TWI663221B - Pigment dispersion for black matrix and pigment dispersion photoresist composition containing black matrix - Google Patents

Abstract

The present invention provides a pigment dispersion for a black matrix having high light shielding properties and high insulation properties, and a pigment dispersion photoresist composition for a black matrix containing the pigment dispersion.

The present invention is a pigment dispersion for a black matrix, which contains acidic carbon black, a pigment dispersant, a polyfunctional epoxy compound, and a solvent, and is characterized in that the polyfunctional epoxy compound is 100 parts by mass of acidic carbon black. It contains 0.1 to 50 parts by mass.

Description

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

The present invention relates to a pigment dispersion for a black matrix that maintains high light-shielding properties and has high insulation properties, and a pigment dispersion photoresist composition for a black matrix containing the pigment dispersion.

In recent years, the use of pigment dispersions for black matrices has been used in a variety of ways. For example, in a flat panel display such as a liquid crystal or a plasma, a light-shielding film (black Matrix), and a liquid crystal display using a TFT is used to provide a light-shielding film (black matrix) on the light side other than the TFT. In addition, liquid crystal displays are mainly used to prevent the leakage of light from the backlight onto the screen and improve the display characteristics (contrast and color purity). Plasma displays are mainly used to prevent halo caused by the turbidity of various colors of light. Enter the screen and improve display characteristics (contrast and color purity).

For example, a color filter used to convert the white light of the backlight of a liquid crystal display into colored light is generally manufactured by the following method: on the surface of a transparent substrate such as glass or a plastic sheet with a black matrix formed in a striped or mosaic pattern Patterns such as shapes sequentially form pixels of different tones of red, green, and blue.

Moreover, in a touch panel combining an image display device and a position input device, Similarly, a color filter formed with a black matrix is used as a light-shielding film. Conventionally, it has been generally formed on the side opposite to the sensor substrate through a cover glass. However, as the requirements for the weight reduction of the touch panel become higher, the following technologies have been developed in order to achieve lighter weight: a technology of simultaneously forming a light shielding film and a touch sensor on the same side of the cover glass. In this case, after forming the black matrix on the cover glass, it is necessary to form electrodes for the sensor, etc. Therefore, firstly, if the black matrix crosses a plurality of electrodes and contacts with each other, high insulation will not cause malfunction. In addition, high adhesion or chemical resistance is also required.

Therefore, in order to obtain a black matrix having high insulation properties, techniques have been disclosed in which carbon black is used as a light-shielding pigment, and an epoxy acrylate compound containing an acid group is used as a photocurable material (for example, refer to Patent Documents). 1); using an insulating carbon black obtained by coating a carbon black with a polyfunctional epoxy resin (in the examples, only a bifunctional epoxy resin is exemplified as a polyfunctional epoxy resin) (for example, refer to Patent Document 2) .

High insulation properties can be obtained by these disclosed technologies, but in recent years, black matrices with high light shielding properties and high insulation properties have been required for thin films, and the content ratio of carbon black, which is a light shielding material, needs to be increased. However, carbon black has electrical conductivity, so if the content ratio is increased, it becomes the main cause of the decrease in insulation properties. These disclosed technologies cannot meet the requirements for achieving high light shielding properties and high insulation properties at the same time.

Patent Document 1: Japanese Patent Application Laid-Open No. 08-278629

Patent Document 2: Japanese Patent Application Laid-Open No. 09-124969

Therefore, an object of the present invention is to provide a pigment dispersion for a black matrix having high light shielding properties and high insulation properties, and a pigment dispersion photoresist composition for a black matrix containing the pigment dispersion.

The inventors have recognized that if the coating ratio of the carbon black in the coating film is increased in order to make the coating film of the black matrix photoresist composition a thinner film and have a high light-shielding property, the carbon black is The conductivity decreases the insulation of the coating film. It was found that after forming a coating film of a photoresist composition for a black matrix by photo-hardening, if the post-hardening treatment is performed at a high temperature, the decrease in insulation will become obvious. .

The present inventors speculated that this phenomenon suggests the possibility of agglomeration of carbon black due to temporary softening of the light-cured coating film due to post-curing heating, and the following materials were studied: formation of a resin with high heat resistance on the surface of carbon black Even if the film is agglomerated, the decrease in insulation properties is suppressed, and further, it does not adversely affect the development characteristics and the like when forming the black matrix.

As a result, the present inventors have found and completed the present invention that, if acid carbon black and a polyfunctional epoxy compound are used, even if the content ratio of acid carbon black is increased, high insulation properties can be maintained.

That is, the present invention relates to a pigment dispersion for a black matrix, which contains acid carbon black, a pigment dispersant, a polyfunctional epoxy compound, and a solvent, and the polyfunctional epoxy compound is based on 100 parts by mass of the acidic carbon. It is black and contains 0.1 to 50 parts by mass.

In the present invention, the polyfunctional epoxy compound preferably has a structure selected from the group consisting of a diphenylmethane skeleton, a dinaphthylmethane skeleton, An epoxy compound of at least one of a skeleton and a biphenyl skeleton.

The present invention is also a pigment-dispersed photoresist composition for a black matrix, which contains the pigment dispersion for a black matrix, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

In the present invention, a polyfunctional epoxy compound having 4 or more functions is preferred.

Hereinafter, the pigment dispersion for a black matrix of the present invention and the pigment-dispersed photoresist composition for a black matrix containing the pigment dispersion will be described in detail.

The mechanism by which the pigment dispersion for black matrices of the present invention has high insulation properties is not clear, but it is estimated as follows.

It is considered that in the pigment dispersion for a black matrix of the present invention, the acidic carbon black and the polyfunctional epoxy compound are in a state where the substituents on the surface of the acidic carbon black interact with the substituents on the polyfunctional epoxy compound. A polyfunctional epoxy compound is adsorbed on the surface of the acidic carbon black. Therefore, by making the polyfunctional epoxy compound have multiple junction sites, the probability of interaction with functional groups on the surface of carbon black can be increased.

In addition, when coating the photoresist composition for a black matrix, the state of adsorption by interacting the epoxy group of the polyfunctional epoxy compound with the functional group on the surface of the acidic carbon black can be fully considered: light curing It reacts with the heat during and after hardening to form an epoxy resin coating of acid carbon black.

In this way, even if the acidic carbon blacks are in contact with each other due to agglomeration, the surfaces of the conductive carbon blacks will not directly contact each other, and will be in contact with the non-conductive multifunctional epoxy compound coating film. Furthermore, if the polyfunctional epoxy compound has a skeleton with a polycyclic structure, the maintenance of the film of the acidic carbon black is excellent at high temperatures, so it is presumed that high insulation can be maintained in combination with a large volume.

(Acid Carbon Black)

The pigment dispersion for a black matrix of the present invention contains acid carbon black.

As the acidic carbon black, an acidic carbon black that has been used for forming a black matrix can be used.

Specific examples of the acidic carbon black include MA7, MA8, MA11, MA14, # 1000, # 2350, etc. manufactured by Mitsubishi Chemical Corporation; Special Black 350, Special Black 250, Special Black 550, etc. manufactured by Degussa ; MOGUL L, REGAL 400R, etc., manufactured by Cabot; RAVEN 1200, RAVEN 1250, RAVEN 1255, RAVEN 1190U, RAVEN 1170, RAVEN 1035, RAVEN 1080U, RAVEN 1060U, RAVEN 1100U, etc., manufactured by Columbian Carbon.

Among the above acidic carbon blacks, those having a pH of 5 or less and having acidic groups such as a carboxyl group are preferred. The particle diameter is preferably 20 to 60 nm. If it is such an acidic carbon black, it can interact well with the polyfunctional epoxy compound mentioned below, and can provide high insulation to the pigment dispersion for black matrices of this invention.

Examples of the acidic carbon black satisfying the above characteristics include Special Black 250 and Special Black 350.

In addition, the said particle diameter means the average primary particle diameter measured or calculated by microscope observation.

The content of the acidic carbon black is preferably 3 to 70% by mass in the pigment dispersion for a black matrix of the present invention. If the content of the acidic carbon black is less than 3% by mass, the light-shielding property may be reduced. On the other hand, if the content of the above-mentioned acidic carbon black exceeds 70% by mass, it may be difficult to disperse the pigment.

A more preferable lower limit of the content of the acidic carbon black is 10% by mass contained in the pigment dispersion for the black matrix of the present invention, and a more preferable upper limit of the content of the acidic carbon black is contained in the pigment dispersion of the black matrix of the present invention. 50% by mass.

(Pigment Dispersant)

The pigment dispersion for a black matrix of the present invention contains a pigment dispersant.

As the pigment dispersant, a pigment dispersant containing a basic group, an anionic surfactant, a polyester pigment dispersant containing a basic group, an acrylic pigment dispersant containing a basic group, and a basic group may be used. Urethane-based pigment dispersants, basic carbodiimide-based pigment dispersants, and the like.

These basic group-containing pigment dispersants may be used alone or in combination of two or more kinds. Among these, in terms of obtaining good pigment dispersibility, a polymer pigment dispersant containing a basic group is preferred.

Specific examples of the polymer pigment dispersant containing a basic group include:

(1) An amine group and / or an imine group of a polyamine compound (for example, poly (lower alkyleneamine) such as polyallylamine, polyvinylamine, polyethylene polyimide, and the like, and The reaction product of at least one of the group consisting of polyester, polyamide, and polyesteramine (Japanese Patent Laid-Open No. 2001-59906);

(2) Reaction products of low-molecular-weight amine compounds such as poly (lower) alkyleneimines and methyliminobispropylamine with polyesters having free carboxyl groups (Japanese Patent Laid-Open No. 54-37082, Japanese Patent Laid-Open 01-311177);

(3) Alcohols such as methoxypolyethylene glycol or polyesters having one hydroxyl group, such as caprolactone polyesters, compounds having two to three isocyanate group reactive functional groups, and isocyanate group reactive functions A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound of a amine group and a tertiary amino group with an isocyanate group of a polyisocyanate compound (Japanese Patent Laid-Open No. 02-612);

(4) a compound obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amine group with a polymer of an acrylate having an alcoholic hydroxyl group;

(5) a reaction product obtained by adding a polyether chain to a low molecular amine compound;

(6) A reaction product obtained by reacting a compound having an amine group with a compound having an isocyanate group (Japanese Patent Laid-Open No. 04-210220);

(7) A reaction product obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having a secondary amine group with a polyepoxide compound (Japanese Patent Application Laid-Open No. 09-87537);

(8) A reaction product of a polycarbonate compound and a polyamine compound having a functional group capable of reacting with an amine group at a single terminal (Japanese Patent Application Laid-Open No. 09-194585);

(9) selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, At least one of methacrylate or acrylate, such as propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, etc., with acrylamide, methacrylamide, N-methylolamine, ethylene At least one of basic group-containing polymerized monomers such as imidazole, vinylpyridine, monomers having an amine group and a polycaprolactone skeleton, and among styrene, styrene derivatives, and other polymerizable monomers Copolymers of at least one kind (Japanese Patent Laid-Open No. 01-164429);

(10) a carbodiimide-based pigment dispersant containing a basic group (International Publication No. WO04 / 000950);

(11) A block copolymer composed of a block having a basic group such as a tertiary amine group and a tertiary ammonium salt group and a block having no functional group (refer to the description in Japanese Patent Application Laid-Open No. 2005-55814);

(12) A pigment dispersant obtained by subjecting a polycarbonate compound to polyallylamine to a Michael addition reaction (Japanese Patent Laid-Open No. 09-194585);

(13) A carbodiimide-based compound having at least one polybutadiene chain and a basic nitrogen group, respectively (Japanese Patent Laid-Open No. 2006-257243);

(14) each having at least one side chain having a sulfonylamine group and a basic nitrogen group in the molecule Carbodiimide-based compounds (Japanese Patent Laid-Open No. 2006-176657) and the like.

(15) Polyurethane-based compound having a constituent unit containing an ethylene oxide chain and a propylene oxide chain and an amine group quaternized by a quaternizing agent (Japanese Patent Laid-Open No. 2009-175613 );

(16) Obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with an active hydrogen group of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton. And the total of the amine ester bond and the urea bond generated by the reaction of the isocyanate group and the active hydrogen group with respect to the isocyanate group derived from the isocyanate compound having an isocyanurate ring in the molecule of the compound, The number of the carbazole ring and the azobenzene skeleton is 15 to 85% (Japanese Patent Application No. 2009-220836).

Among the above-mentioned basic group-containing polymer pigment dispersants, amine ester-based polymer pigment dispersants containing basic groups, polyester-based polymer pigment dispersants containing basic groups, and basic group-containing polymer pigment dispersants are more preferred. The acrylic polymer pigment dispersant is more preferably an amine ester polymer pigment dispersant containing an amine group, a polyester polymer pigment dispersant containing an amine group, and an acrylic polymer pigment dispersant containing an amine group. Among the above-mentioned basic group-containing amine ester-based polymer pigment dispersants, it is particularly preferred to have at least one basic group containing a basic group selected from the group consisting of a polyester chain, a polyether chain, and a polycarbonate chain. (Amine-based) amine ester polymer pigment dispersant.

The basic group-containing dispersant preferably contains 1 to 200 parts by mass based on 100 parts by mass of the acidic carbon black.

If the content of the basic group-containing dispersant is less than 1 part by mass, the stability of the pigment dispersion may be deteriorated. On the other hand, if the content of the basic group-containing dispersant exceeds 200 parts by mass, the light-shielding property or insulating property of the coating film may be deteriorated.

The basic group-containing dispersant is more preferably contained in an amount of 1 to 60 parts by mass based on 100 parts by mass of the acidic carbon black.

(Multifunctional epoxy compound)

The pigment dispersion for a black matrix of the present invention contains a polyfunctional epoxy compound.

The pigment dispersion for a black matrix of the present invention can impart high insulation properties by allowing the above-mentioned polyfunctional epoxy resin and the functional group present on the surface of the acidic carbon black to preferably interact with each other.

As said polyfunctional epoxy compound, the polyfunctional epoxy compound used conventionally in order to form the pigment dispersion for black matrices is mentioned.

The polyfunctional epoxy compound preferably has a structure selected from the group consisting of a diphenylmethane skeleton, a dinaphthylmethane skeleton, A skeleton and at least one skeleton of a biphenyl skeleton.

The diphenylmethane skeleton, the dinaphthylmethane skeleton, and the biphenyl skeleton have a structure similar to the surface structure of the acidic carbon black described above, so they are easily accessible to the acidic carbon black, and the photoresist composition is dispersed in a pigment for baking black matrix. It is easy to react with the functional group existing on the surface of the acidic carbon black, and it is considered that the pigment dispersion for a black matrix of the present invention can be preferably provided with high insulation properties.

Also, having the above three In the framework of multifunctional epoxy compounds, The skeleton has basicity, so it is easy to approach acidic carbon black. When baking the black matrix pigment to disperse the photoresist composition, it is easy to react with the functional group existing on the surface of the acidic carbon black. The black matrix pigment dispersion provides high insulation.

As having a structure selected from the group consisting of the diphenylmethane skeleton, the dinaphthylmethane skeleton, Examples of the polyfunctional epoxy compound having at least one skeleton among the skeleton and the biphenyl skeleton include the following formulae (1) to (3).

Product name: TEPIC (manufactured by Nissan Chemical Co., Ltd.)

Product name: EPICLON 830 (manufactured by DIC)

Product Name: JER-YX-4000 (manufactured by Mitsubishi Chemical Corporation)

The polyfunctional epoxy compound is preferably a polyfunctional epoxy compound having four or more functions. If it is the above-mentioned polyfunctional epoxy compound having four or more functions, the film is excellent in maintaining the film at a high temperature, so it is considered that high insulation can be maintained in combination with a large volume.

The above-mentioned polyfunctional epoxy compound having four or more functions is more preferably a diphenylmethane skeleton, a dinaphthylmethane skeleton, 4-functional polyfunctional epoxy compound with a skeleton and a biphenyl skeleton. Examples of such a compound include the following formula (4).

Product Name: JER-604 (Mitsubishi Chemical Corporation)

The polyfunctional epoxy compound contains 0.1 to 50 parts by mass based on 100 parts by mass of the acidic carbon black.

If the content of the polyfunctional epoxy compound is less than 0.1 parts by mass relative to 100 parts by mass of the above-mentioned acidic carbon black, a pigment dispersion for a black matrix having a high resistance cannot be obtained. On the other hand, if the content of the polyfunctional epoxy compound is more than 50 parts by mass relative to 100 parts by mass of the above-mentioned acidic carbon black, there is a possibility that the stability of the dispersion liquid is impaired due to the polymerization of the epoxy group.

The lower limit of the preferable content of the polyfunctional epoxy compound is 5 parts by mass relative to 100 parts by mass of the above-mentioned acidic carbon black, and the upper limit of the preferable content of the polyfunctional epoxy compound is relative to 100 parts by mass of the above acidic Carbon black was 20 parts by mass.

(Solvent)

The pigment dispersion for a black matrix of the present invention contains a solvent.

As the solvent, users have been able to disperse acid carbon black stably, and the pigment dispersant, the polyfunctional epoxy compound, and the alkali-soluble resin described below have been dissolved.

As the solvent, an ester-based organic solvent, an ether-based organic solvent, an ether-ester-based organic solvent, a ketone-based organic solvent, and an aromatic hydrocarbon-based organic solvent having a boiling point of 100 to 250 ° C. at normal pressure (1.013 × 10 ² kPa) are preferred. Organic solvents, nitrogen-containing organic solvents, and the like.

Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethyl ether. Ether-based organic solvents such as glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ether; ethylene glycol Ether-based organic solvents such as alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Isobutyl ketone, cyclohexanone, 2-heptane Ketones, δ-butyrolactone and other ketone organic solvents; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl propionate- 3-methoxybutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxylate Ester-based organic solvents such as ethyl acetate, glycolate, and n-pentyl formate; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide And other nitrogen-containing organic solvents; these organic solvents can be used alone or in combination of two or more.

(Additives can be added as needed)

The pigment dispersion for a black matrix of the present invention may contain a group selected from the group consisting of an acid group-containing pigment derivative, an acid group-containing pigment derivative, and an acid group-containing pigment intermediate in order to improve the dispersibility of acidic carbon black. At least one of them, and an alkali-soluble resin.

First, as the pigment derivative containing an acid group and the pigment derivative containing an acid group, a phthalocyanine pigment derivative having an acid group, an anthraquinone pigment derivative having an acid group, and a naphthalene pigment having an acid group can be exemplified. Derivatives, etc. Among them, a phthalocyanine-based pigment derivative having a sulfonic acid group is preferable in terms of dispersibility of acidic carbon black.

The acid group-containing pigment derivative, the acid group-containing pigment derivative, and the acid group-containing pigment intermediate preferably contain 0 to 20 parts by mass based on 100 parts by mass of the acid carbon black.

The acid group-containing pigment derivative, the acid group-containing pigment derivative, and the acid group-containing pigment intermediate are more preferably contained in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the acidic carbon black.

Examples of the alkali-soluble resin include alkali-soluble copolymer resins and alkali-soluble cardo resins described below.

The alkali-soluble resin preferably contains 0 to 100 parts by mass based on 100 parts by mass of the acidic carbon black.

The alkali-soluble resin is more preferably contained in an amount of 0.5 to 60 parts by mass based on 100 parts by mass of the acidic carbon black.

(Manufacture of pigment dispersion for black matrix)

The pigment dispersion for the black matrix of the present invention is acidic carbon black, a pigment dispersant, the above-mentioned polyfunctional epoxy compound, a solvent, and optionally selected from an acid group-containing pigment derivative, an acid group-containing pigment derivative, A mixture of at least one of a group consisting of an acid group-containing pigment intermediate and an alkali-soluble resin. The pigment dispersion for a black matrix can be obtained by subjecting the mixture to a dispersion treatment using a roll mill, a kneader, a high-speed mixer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure disperser, and the like.

Next, the pigment-dispersed photoresist composition for a black matrix of the present invention will be described.

The pigment-dispersed photoresist composition for a black matrix of the present invention is mainly composed of the pigment dispersion for a black matrix described above, and an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and is appropriately added as necessary. It is obtained by various additives such as a polymerization inhibitor.

(Alkali soluble resin)

Examples of the alkali-soluble resin used in the pigment-dispersed photoresist composition for a black matrix of the present invention include an alkali-soluble copolymer, an alkali-soluble cardo resin, and the like.

Examples of the alkali-soluble copolymer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, methyl maleic acid, and formic acid. Unsaturated monomers containing carboxyl groups such as maleic anhydride, methyl maleic acid monoalkyl ester, and the like; and selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid. Allyl esters, Allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, mono (meth) acrylate with a dicyclopentadiene skeleton, N-phenylcis-butyl A copolymer obtained by reacting at least one of a group consisting of enediimine, polystyrene macromonomer, and polymethylmethacrylate macromonomer.

Examples of the alkali-soluble cardo resin include an epoxy (meth) acrylic acid having a fluorene skeleton, an addition product of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic anhydride and / or a tetracarboxylic dianhydride. Adducts, etc.

The said alkali-soluble resin can be used individually or in combination of 2 or more types. In terms of coating film formation properties and alkali developability, the alkali-soluble resin preferably has an acid value of 20 to 300 mgKOH / g and a weight average molecular weight of 1,000 to 200,000. The said alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types according to the required performance.

The content of the alkali-soluble resin in the pigment-dispersed photoresist composition for a black matrix is preferably in a range of 5 to 50% by mass in the solid content of the pigment-dispersed photoresist composition for a black matrix.

(Photopolymerizable compound)

Examples of the photopolymerizable compound used in the pigment-dispersed photoresist composition for the black matrix pigment of the present invention include monomers and oligomers having a photopolymerizable unsaturated bond.

Specifically, as the monomer having one photopolymerizable unsaturated bond in the molecule, for example, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, Alkyl methacrylate or alkyl acrylate, such as butyl acrylate, 2-ethylhexyl acrylate; aralkyl methacrylate, or aralkyl acrylate, such as benzyl methacrylate or benzyl acrylate; methyl Alkoxyalkyl methacrylate or alkoxyalkyl acrylate, such as butoxyethyl acrylate, butoxyethyl acrylate; N, N-dimethylaminoethyl methacrylate, N, N acrylate - Dimethylaminoethyl and other aminoalkyl methacrylates or aminoalkyl acrylates; polyalkylene glycols such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether Methacrylate or acrylate of monoalkyl ether; methacrylate or acrylate of polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether; isobornyl methacrylate or isobornyl acrylate Esters; glycerol methacrylate or glyceryl acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, and the like.

As the monomer having two or more photopolymerizable unsaturated bonds in the molecule, for example, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butane Alcohol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate Esters, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyltetraol trimethacrylate, neopentaerythritol tetramethacrylate, dipentaerythritol tetramethyl Acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol Alcohol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trihydroxy Methylpropane triacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dineopentyl Tetraol tetraacrylate, dinepentaerythritol hexaacrylate, dinepentaerythritol pentaacrylate and the like.

As the oligomer having the photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the monomers can be used. These photopolymerizable compounds can be used individually or in combination of 2 or more types.

In the present invention, the amount of the photopolymerizable compound used is based on the total solid content of the pigment-dispersed photoresist composition for the black matrix of the present invention, and is preferably in a range of 3 to 50% by mass.

(Photopolymerization initiator)

The photopolymerization initiator used in the black matrix pigment-dispersed photoresist composition of the present invention is not particularly limited. For example, benzophenone, N, N'-tetraethyl-4,4'-di Aminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzil, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoyl isobutyl ether, benzil dimethylketal, α-hydroxybenzoisobutyl ketone, 9-oxysulfur , 2-chloro-9-oxysulfur , 1-hydroxycyclohexyl benzophenone, third butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1 , 4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, tris Based photopolymerization initiator, oxime ester based photopolymerization initiator and the like. These photopolymerization initiators can be used alone or in combination of two or more.

In the present invention, the amount of the photopolymerization initiator used is based on the total solid content of the pigment-dispersed photoresist composition for the black matrix of the present invention, and is preferably in the range of 1 to 20% by mass.

(Solvent)

As the solvent used in the pigment-dispersed photoresist composition for the black matrix of the present invention, the same solvents as those listed above can be used. Particularly preferred are ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon-based organic solvents, and organic solvents having a boiling point of 100 to 250 ° C at normal pressure (1.013 × 10 ² kPa). Nitrogen-based organic solvents. If a large amount of an organic solvent having a boiling point of more than 250 ° C is contained, there is a case where the organic solvent does not sufficiently evaporate and remains in the dry coating film when the coating film formed by the coating is pre-baked, and the heat resistance of the dry coating film reduce. When a large amount of an organic solvent having a boiling point of less than 100 ° C is contained, it may be difficult to perform uniform coating without unevenness, and a coating film having excellent surface smoothness may not be obtained.

Specific examples of such a 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, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether , Diethylene glycol dimethyl ether, diethylene glycol methyl ether and other ether organic solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Esters, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other ether ester organic solvents; methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone and other ketone organic solvents Class; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, glycolate, n-formate Ester-based organic solvents such as amyl esters; N-methyl pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and other nitrogen-containing organic solvents; etc .; It can be used alone or in combination of two or more.

Among these solvents, in terms of solubility, dispersibility, coatability, and the like, diethylene glycol dimethyl ether, diethylene glycol methyl ether, ethylene glycol monomethyl ether acetate, and the like are preferred. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutyl propionate, 3-methyl Ethoxy propionate, methyl 3-ethoxy propionate, n-pentyl formate and the like. Particularly preferred is propylene glycol monomethyl ether acetate.

These solvents are preferably used for the pigment dispersion photoresist for the black matrix in terms of the dispersibility of the pigment, the polyfunctional epoxy compound, the solubility of the alkali-soluble resin, pigment dispersibility, and coating properties. The total organic solvent of the composition contains 50% by mass or more, and more preferably 70% by mass or more.

(additive)

In the pigment-dispersed photoresist composition for a black matrix of the present invention, it may be appropriately used as required. Various additives such as photopolymerizable compounds, thermal polymerization inhibitors, and antioxidants other than those mentioned above are used.

(Pigment-dispersed photoresist composition for black matrix)

The method for producing the pigment-dispersed photoresist composition for a black matrix of the present invention is an example of a preferred embodiment of the present invention, and the present invention is not limited thereto. For example, it is possible to use a method in which a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin are added to the pigment dispersion for the black matrix, and an organic solvent and other additives are added if necessary, followed by stirring and mixing using a stirring device or the like.

The carbon black in the pigment-dispersed photoresist composition for a black matrix is preferably 30 to 80% by mass based on the mass% of the solid content of the pigment-dispersed photoresist composition for a black matrix.

According to the present invention, it is possible to provide a pigment dispersion for a black matrix having high light shielding properties and high insulation properties, and a pigment dispersion photoresist composition for a black matrix containing the pigment dispersion.

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples as long as it does not deviate from the gist and scope of application. Furthermore, in this embodiment, unless otherwise specified, "part" and "%" represent "mass part" and "mass%", respectively.

The materials of the pigment dispersion for black matrix used in the following examples and comparative examples are as follows.

<Acid Carbon Black>

Special Black 250 (manufactured by Degussa, oil absorption: 46ml / 100g, pH: 3.1, average primary particle size 56nm)

<Pigment Dispersant>

BYK-161 (manufactured by BYK Chemie, Disperbyk-161, amine value: 11 mgKOH / g, acid value: 0 mgKOH / g)

<Polyfunctional epoxy compound>

JER-604 (Mitsubishi Chemical Corporation, a multifunctional epoxy compound with a biphenyl skeleton)

EPICLON 830 (manufactured by DIC, a multifunctional epoxy compound with a diphenylmethane skeleton)

JER-YX-4000 (Mitsubishi Chemical Corporation, a multifunctional epoxy compound with a biphenyl skeleton)

TEPIC (manufactured by Nissan Chemical Co., Ltd. Multifunctional epoxy compound of the skeleton)

<Monofunctional epoxy compound>

DENACOL EX-141 (manufactured by Nagase Kasei, a monofunctional epoxy compound)

<Pigment derivative containing acid group>

Solsperse 5000 (manufactured by Lubrizol, phthalocyanine derivative)

<Solvent>

PGMEA (propylene glycol monomethyl ether acetate)

The materials of the pigment dispersion photoresist composition for black matrix used in the following examples and comparative examples are as follows.

<Alkali soluble resin>

BzMA / MAA (benzyl methacrylate / methacrylic acid copolymer, theoretical acid value: 120 mgKOH / g, mass average molecular weight: 25000)

<Photopolymerizable compound>

DPHA (dinepentaerythritol hexaacrylate)

<Photopolymerization initiator>

Irgacure 907 (manufactured by BASF, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinylpropane-1-one)

<Solvent>

PGMEA (propylene glycol monomethyl ether acetate)

<Preparation of Pigment Dispersions for Black Matrix of Examples 1 to 6 and Comparative Examples 1 to 4>

Various materials were mixed in such a manner as to have a composition in Table 1 (the usage amount of each material in Table 1 is mass%), and kneaded by a bead mill for a whole day to prepare Examples 1 to 6, and Comparative Examples 1 to 4 Pigment dispersion for black matrix.

<Preparation of pigment-dispersed photoresist composition for black matrix of Examples 1 to 6 and Comparative Examples 1 to 4>

Using a high-speed mixer, uniformly mix the pigment dispersions for each of the black matrices of Examples 1 to 6 and Comparative Examples 1 to 4 so as to have the composition of Table 1 (the amount of each material used in Table 1 is mass%) The material was filtered through a filter having a pore size of 3 μm to obtain the pigment-dispersed photoresist composition for each of the black matrices of Examples 1 to 6 and Comparative Examples 1 to 4.

<Evaluation test>

Regarding the pigment dispersion for black matrix and the pigment dispersion photoresist composition for black matrix obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the dispersion stability, optical density, and surface resistance value were evaluated by the following methods. The results are shown in Table 2.

(Dispersion stability)

The pigment dispersions for each of the black matrices in Examples 1 to 6 and Comparative Examples 1 to 4 were collected into glass bottles and stoppered, and the state after storage at room temperature for 7 days was evaluated according to the following evaluation criteria.

A: No thickening or sedimentation

B: See thickening or sediment that can be restored to the original level if gently shaken

C: Seeing no thickening or sedimentation even if it is shaken strongly

<Optical density (OD value)>

Using a spin coater, Examples 1 to 6 and Comparative Example 1 were formed so that the film thickness became 1 μm. The pigment-dispersed photoresist composition for each of the black matrices was coated on a glass substrate, pre-baked at 100 ° C for 3 minutes, exposed by a high-pressure mercury lamp, and then baked at 230 ° C for 3 hours to obtain only formation Black photoresist pattern on the solid part. The obtained optical density (OD value) of the black photoresist pattern of each solid part was measured with a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth).

(Surface resistance value)

The pigment-dispersed photoresist composition for each of the black matrices of Examples 1 to 6 and Comparative Examples 1 to 4 was applied to a glass substrate by a spin coater so that the film thickness became 1 μm. After baking for 3 minutes, exposure was performed by a high-pressure mercury lamp, and then baking was performed at 230 ° C for 3 hours to obtain a black photoresist pattern formed only on the solid portion. The surface resistance value of the black photoresist pattern of each solid part obtained was measured by Advance company, the main body: a micro galvanometer R8340, and an optional part: a shield box R12702A.

The photoresist composition for a black matrix of Examples 1 to 6 is excellent in both of high light shielding properties and high insulation properties.

On the other hand, the photoresist compositions for black matrices of Comparative Examples 1, 2, and 4 failed to obtain those that simultaneously achieved high light shielding properties and high insulation properties.

In addition, the dispersion stability of the pigment dispersion for black matrix of Comparative Example 3 was poor, and no A photoresist composition for a black matrix that is sufficient for evaluation of optical density and surface resistance value.

[Industrial availability]

According to the present invention, it is possible to provide a pigment dispersion for a black matrix having high light shielding properties and high insulation properties, and a pigment dispersion photoresist composition for a black matrix containing the pigment dispersion.

Claims (3)

A pigment dispersion for a black matrix comprising an acidic carbon black, a pigment dispersant, a polyfunctional epoxy compound, and a solvent, wherein the polyfunctional epoxy compound contains 0.1 to 100 parts by mass of the acidic carbon black. ~ 50 parts by mass, and is selected from the group consisting of diphenylmethane skeleton, dinaphthylmethane skeleton, An epoxy compound of at least one of a skeleton and a biphenyl skeleton. For example, the pigment dispersion for black matrices in the first patent application scope, wherein the polyfunctional epoxy compound is a tetrafunctional or more epoxy compound. A pigment-dispersed photoresist composition for a black matrix includes a pigment dispersion for a black matrix, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.