basic group-containing urethane polymer pigment dispersants, basic group-containing polyester polymer pigment dispersants, and basic group-containing acrylic polymer pigment dispersants are more suitable. Amino group-containing urethane polymer pigment dispersant, amino group-containing polyester polymer pigment dispersant, and amino group-containing acrylic polymer pigment dispersant are more preferable. Among the above-mentioned basic group-containing polymer pigment dispersants, a basic group (amino group) -containing polymer pigment dispersant having at least one selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains is particularly preferable. preferable.

The content of the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the black colorant.

(Binder resin)
The pigment dispersion composition for black matrix of the present invention preferably contains a binder resin.

Examples of the binder resin include thermosetting resins, thermoplastic resins, photopolymerizable compounds, and alkali-soluble resins. These can be used alone or in combination of two or more.

Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. Polyurethane resin, phenol resin, polyester resin, acrylic resin, alkid resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, celluloses, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin And so on.

Examples of the photopolymerizable compound include a monomer having one or more photopolymerizable unsaturated bonds in the molecule, an oligomer having a photopolymerizable unsaturated bond, and the like.

Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, or acrylates and benzyl methacrylates. Aralkyl methacrylate or acrylate such as benzyl acrylate, alkoxyalkyl methacrylate or acrylate such as butoxyethyl methacrylate and butoxyethyl acrylate, aminoalkyl methacrylate or acrylate such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethyl acrylate, diethylene glycol. Methacrylate or acrylic acid ester of polyalkylene glycol monoalkyl ether such as monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and methacrylic acid ester of polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether. Alternatively, acrylic acid ester, isobonyl methacrylate or acrylate, glycerol methacrylate or acrylate, 2-hydroxyethyl methacrylate or acrylate and the like can be used.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, and glycerol dimethacrylate. , Neopentyl glycol dimethacrylate, Polyethylene glycol dimethacrylate, Polypropylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, Trimethylol propanetrimethacrylate, Pentaallyslitol Trimethacrylate, Pentaerythritol tetramethacrylate, Dipentaerythritol tetramethacrylate, Dipentaerythritol Hexamethacrylate, dipentaerythritol pentamethacrylate, epoxymethacrylate, 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, Trimethylol Propane Triacrylate, Penta Alice Ritol Triacrylate, Pentaerythritol Tetraacrylate, Dipentaerythritol Tetraacrylate, Dipentaerythritol Hexaacrylate, Dipentaerythritol Pentaacrylate , Epoxy acrylate and the like can be used.

As the oligomer having a photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the above-mentioned monomer can be used.
The binder resin can be used alone or in combination of two or more.

The binder resin is preferably an epoxy acrylate resin from the viewpoint of heat resistance and developability.

The alkali-soluble resin will be described later.

The content of the binder resin is preferably 3 to 50% by mass as a mass fraction with respect to the total solid content of the pigment dispersion composition for black matrix of the present invention.

(Method for Producing Pigment Dispersion Composition for Black Matrix)
The method for producing a pigment dispersion composition for a black matrix of the present invention can be obtained by adding the above-mentioned various components, mixing and kneading.
The method for kneading the meat is not particularly limited, and for example, a bead mill, a ready mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a nanomizer, etc. It may be used and kneaded by a known method.

<Resist composition for black matrix>
The present invention is also a resist composition for a black matrix obtained from the pigment dispersion composition for a black matrix of the present invention.

(Pigment dispersion composition for black matrix)
The resist composition for black matrix of the present invention contains the pigment dispersion composition for black matrix of the present invention described above.
The content of the pigment dispersion composition for black matrix is preferably 30 to 80% by mass, preferably 40 to 75% by mass, based on the total mass of the resist composition for black matrix of the present invention. More preferred.

(Photopolymerization initiator)
The resist composition for black matrix of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can generate radicals and cations by being irradiated with active energy rays such as ultraviolet rays and electron beams, and is not particularly limited, for example, 1- [9-ethyl. -6- (2-Methylbenzoyl) -9H-Carbazole-3-yl] -1- (O-Acetyloxym) Etanone, Benzophenone, N, N'-Tetraethyl-4,4'-Diaminobenzophenone, 4-methoxy- 4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenylketone, t -Butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chlor-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, Examples include benzophenone-based, thioxanthone-based, anthraquinone-based, triazine-based photopolymerization initiators such as 2-phenylanthraquinone and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one. Be done.
The photopolymerization initiator may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 1 to 20% by mass as a mass fraction with respect to the total solid content of the resist composition for black matrix of the present invention.

(Photopolymerizable compound)
The resist composition for a black matrix of the present invention preferably contains a photopolymerizable compound.
As the photopolymerizable compound, those described in the above-mentioned pigment dispersion composition for black matrix can be appropriately selected and used.

The content of the photopolymerizable compound is preferably 0.1 to 50% by mass as a mass fraction with respect to the total solid content of the resist composition for black matrix of the present invention.

(Alkali-soluble resin)
The resist composition for black matrix of the present invention preferably contains an alkali-soluble resin.
The alkali-soluble resin acts as a binder for the black colorant and is soluble in a developer used in the developing process when producing a black matrix, particularly an alkali developing solution. Is preferable.

The alkali-soluble resin may be a block copolymer. By adopting a block copolymer, the pigment dispersibility is improved as compared with other copolymers, and solubility in PGMEA or an alkaline developer can be imparted.
Among the block copolymers, a block copolymer having a block made of an ethylenically unsaturated monomer having one or more carboxyl groups and a block made of another copolymerizable ethylenically unsaturated monomer. Coalescence is preferred.

The block copolymer is not particularly limited, and conventionally used block copolymers can be used. Among them, specifically, styrene and 2-hydroxyethyl which can be copolymerized with an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid and methacrylic acid and an ethylenically unsaturated monomer having a carboxyl group. Acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethylmethacrylate macromonomer, carboepoxy Examples thereof include a copolymer with at least one ethylenically unsaturated monomer selected from the group of monomers such as diacrylate and oligomers.
However, it is desirable not to use N-vinylpyrrolidone and sulfur element-containing monomers.
As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be adopted.
A part of the block portion of the block copolymer may be composed of a random copolymer.

As the alkali-soluble resin, an alkali-soluble cardo resin can also be adopted.
Examples of the alkali-soluble cardo resin include an epoxy (meth) acrylate acid adduct having a fluorene skeleton, which is an adduct of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. Can be mentioned.
Further, the present alkali-soluble resin may have a photopolymerizable functional group.

The acid value of the alkali-soluble resin is preferably 5 to 300 mgKOH / g, more preferably 5 to 250 mgKOH / g, still more preferably 10 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g from the viewpoint of development characteristics.
In the present specification, the acid value is a theoretical acid value, which is a value calculated mathematically based on the ethylenically unsaturated monomer having a carboxyl group and its content.

The weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and 5,000 to 30,000 from the viewpoint of development characteristics and solubility in an organic solvent. Is even more preferable.
In the present invention, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight obtained based on GPC.
In the present specification, Water2690 (manufactured by Waters) is used as the device for measuring the weight average molecular weight, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) is used as the column.

The content of the alkali-soluble resin is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the black colorant.
In this case, if the content of the alkali-soluble resin is less than 1 part by mass, the development characteristics may deteriorate, and if the content of the alkali-soluble resin exceeds 200 parts by mass, the concentration of the black colorant is relative. Therefore, it may be difficult to achieve the desired color density as a thin film.

It is preferable that the alkali-soluble resin does not contain any primary, secondary, or tertiary amino group, and further does not contain a quaternary ammonium group. Furthermore, it is more preferable that it does not have a basic group.
An alkali-soluble resin having a structure other than the block copolymer may be blended as long as the effect of the present invention is not impaired.

(Organic solvent)
As the organic solvent, the organic solvent described in the pigment dispersion composition for black matrix described above can be appropriately selected and used.

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

(Other additives)
In the resist composition for black matrix of the present invention, various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be appropriately used, if necessary.

(Manufacturing method of resist composition for black matrix)
As a method for producing a resist composition for a black matrix of the present invention, for example, the pigment dispersion composition for a black matrix of the present invention is prepared, and then the remaining materials are added and stirred and mixed using a stirrer or the like. Can be made.
The method of stirring and mixing is not particularly limited, and known methods such as an ultrasonic disperser, a high-pressure emulsifier, a bead mill, a three-roll roll, a sand mill, and a kneader can be used.
Further, after stirring and mixing, filtration may be performed with a filter.
When preparing the resist composition for black matrix of the present invention, the black colorant, the epoxy resin, the oxazine compound and the like described in the pigment dispersion composition for black matrix of the present invention are added as necessary. You may.

<Black Matrix>
The black matrix of the present invention is formed from the resist composition for black matrix of the present invention.

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

As a method for applying, drying, exposing and developing the resist composition for black matrix of the present invention, a known method can be appropriately selected.
Further, as the transparent substrate, a known transparent substrate such as a glass substrate or a plastic substrate can be appropriately selected and used.

The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, still more preferably 1 to 4 μm.
By setting the thickness within the range, a predetermined pattern can be suitably developed, and a predetermined optical density can be suitably imparted.

The black matrix of the present invention is prepared by applying the resist composition for black matrix on a glass substrate (EAGLE XG) with a spin coater so as to have a film thickness of 1 μm, prebaking at 100 ° C. for 3 minutes, and then exposing with a high-pressure mercury lamp. (UV integrated light amount 80 mJ / cm ² ), and post-baking at 230 ° C. for 60 minutes to produce a black resist pattern formed only of solid parts, the surface resistance value was 1.0 × ¹⁰⁸ Ω / □ or more is preferable, 5.0 × 10 ⁸ Ω / □ or more is more preferable, and 1.0 × 10 ⁹ Ω / □ or more is further preferable.
When the surface resistance value is 1.0 × ¹⁰⁸ Ω / □ or more, short circuit and current leakage can be suitably prevented.
The surface resistance value can be measured with a main body: micro ammeter R8340 and an option: shield box R12702A (both manufactured by Advance Co., Ltd.).

In the black matrix of the present invention, the heat flow characteristic [ΔCD (%)] is preferably 2.0% or more, more preferably 3.0% or more, and preferably 4.0% or more. More preferred.
When the heat flow characteristic [ΔCD (%)] is 2.0% or more, it is possible to suitably prevent the black matrix pattern from being missing.

The heat flow characteristic [ΔCD (%)] can be calculated by the following formula.
The resist composition for black matrix is applied onto a glass substrate (EAGLE XG) with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated light intensity 80 mJ /). cm ² ) and expose with a high-pressure mercury lamp (UV integrated light intensity 80 mJ / cm ² ) using a photomask having a line pattern of 20 μm. Next, development is performed at a shower developing pressure of 0.5 kgf / cm ² in a 0.05% potassium hydroxide aqueous solution at 23 ° C., and spray water washing is performed at 3.0 kgf / cm ² pressure.
The 20 μm pattern line width on the obtained glass substrate is measured with a digital microscope, and the measured value is set to CD1 (μm).
Then, the glass substrate is post-baked at 230 ° C. for 30 minutes, and then the 20 μm pattern line width on the glass substrate is measured with a digital microscope to obtain a measured value of CD2 (μm).
The heat flow characteristic [ΔCD (%)] can be calculated by the following formula.
ΔCD (%) = {(CD2 / CD1) -1} × 100

Since the pigment dispersion composition for black matrix, the resist composition for black matrix, and the black matrix of the present invention have the above-mentioned characteristics, they can be suitably used as a black matrix for an image display device, a touch panel, or the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto as long as it does not deviate from the gist and scope of application. Unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively, in this embodiment.

The various materials used in the following examples and comparative examples are as follows.
<Black colorant>
Carbon black (trade name "NEROX305", average primary particle diameter of about 28 nm, pH of about 2.8, manufactured by Orion Engineered Carbons)
<Pigment dispersant>
DISPERBYK-167 (solid content 52% by mass, manufactured by Big Chemie)
<Amine compound>
2-Undecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
Bis (2-ethylhexyl) amine (manufactured by Tokyo Chemical Industry Co., Ltd.)
4- (3-Phenylpropyl) pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Binder resin>
ZCR-1569H (epoxy acrylate resin, solid content 70% by mass, manufactured by Nippon Kayaku Co., Ltd.)
<Organic solvent>
PGMEA (Propylene Glycol Monomethyl Ether Acetate)
<Photopolymerization initiator>
OXE02 (Product name "Irgacure OXE02", 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) etanone, manufactured by BASF)
<Photopolymerizable compound>
DPHA (Dipentaerythritol Hexaacrylate)
<Alkali-soluble resin>
WR-301 (Product name "WR-301", cardo resin, acid value 100 mgKOH / g, solid content 45% by mass, manufactured by ADEKA Corporation)

<Preparation of composition for dispersion>
(Composition for dispersion 1)
Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol Co., Ltd.) and 2-undecylimidazole were mixed at a mass ratio of 25:11. The dispersion composition 1 was obtained.
(Composition for dispersion 2)
Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol Co., Ltd.) and benzotriazole are mixed at a mass ratio of 25: 6 to form a dispersion. I got the thing 2.
(Composition for dispersion 3)
Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol K.K.) and bis (2-ethylhexyl) amine are mixed at a mass ratio of 25:12. The dispersion composition 3 was obtained.
(Composition for dispersion 4)
Solsperse 12000 (sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol K.K.) and 4- (3-phenylpropyl) pyridine in a mass ratio of 5: 2. Mixing gave the dispersion composition 4.

<Material for dispersion>
Solsperse 12000 (Sulfonized copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol)
Solsperse 5000 (quaternary ammonium salt of sulfonated copper phthalocyanine (containing about 0.9 sulfonic acid groups in one molecule), manufactured by Japan Lubrizol)

<Preparation of pigment dispersion composition for black matrix>
Each material was mixed so as to have the composition shown in Table 1 and kneaded with a bead mill day and night to prepare a pigment dispersion composition for black matrix.

<Preparation of resist composition for black matrix>
Using a high-speed stirrer, the pigment dispersion composition for black matrix and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator and organic solvent) were uniformly mixed so as to have the composition shown in Table 2. Then, the mixture was filtered through a filter having a pore size of 3 μm to obtain black matrix resist compositions of Examples and Comparative Examples.

<Evaluation test>
(Surface resistance value)
The pigment-dispersed resist composition for each black matrix of Examples and Comparative Examples was applied onto a glass substrate (EAGLE XG) with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then a high-pressure mercury lamp. (UV integrated light intensity 80 mJ / cm ² ) was further exposed and post-baked at 230 ° C. for 60 minutes to prepare a black resist pattern (black matrix) formed only of the solid portion.
The surface resistance value of each black resist pattern produced was measured with a main body: micro ammeter R8340 and an option: shield box R12702A (both manufactured by Advance). The results are shown in Table 2.

(Heat flow characteristics)
A resist composition for each black matrix is applied on a glass substrate (EAGLE XG) with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated light intensity 80 mJ /). cm ² ) was exposed with a high-pressure mercury lamp (UV integrated light intensity 80 mJ / cm ² ) using a photomask having a line pattern of 20 μm. Then, development was carried out at a shower developing pressure of 0.5 kgf / cm ² in a 0.05% potassium hydroxide aqueous solution at 23 ° C., and spray water washing was carried out at 3.0 kgf / cm ² pressure.
The 20 μm pattern line width on the obtained glass substrate was measured with a digital microscope, and the measured value was set to CD1 (μm).
Then, the glass substrate was post-baked at 230 ° C. for 30 minutes, and then the 20 μm pattern line width on the glass substrate was measured with a digital microscope to obtain a measured value of CD2 (μm).
The heat flow characteristic [ΔCD (%)] was calculated by the following formula.
ΔCD (%) = {(CD2 / CD1) -1} × 100

In the examples using the pigment dispersion composition for black matrix containing a black colorant and a sulfonated copper phthalocyanine and a predetermined amount of a specific amine compound, the surface resistance value can be maintained even after post-baking. Moreover, it was confirmed that a black matrix having excellent heat flow characteristics can be formed.

According to the present invention, it is possible to provide a pigment dispersion composition for a black matrix that can maintain a surface resistance value even after post-baking and can form a black matrix having excellent heat flow characteristics. ..

Claims (12)

Contains a black colorant, a sulfonated copper phthalocyanine, and an amine compound.
The amine compound is an imidazole-based compound and / or a triazole-based compound.
The pigment dispersion composition for a black matrix has a content of the amine compound of 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the black colorant. The pigment dispersion composition for a black matrix according to claim 1, wherein the black colorant is carbon black. The pigment dispersion composition for a black matrix according to claim 2, wherein the black colorant is acidic carbon black. The pigment dispersion composition for a black matrix according to any one of claims 1 to 3, wherein the imidazole compound is an alkyl imidazole. The pigment dispersion composition for a black matrix according to claim 4, wherein the alkylimidazole has an alkyl group having 8 to 16 carbon atoms. The pigment dispersion composition for a black matrix according to claim 5, wherein the alkyl imidazole is a monoalkyl imidazole and has a linear alkyl group having 8 to 16 carbon atoms. The pigment dispersion composition for a black matrix according to claim 6, wherein the alkyl imidazole is 2-undecyl imidazole. The pigment dispersion composition for a black matrix according to any one of claims 1 to 7, wherein the triazole-based compound has a benzotriazole skeleton. The pigment dispersion composition for a black matrix according to claim 8, wherein the triazole-based compound is a benzotriazole. The pigment dispersion composition for a black matrix according to any one of claims 1 to 9, wherein the sulfonated copper phthalocyanine has 0.5 to 3 sulfonic acid groups in the molecule. A black matrix resist composition obtained from the black matrix pigment dispersion composition according to any one of claims 1 to 10. A black matrix formed from the resist composition for black matrix according to claim 11.