TW201522528A - Pigment dispersion for black matrix, and pigment-dispersed resist composition for black matrix containing same - Google Patents

Abstract

The present invention provides a pigment dispersion for a black matrix having high light-blocking properties and high insulating properties, and a pigment-dispersed resist composition for a black matrix containing the same. The present invention is a pigment dispersion for a black matrix containing acidic carbon black, a pigment dispersant, a polyfunctional epoxy compound, and a solvent, wherein the pigment dispersion for a black matrix is characterized in containing 0.1-50 parts by mass of the polyfunctional epoxy compound relative to 100 parts by mass of acidic carbon black.

Description

Pigment dispersion for black matrix and pigment dispersion resist composition for black matrix containing the same

The present invention relates to a pigment dispersion for a black matrix which maintains high light-shielding property and has high insulation property, and a pigment dispersion resist composition for a black matrix containing the same.

In recent years, the use of a pigment dispersion for a black matrix involves various aspects, for example, in a flat panel display such as a liquid crystal or a plasma, in order to provide a light-shielding film for the gap of the colored pattern or the edge of the peripheral portion of the display region in the display region of the screen (black) In addition, a liquid crystal display having a TFT is used, and a light shielding film (black matrix) is provided for the light side or the like other than the TFT. Moreover, the liquid crystal display mainly functions to prevent the leakage light from the backlight from being reflected into the screen and to improve the display characteristics (contrast and color purity), and the plasma display is mainly for preventing the fainting caused by the turbidity of the respective colors of light. Enter the screen to improve display characteristics (contrast and color purity).

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

Moreover, in the touch panel combined with the image display device and the position input device, Similarly, a color filter in which a black matrix is formed is used as a light-shielding film, and conventionally, it is formed on the side opposite to the sensor substrate via a cover glass. However, as the demand for weight reduction of the touch panel has become high, the following techniques have been developed to achieve a lighter weight: a technique of simultaneously forming a light-shielding film and a touch sensor on the same side of the cover glass. In this case, after forming a black matrix on the cover glass, it is necessary to form an electrode for the sensor or the like. Therefore, it is first required to have high insulation which does not cause malfunction even if the black matrix is crossed and a plurality of electrodes are contacted. In addition, high adhesion or chemical resistance is also required.

Therefore, in order to obtain a black matrix having high insulating properties, there are disclosed techniques in which carbon black is used as a light-shielding pigment, and an epoxy group-containing epoxy acrylate compound is used as a photocurable material (for example, refer to the patent literature) 1) An insulating carbon black obtained by coating a carbon black with a polyfunctional epoxy resin (in the example, a bifunctional one is used as a polyfunctional epoxy resin) (for example, see Patent Document 2) .

The high insulation property can be obtained by the technique disclosed in the above, but in recent years, a black matrix having high light-shielding property and high insulation property of a film is required, and it is necessary to increase the content ratio of carbon black as a light-shielding material. However, since carbon black has electrical conductivity, if the content ratio is increased, the insulating property is lowered, and the disclosed techniques cannot satisfy the requirements of achieving high light-shielding property and high insulating property at the same time.

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

Patent Document 2: Japanese Patent Publication No. 09-124969

Accordingly, an object of the present invention is to provide a pigment dispersion for a black matrix having high light-shielding property and high insulation property, and a pigment dispersion resist composition for a black matrix containing the same.

The present inventors have recognized that, in order to increase the content ratio of carbon black in the coating film in order to increase the content ratio of carbon black in the coating film in order to make the coating film of the photoresist composition for the black matrix a thinner film and have high light-shielding property, The electrical conductivity causes a decrease in the insulating property of the coating film. It is found that after the coating film of the photoresist composition for a black matrix is formed by photohardening, if the post-hardening treatment is performed at a high temperature, the decrease in insulation property becomes conspicuous. .

The present inventors presume that this phenomenon suggests that the heat-cured coating film is temporarily softened by the heat of post-hardening to cause agglomeration of carbon black, and the following materials are studied: a resin having high heat resistance is formed on the surface of the carbon black. Even if aggregation occurs in the film, the decrease in insulation property is suppressed, and the development characteristics and the like in forming the black matrix are not adversely affected.

As a result, the inventors of the present invention have found that the present invention can be achieved by using acidic carbon black and a polyfunctional epoxy compound, and even if the content ratio of the acidic carbon black is increased, high insulating properties can be maintained.

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

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

Moreover, the present invention is also a pigment dispersion resist composition for a black matrix, which comprises the pigment dispersion for a black matrix, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

Further, in the present invention, a tetrafunctional or higher polyfunctional epoxy compound is preferred.

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

The mechanism for the high insulating property of the pigment dispersion for a black matrix of the present invention is not clear, but it is presumed 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 in which the substituent on the surface of the acidic carbon black interacts with a substituent having a polyfunctional epoxy compound. And a polyfunctional epoxy compound is adsorbed on the surface of the acidic carbon black. Therefore, by having the polyfunctional epoxy compound have a plurality of junction sites, the probability of interaction with the functional groups on the surface of the carbon black can be improved.

Further, when the photoresist composition for a black matrix is applied, the state in which the epoxy group of the polyfunctional epoxy compound interacts with the functional group on the surface of the acidic carbon black is adsorbed, and it is possible to fully consider the use of photohardening. The reaction is carried out with heat at the time of post-hardening to form an epoxy resin coating of acid carbon black.

As described above, even if the acidic carbon blacks are in contact with each other due to aggregation, the surface of the conductive carbon black does not directly contact, and is in contact with the non-conductive polyfunctional epoxy compound film. Further, when the polyfunctional epoxy compound has a skeleton having a polycyclic structure, the coating of the acid black black is excellent at a high temperature, and it is presumed that the insulating property can be maintained in combination with a large volume.

(acidic carbon black)

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

As the acidic carbon black, an acid carbon black which has been used since the formation of a black matrix has been 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 Corporation. ; 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 an acidic group such as a carboxyl group are preferred. Further, it is preferably one having a particle diameter of 20 to 60 nm. In the case of such an acidic carbon black, it is possible to preferably interact with the polyfunctional epoxy compound described below to impart high insulating properties to the pigment dispersion for a black matrix of the present invention.

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

In addition, the said particle diameter means the average primary particle diameter measured or computed by microscopic observation.

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

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

The pigment dispersant is a pigment-dispersing agent containing a basic group, and an anionic surfactant, a polyester-based pigment dispersant containing a basic group, an acrylic-based pigment dispersant containing a basic group, and an alkalinity can be used. A urethane-based pigment dispersant, a basic carbodiimide-based pigment dispersant, and the like.

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

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, a poly(lower alkyleneamine) such as polyallylamine, polyvinylamine or polyethylene polyimine), and a group selected from the group consisting of having a free carboxyl group. a reaction product of at least one of a group consisting of polyester, polyamine, and polyester decylamine (Japanese Patent Laid-Open Publication No. 2001-59906);

(2) a reaction product of a low molecular amine compound such as a poly(lower) alkylene imine or a methyliminodipropylamine, and a polyester having a free carboxyl group (Japanese Unexamined Patent Application Publication No. Hei No. Hei No. 54-37082 Bulletin 01-311177);

(3) A polyester having one hydroxyl group such as an alcohol such as methoxypolyethylene glycol or a caprolactone polyester, a compound having 2 to 3 isocyanate-reactive functional groups, and an isocyanate-reactive functional group. a reaction product obtained by reacting an aliphatic or heterocyclic hydrocarbon compound of a 3-stage amine group with an isocyanate group of a polyisocyanate compound (JP-A-02-612);

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

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

(6) a reaction product obtained by reacting a compound having an amine group with a compound having an isocyanate group (JP-A-2004-210220);

(7) a reaction product obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having a 2-stage amine group with a polyepoxy compound (JP-A-09-87537);

(8) a reaction product of a polycarbonate compound having a functional group reactive with an amine group at a single terminal and a polyamine compound (JP-A-09-194585);

(9) selected from the group consisting of 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 or benzyl acrylate, and acrylamide, methacrylamide, N-hydroxymethyl decylamine, ethylene At least one of a basic group-containing polymerizable monomer such as a base imidazole, a vinyl pyridine, a monomer having an amine group and a polycaprolactone skeleton, and a styrene, a styrene derivative, or another polymerizable monomer a copolymer of at least one type (JP-A-01-164429);

(10) A carbon diimide-based pigment dispersant containing a basic group (International Publication WO 04/000950);

(11) a block copolymer composed of a block having a basic group such as a 3-stage amine group or a 4-stage ammonium salt group and a block having no functional group (refer to Japanese Patent Laid-Open Publication No. 2005-55814);

(12) A pigment dispersing agent obtained by subjecting a polycarbonate compound to a polyallylamine by a Michael addition reaction (JP-A-09-194585);

(13) a carbodiimide compound having at least one polybutadiene chain and a basic nitrogen group, respectively (JP-A-2006-257243);

(14) having at least one side chain having a guanamine group and a basic nitrogen group in the molecule A carbodiimide-based compound (JP-A-2006-176657) or the like.

(15) A polyurethane compound having an amine group containing an ethylene oxide chain and a propylene oxide chain and having an amine group which is quaternized by a quaternizing agent (JP-A-2009-175613) );

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

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

The above-mentioned basic group-containing dispersing agent is preferably contained in an amount of from 1 to 200 parts by mass per 100 parts by mass of the above acidic carbon black.

If the content of the above-mentioned basic group-containing dispersant is less than 1 part by mass, there is a case where the stability of the pigment dispersion is impaired. On the other hand, when the content of the above-mentioned basic group-containing dispersant exceeds 200 parts by mass, the light-shielding property or the insulating property of the coating film may be impaired.

Further, the above-mentioned basic group-containing dispersing agent is more preferably contained in an amount of from 1 to 60 parts by mass per 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 polyfunctional epoxy resin to preferably interact with a functional group present on the surface of the acidic carbon black.

As the polyfunctional epoxy compound, a polyfunctional epoxy compound which has been used in order to form a pigment dispersion for a black matrix has been mentioned.

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

The above-mentioned diphenylmethane skeleton, dinaphthylmethane skeleton, and biphenyl skeleton have a structure similar to that of the above-mentioned acidic carbon black, so that it becomes easy to be close to acidic carbon black, and is composed of a pigment dispersion resist for baking black matrix. In the case of a substance, it is easy to react with a functional group existing on the surface of the acidic carbon black. Therefore, it is considered that the pigment dispersion for a black matrix of the present invention can be preferably provided with high insulating properties.

Again, with the above three Skeletal polyfunctional epoxy compound, due to three Since the skeleton is alkaline, it becomes easy to access the acidic carbon black, and when the pigment dispersion composition of the pigment for black matrix is baked, it is easy to react with the functional group present on the surface of the acidic carbon black, and thus it can be considered that the present invention can be preferably used. The black matrix pigment dispersion imparts high insulation.

As having the above-mentioned diphenylmethane skeleton, dinaphthylmethane skeleton, and three Examples of the polyfunctional epoxy compound of at least one of the skeleton and the biphenyl skeleton include the following formulas (1) to (3).

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

Product name: EPICLON 830 (manufactured by DIC Corporation)

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

The polyfunctional epoxy compound is preferably a tetrafunctional or higher polyfunctional epoxy compound. When the above-mentioned tetrafunctional or higher polyfunctional epoxy compound is excellent in the maintenance of the film at a high temperature, it is considered that the high insulating property can be maintained in combination with a large volume.

More preferably, the above-mentioned tetrafunctional or higher polyfunctional epoxy compound has a diphenylmethane skeleton, a dinaphthylmethane skeleton, and three A tetrafunctional or higher polyfunctional epoxy compound having a skeleton and a biphenyl skeleton. As such a compound, the following formula (4) is mentioned.

Product Name: JER-604 (Mitsubishi Chemical Co., Ltd.)

The polyfunctional epoxy compound is contained in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the acidic carbon black.

When the content of the polyfunctional epoxy compound is less than 0.1 part by mass based on 100 parts by mass of the acidic carbon black, a high-resistance pigment dispersion for a black matrix cannot be obtained. On the other hand, when the content of the polyfunctional epoxy compound exceeds 50 parts by mass based on 100 parts by mass of the acidic carbon black, there is a possibility that the stability of the dispersion is deteriorated by polymerization of an epoxy group.

The lower limit of the preferred content of the polyfunctional epoxy compound is 5 parts by mass based on 100 parts by mass of the above acidic carbon black, and the upper limit of the preferred content of the polyfunctional epoxy compound is relative to 100 parts by mass of the above acidity. Carbon black is 20 parts by mass.

(solvent)

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

As the solvent, the acid carbon black can be stably dispersed by the user, and the above-described pigment dispersant, the above polyfunctional epoxy compound, and the following alkali-soluble resin can be dissolved.

The solvent is preferably an ester organic solvent having a boiling point of 100 to 250 ° C under normal pressure (1.013 × 10 ² kPa), an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, or an aromatic hydrocarbon system. An organic solvent, a nitrogen-containing organic solvent, or 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. An ether-based organic solvent such as diol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol methyl ether; An ether ester type organic solvent such as alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Isobutyl ketone, cyclohexanone, 2-glycan Ketone, δ-butyrolactone and other ketone organic solvents; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl propionate 3-methoxybutyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxy An ester-based organic solvent such as ethyl acetate, hydroxyacetate or n-amyl formate; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide The nitrogen-containing organic solvent or the like may be used alone or in combination of two or more.

(can be added as needed)

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

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

The acid group-containing pigment derivative, the acid group-containing dye derivative, and the acid group-containing dye intermediate are preferably contained in an amount of from 0 to 20 parts by mass per 100 parts by mass of the acidic carbon black.

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

The alkali-soluble copolymer resin described later, an alkali-soluble cardo resin, and the like are mentioned as the alkali-soluble resin.

The alkali-soluble resin is preferably contained in an amount of from 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 from 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 a black matrix of the present invention is an acidic carbon black, a pigment dispersant, the above polyfunctional epoxy compound, a solvent, and optionally a pigment derivative selected from an acid group-containing pigment derivative and an acid group-containing pigment derivative. A mixture of at least one of a group consisting of an acid group-containing dye intermediate and an alkali-soluble resin. The pigment dispersion for the 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 dispersing device, or the like.

Next, the pigment dispersion resist composition for a black matrix of the present invention will be described.

The pigment dispersion resist composition for a black matrix of the present invention is mainly composed of the pigment dispersion for a black matrix, 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)

The alkali-soluble resin used in the pigment dispersion resist composition for a black matrix of the present invention may, for example, be an alkali-soluble copolymer or an alkali-soluble cardo resin.

As the alkali-soluble copolymer, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, methyl maleic acid, and methyl a carboxyl group-containing unsaturated monomer such as methacrylic anhydride or methyl maleic acid monoalkyl ester, and selected from the group consisting of styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylic acid. Allyl ester, Allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerin monoacrylate, glycerol methacrylate, mono(meth)acrylate with dicyclopentadiene skeleton, N-phenyl cis-butyl A copolymer obtained by reacting at least one of a group consisting of an enediamine, a polystyrene macromonomer, and a polymethyl methacrylate macromonomer.

The alkali-soluble cardo-resin may, for example, be an epoxy (meth) acrylate acid having an anthracene skeleton, which is an addition product of a fluorene (meth)acrylic acid derivative and a dicarboxylic anhydride and/or a tetracarboxylic dianhydride. Additives, etc.

These alkali-soluble resins may be used singly or in combination of two or more. 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 in terms of film formability and alkali developability. The above-mentioned alkali-soluble resin can be used singly or in combination of two or more kinds depending on the desired properties.

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

(photopolymerizable compound)

The photopolymerizable compound used as the pigment dispersion resist composition for a black matrix of the present invention may, for example, be a monomer or oligomer having a photopolymerizable unsaturated bond.

Specifically, as a monomer having one photopolymerizable unsaturated bond in the molecule, for example, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, or the like can be used. An alkyl methacrylate or an alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate; an aralkyl methacrylate or an aryl acrylate such as benzyl methacrylate or benzyl acrylate; Alkoxyalkyl methacrylate or alkoxyalkyl acrylate such as butoxyethyl acrylate or butoxyethyl acrylate; N,N-dimethylaminoethyl methacrylate, N,N acrylic acid - Aminoalkyl methacrylate such as dimethylaminoethyl ester or aminoalkyl acrylate; polyalkylene glycol such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether or dipropylene glycol monomethyl ether a methacrylate or acrylate of a monoalkyl ether; a methacrylate or acrylate of a polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether; an isobornyl methacrylate or an isobornyl acrylate Ester; glycerin methacrylate or glycerin acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate.

As a monomer having two or more photopolymerizable unsaturated bonds in the molecule, for example, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, and 1,3-butyl can be used. Alcohol dimethacrylate, diethylene glycol dimethacrylate, glycerin dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate Ester, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol tetramethyl Acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butane Alcohol diacrylate, diethylene glycol diacrylate, glycerin diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trihydroxyl Methyl propane triacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dioxane Tetraol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.

As the oligomer having the photopolymerizable unsaturated bond, those obtained by appropriately polymerizing the above monomers can be used. These photopolymerizable compounds may be used singly or in combination of two or more.

In the present invention, the amount of the photopolymerizable compound used is preferably from 3 to 50% by mass based on the total solid content of the pigment dispersion resist composition for a black matrix of the present invention.

(photopolymerization initiator)

The photopolymerization initiator used as the pigment dispersion resist composition for a black matrix of the present invention is not particularly limited, and for example, benzophenone, N, N'-tetraethyl-4, 4'-di can be used. Aminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzil, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoin isobutyl ether, benzil dimethylketal, alpha-hydroxy phenyl isobutyl ketone, 9-oxygen sulphide 2-chloro-9-oxosulfur , 1-hydroxycyclohexyl benzophenone, tert-butyl hydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole, 2-ethyl hydrazine, 1 , 4-naphthoquinone, 1,2-benzopyrene, 1,4-dimethylindole, 2-phenylindole, three A photopolymerization initiator, an oxime ester photopolymerization initiator, and the like. These photopolymerization initiators may be used singly 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 dispersion resist composition for a 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 dispersion resist composition for a black matrix of the present invention, the same solvents as those exemplified above can be used. Particularly preferred are ester-based organic solvents having a boiling point of 100 to 250 ° C under normal pressure (1.013 × 10 ² kPa), ether-based organic solvents, ether-ester organic solvents, ketone-based organic solvents, aromatic hydrocarbon-based organic solvents, and the like. A nitrogen-based organic solvent or the like. When a large amount of the organic solvent having a boiling point of more than 250 ° C is contained, when the coating film formed by coating is pre-baked, the organic solvent does not sufficiently evaporate and remains in the dried coating film, and the heat resistance of the dried coating film is dried. reduce. In addition, when a large amount of the organic solvent having a boiling point of less than 100 ° C is contained, it is difficult to apply uniformly without unevenness, and a coating film excellent in surface smoothness cannot be obtained.

As such a solvent, specifically, 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 Ether-based organic solvents such as diethylene glycol dimethyl ether and diethylene glycol methyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate Ether esters such as ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone; Class; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetate, formic acid An organic solvent such as an ester of amyl ester; a nitrogen-containing organic solvent such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide; Either alone or in combination of two or more.

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

The solvent is preferably used in the above-mentioned black matrix pigment dispersion resist in terms of solubility of the above pigment dispersant, the polyfunctional epoxy compound, and the alkali-soluble resin, pigment dispersibility, and coatability. The total organic solvent of the composition is contained in an amount of 50% by mass or more, and more preferably 70% by mass or more.

(additive)

In the pigment dispersion resist composition for a black matrix of the present invention, it may be appropriately made as needed Various additives such as a photopolymerizable compound, a thermal polymerization inhibitor, and an antioxidant other than the above are used.

(Pigment Dispersion Resistive Composition for Black Matrix)

The method of producing the pigment-dispersing 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, a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin may be added to the pigment dispersion for a black matrix, and an organic solvent and other additives may be added as needed, and stirred and mixed using a stirring device or the like.

Further, the carbon black in the pigment dispersion resist composition for a black matrix is preferably 30 to 80% by mass based on the mass% of the solid content of the pigment dispersion resist composition for a black matrix.

According to the invention, it is possible to provide a pigment dispersion for a black matrix having high light-shielding property and high insulation property, and a pigment dispersion resist composition for a black matrix containing the same.

Hereinafter, the present invention will be specifically described by using the examples, but the present invention is not limited to the examples as long as they do not depart from the gist of the invention and the scope of application. Further, in the present embodiment, "parts" and "%" indicate "parts by mass" and "mass%", respectively, unless otherwise specified.

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)

<Multifunctional epoxy compound>

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

EPICLON 830 (manufactured by DIC, a polyfunctional epoxy compound having a diphenylmethane skeleton)

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

TEPIC (manufactured by Nissan Chemical Co., Ltd., with three Skeleton polyfunctional epoxy compound)

<monofunctional epoxy compound>

DENACOL EX-141 (manufactured by Changchun Chemical Co., Ltd., monofunctional epoxy compound)

<Acid derivative containing acid group>

Solsperse 5000 (manufactured by Lubrizol, phthalocyanine derivative)

<solvent>

PGMEA (propylene glycol monomethyl ether acetate)

The materials of the pigment dispersion resist composition for a 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 mg KOH/g, mass average molecular weight: 25,000)

<Photopolymerizable compound>

DPHA (dipentaerythritol hexaacrylate)

<Photopolymerization initiator>

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

The materials of Table 1 were mixed (the amount of each material used in Table 1 was mass%), and the materials were mixed by a bead mill for a whole day to prepare Examples 1 to 6 and Comparative Examples 1 to 4. A pigment dispersion for a black matrix.

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

The pigment dispersions of the black matrix samples of Examples 1 to 6 and Comparative Examples 1 to 4 and the other examples were uniformly mixed in a high-speed mixer so as to have the composition of Table 1 (the amount of each material used in Table 1 is % by mass). After the material was filtered through a filter having a pore size of 3 μm, the pigment dispersion resist compositions for the black matrix of Examples 1 to 6 and Comparative Examples 1 to 4 were obtained.

<evaluation test>

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

(dispersion stability)

Each of the black matrix pigment dispersions of Examples 1 to 6 and Comparative Examples 1 to 4 was collected in a glass bottle and stoppered, and the state after storage at room temperature for 7 days was evaluated according to the following evaluation criteria.

A: No increase in viscosity or sediment

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

C: Viscosity or sediment that does not return to its original state even if it is shaken strongly

<Optical density (OD value)>

Examples 1 to 6 and Comparative Example 1 were obtained by a spin coater so that the film thickness became 1 μm. Each of the black matrix of ~4 was coated on the glass substrate with a pigment dispersion resist composition, prebaked at 100 ° C for 3 minutes, exposed to a high pressure mercury lamp, and further baked at 230 ° C for 3 hours to obtain only formation. A black photoresist pattern on the solid portion. The optical density (OD value) of the black resist pattern of each solid portion obtained was measured by a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth).

(surface resistance value)

The pigment dispersion resist compositions of the black matrix of Examples 1 to 6 and Comparative Examples 1 to 4 were applied onto a glass substrate by a spin coater so that the film thickness was 1 μm, and the film was preliminarily prepared at 100 ° C. After baking for 3 minutes, it was exposed by a high pressure mercury lamp, and further baked at 230 ° C for 3 hours to obtain a black resist pattern formed only on the solid portion. The surface resistance value of the black resist pattern of each of the obtained solid portions was measured by an Advance company, a body: a micro galvanometer R8340, and an option: a shield box R12702A.

The photoresist compositions for the black matrix of Examples 1 to 6 are excellent in both high light-shielding property and high-insulation property.

On the other hand, the photoresist compositions for the black matrix of Comparative Examples 1, 2, and 4 failed to obtain high light-shielding properties and high insulation properties.

Further, the pigment dispersion of the black matrix of Comparative Example 3 was inferior in dispersion stability and could not be obtained. A photoresist composition for a black matrix which is sufficient for evaluation of optical density and surface resistance value.

[Industrial availability]

According to the invention, it is possible to provide a pigment dispersion for a black matrix having high light-shielding property and high insulation property, and a pigment dispersion resist composition for a black matrix containing the same.

Claims (4)

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 based on 100 parts by mass of the acidic carbon black. ~50 parts by mass. The pigment dispersion for a black matrix according to the first aspect of the invention, wherein the polyfunctional epoxy compound has a selected from the group consisting of a diphenylmethane skeleton, a dinaphthylmethane skeleton, and a third An epoxy compound of at least one of a skeleton and a biphenyl skeleton. The pigment dispersion for a black matrix according to claim 1 or 2, wherein the polyfunctional epoxy compound is a tetrafunctional or higher epoxy compound. A pigment dispersion-dispersing composition for a black matrix, which comprises the pigment dispersion for a black matrix, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator according to any one of claims 1 to 3.