KR20070095425A - Photocurable resin composition for forming black matrix, photosensitive film using the same, method for forming black matrix, black matrix and plasma display panel having the black matrix - Google Patents

Abstract

Provided is a photocurable resin composition which can perform fine patterning and can form a black matrix exhibiting a satisfactory black color, and further can be developed with water. The above photocurable resin composition comprises (A) a powder of a metal having an ionic valence number of 2 or greater which is converted to a black material by oxidation, and (B) an organic component comprising (i) a water-soluble cellulose derivative, (ii) a photo-polymerizable monomer, (iii) an acrylic resin having a hydroxy group and (iv) a photopolymerization initiator. The above metals having an ionic valence number of 2 or greater include at least one selected from the group consisting of copper, iron and cobalt.

Description

PHOTOCURABLE RESIN COMPOSITION FOR FORMING BLACK MATRIX, PHOTOSENSITIVE FILM USING THE SAME, METHOD FOR FORMING BLACK MATRIX, BLACK MATRIX AND PLASMA DISPLAY PANEL HAVING THE BLACK MATRIX}

The present invention relates to a photocurable resin composition for forming a black matrix. Moreover, it is related with the photosensitive film using this composition, the formation method of a black matrix, a black matrix, and the plasma display panel which has this black matrix.

Currently, liquid crystal displays, electroluminescence, light emitting diodes (LEDs), fluorescent displays (VFDs), plasma displays (PDPs), field emission displays (FEDs), and digital displays as flat panel displays. Micromirror devices (DMDs) and the like are known.

A color display in which these displays are colorized is to generate three primary colors of red, blue, and green light for each pixel, and to control the contrast of each pixel to express a change in color. In such a color display, a black matrix is formed in order to prevent the fall of contrast and color purity. This black matrix is naturally required to be excellent in light shielding properties.

In particular, PDPs are relatively simple in structure and easy to be enlarged, have high display quality due to their self-luminous type, and can also display colors. ought. Such PDPs are generally provided with barrier ribs formed of insulating material on the surface of the substrates facing each other, partitioned into a plurality of display cells, a phosphor layer is formed within the cells, and pattern electrodes are provided to surround each cell. do. The screen display is realized by generating a plasma discharge by applying a voltage to the pattern electrode, and emitting each of the light emitting layers by the action of ultraviolet rays by the plasma discharge. To this end, electrodes, resistors, dielectrics, etc. for generating plasma are provided in the substrate or the cell. In order to refine this PDP, it is necessary to precisely prepare partitions, electrodes, resistors, dielectrics, phosphors, color filters, and black matrices constituting the PDP.

Conventionally, the photosensitive resin composition for light shielding film formation used for formation of black matrices, such as a CRT display and a liquid crystal display panel, was used for formation of the said black matrix. However, in the production of PDP, there is a high temperature baking step, and carbon black contained in the photosensitive resin composition for forming a light shielding film is decomposed at this step to form a satisfactory black matrix. Then, the photosensitive resin composition for light shielding film formation which mix | blended copper oxide and other metal oxides, such as iron, as a light-shielding material is proposed (for example, refer patent document 1).

Moreover, although it does not aim at formation of a black matrix, the photosensitive paste which contains low melting glass and changes to black after baking is also disclosed (for example, refer patent document 2).

Patent Document 1: Japanese Patent Publication No. 1997-160243

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-347394

Problems to be Solved by the Invention

However, it is necessary to form a fine black matrix pattern by the advancement of technical requirements, and when forming a black matrix using the resin composition like patent document 1, since it already contains black fine particles, light transmittance is low and the required fine It was difficult to form a black matrix pattern.

Further, in Patent Document 2, since the characteristic of changing to black is achieved by using a compound which is converted into a black oxide by firing such as, for example, an organometallic compound nickel acetylacetonate, it is expensive and more inexpensive. It was required. In the case where such bivalent or more metals such as copper, iron, and cobalt are used as metal powders, application patterning can be performed because gelation is performed with a polymer having a carboxyl group in the side chain. There was a problem that there was not.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, first, when patterning, when the patterning was carried out about the material which has transparency, can form fine patterning, and is available cheaply, it is blackened by oxidation instead of the said organometallic compound. Consideration was given to the use of metal powder. Therefore, in practice, powders of metals having ionic valences of 2 or more, such as copper, iron, and cobalt, which have a characteristic of becoming black by oxidation, have oligomers having a carboxyl group, which is used as a photosensitive component, in the side chain ( The problem arises that the coating patterning is not possible due to gelatin with oligomers or polymers. Therefore, the inventors examined photosensitive resins having the property of not gelling even when a powder of a metal having an ionic valence of 2 or more was used, and also examined the property of developing with water. As a result, the inventors have found that the above problems can be solved by combining a powder of a metal having two or more ionic valences blackened by oxidation and a specific resin component.

This invention is made | formed based on such knowledge and knowledge, The photocurable resin composition of this invention is a photocurable resin composition used for formation of a black matrix, (A) The ion valence which blackens by oxidation is 2 or more of metals. Powder, an organic component comprising (B) (i) a water-soluble cellulose derivative, (ii) a photopolymerizable monomer, (iii) an acrylic resin having a hydroxy group, and (iii) a photopolymerization initiator It is a photocurable resin composition for forming a black matrix.

Moreover, the photosensitive film of this invention consists of a photosensitive paste film obtained by forming into a film the said photocurable resin composition, and the protective film which protects this photosensitive paste film.

In addition, the black matrix of the present invention has an optical density (OD) of at least 3.0, wherein the photosensitive paste film is cured by firing after patterning.

Moreover, the black-matrix formation method of this invention uses the said photocurable resin composition, the photosensitive paste film forming process of forming a photosensitive paste film on a board | substrate, and after exposing the said photosensitive paste film, developing it with water, A black matrix having a pattern forming step of forming a predetermined pattern on the substrate, and a pattern firing and blackening step of curing, oxidizing and blackening the pattern obtained by the pattern forming step at a temperature of 1000 ° C. or lower in the presence of oxygen. Formation method.

Further, the plasma display of the present invention has a black matrix formed by using the black matrix forming method.

Effect of the Invention

According to the present invention, it is possible to provide a photocurable resin composition for forming a black matrix which is water developable, can form a fine pattern, and can form a black matrix having a sufficient black color at a low cost.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described.

The photocurable resin composition of this invention is a photocurable resin composition used for formation of a black matrix, Comprising: (A) Powder of the metal whose ionic valence blackens by oxidation is two or more, (B) (i) Water-soluble cellulose derivative And (ii) an organic component comprising a photopolymerizable monomer, an acrylic resin having a (hydroxyl) hydroxyl group, and (iii) a photopolymerization initiator.

The metal having two or more ionic valences blackened by oxidation used in the present invention is not particularly limited as long as it is blackened by oxidation by firing after pattern formation, but copper, iron, and cobalt are preferred, and copper is more preferable. desirable. It is preferable that a black matrix is insulating, and when copper is used, copper oxide obtained by oxidation is more preferable because it is insulating. Moreover, copper is preferable also at the point of being cheap and easy to purchase. The metal whose ionic valence blackens by these (A) oxidation is 2 or more may be used independently, and may be used in combination of multiple.

As a shape of the said metal powder, although a particulate form, spherical shape, a flake shape, etc. are mentioned specifically, it is not limited to these especially, A different shape may be sufficient. The metal powder may be a metal powder having a single shape alone, or may be a mixture of two or more kinds of metal powders. The particle diameter of the said metal powder is 0.01-100 micrometers, Preferably it is 0.1-30 micrometers, More preferably, it is the range of 0.5-10 micrometers. This is because when the average particle diameter exceeds 100 µm, it is difficult to form a fine and high-precision pattern. When the average particle diameter is less than 0.01 µm, light causes diffuse reflection and does not pass the pattern light.

The organic component used for this invention consists of (i) water-soluble cellulose derivative, (ii) photopolymerizable monomer, (iii) acrylic resin which has a hydroxyl group, and (iii) photoinitiator.

As said (i) water-soluble cellulose derivative, a well-known thing can be used, Although it does not specifically limit, For example, carboxymethylcellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, ethyl hydroxy Ethyl cellulose, carboxymethyl ethyl cellulose, hydroxypropyl methyl cellulose, etc. are mentioned. You may use these individually or in mixture of 2 or more types.

Moreover, as said (ii) photopolymerizable monomer, it is well-known and it does not specifically limit as a well-known photopolymerizable monomer, For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene Glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, pentaerythritol Pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol Tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol acrylate Glycerol methacrylate, cardo epoxy diacrylate, fumaric acid ester in which (meth) acrylate of these exemplary compounds is replaced by fumarate, Itaconic acid ester (itaconic acid ester) replaced with itaconate (itaconate), maleic acid ester (maleic acid ester) replaced with maleate, etc. are mentioned.

(Iii) As acrylic resin which has a hydroxyl group, the copolymer obtained by making the monomer which has a hydroxyl group as a main copolymerizable monomer, and superposing | polymerizing the other monomer copolymerizable with them as needed is mentioned. As the monomer having a hydroxyl group, monoesters of acrylic acid or methacrylic acid and mono alcohols having 1 to 20 carbon atoms are suitable. For example, hydroxymethyl acrylate ), Hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy Hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4- Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. are mentioned, Moreover, acrylic acid or methacrylic acid, and C1-C10 Glycol monoesters, glycerol acrylate, glycerol methacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate, ε-capro And epoxy ester compounds such as lactone-modified hydroxylethyl acrylate, ε-caprolactone-modified hydroxylethyl methacrylate, and 2-hydroxy-3-phenoxypropyl acrylate.

As another monomer copolymerizable with the monomer which has the said hydroxyl group, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl Acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate sec-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, 2, 2, 2-trifluoromethyl acrylate (2, 2, 2-trifluoromethyl acrylate), 2, 2, 2-trifluoromethyl Styrene, such as (alpha), (beta)-unsaturated carboxylic acid ester (styrene), styrene, (alpha) -methylstyrene, p-vinyltoluene, such as methacrylate, is mentioned preferably. . Moreover, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, etc. can also be used. These may be used independently and may be used in combination of 2 or more type.

The photocurable resin composition of this invention contains the acrylic resin which has the said (iii) hydroxyl group, and developability improves and can form an image with high precision.

The ratio of (i) water-soluble cellulose derivative and (ii) photopolymerizable monomer in the photocurable resin composition of the present invention is 10-50 parts by mass of (i) water-soluble cellulose derivative, based on 100 parts by mass of the total of the two components, Ii) 90-50 mass parts of photopolymerizable monomers, Preferably it is 20-40 mass parts of (i) water-soluble cellulose derivatives, (ii) 80-60 mass parts of photopolymerizable monomers, More preferably, (i) water-soluble cellulose The range of 25-35 mass parts of derivatives, and 75-65 mass parts of (ii) photopolymerizable monomers is good. When each component exists in the said range, the required pattern formation precision is obtained and sufficient transmittance | permeability with respect to an actinic light is obtained. For example, since the photopolymerizable monomer (ii) is 50 mass parts or more, the photopolymerization property at the time of image development is obtained, and sufficient image forming ability is obtained practically. Moreover, the resolution of a fine image improves that a photopolymerizable monomer is 90 mass parts or less.

The ratio of (i) the water-soluble cellulose derivative and the acrylic resin having the (iii) hydroxyl group is 30 to 90 parts by mass of the (i) water-soluble cellulose derivative, and (iii) the hydroxide relative to a total of 100 parts by mass of the two components. 70-10 mass parts of acrylic resin which has a hydroxyl group, Preferably (i) 40-80 mass parts of water-soluble cellulose derivatives, 60-20 mass parts of acrylic resin which has (iii) hydroxyl groups, More preferably, The range of 50-30 mass parts of (i) 50-70 mass parts of water-soluble cellulose derivatives, and (i) hydroxyl group which has a hydroxyl group is good. The required pattern formation precision is obtained by having each component in the said range, and sufficient transmittance | permeability with respect to an active light ray is obtained. For example, (10) development resistance improves when acrylic resin which has a hydroxyl group is 10 mass parts or more. In the case of 90 mass parts or less, developability can be improved and the development residue can be prevented.

(Iii) As the photopolymerization initiator, generally known ones can be used, for example, benzophenones, benzoin, benzoin alkyl ethers, and acetophenones. , Aminoacetophenones, benzils, benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones, ketals, thioxanthones And the like. As a specific example, 2, 4-bis- trichloromethyl-6- (3-bromo- 4-methoxy) phenyl-s-triazine, 2, 4-bis- trichloromethyl-6- (2-bromo) -4 -methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis -Trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine (2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s- triazine), 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2, 4-diethyl thioxanthone, 2, 4- dimethyl thioxanthone, 2-chloro- thioxanthone, 1-chloro- 4-propoxy thioxanthone, 3, 3- dimethyl- 4-methoxy benzophenone , Benzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid methyl, 4-dimethylamino eye Ethyl benzoate, 4-dimethylamino benzoate, 4-dimethylamino benzoic acid-2-ethylhexyl, 4-dimethylamino benzoic acid-2-isoamyl, 2,2-diethoxyacetophenone, benzyl dimethyl ketal, benzyl-β- Methoxyethyl acetal, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzomonobenzoic acid methyl, bis (4-dimethylaminophenyl) ketone, 4, 4'-bis Diethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, p-dimethylaminoacetophenone, p- tert-butyl trichloroacetophenone, p-tert-butyl dichloroacetophenone, Thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzosuberone, (alpha), (alpha) -dichloro- 4-phenoxyacetophenone, pentyl 4- dimethylamino benzoate, 2 -(O-chlorophenyl) -4, 5-diphenyl imidazolyl dimer, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Said photoinitiator (i) is suitably used in the range of 0.1-10 mass parts with respect to 100 mass parts of total amounts of (i) water-soluble cellulose derivative and (iv) photopolymerizable monomer, More preferably, the range of 0.2-5 mass parts is used suitably. do. (Iii) When 0.1 mass part or more of photoinitiators are practically sufficient sclerosis | hardenability is obtained. Moreover, when (iii) the photoinitiator is 10 mass parts or less, the failure of bottom hardening by excessive absorption of an initiator can be prevented.

The photocurable resin composition of this invention does not have an oligomer or a polymer which has a carboxyl group in a side chain. Therefore, gelation does not occur even when a powder of a metal having an ionic valence of 2 or more is used. Moreover, since it can develop with water, there is little influence on the environment. Moreover, compared with alkali developing type photocurable resin composition, it is excellent in storage stability. It is considered that there is little acid component contained in a composition.

In addition to the above, the photocurable resin composition of the present invention, if necessary, additive components such as ultraviolet absorbers, sensitizers, sensitizers, polymerization inhibitors, plasticizers, thickeners, organic solvents, dispersants, antifoaming agents, organic or inorganic precipitation inhibitors, etc. Can be added.

The sensitizer is added to improve the sensitivity, but specific examples thereof include 2,4-diethylthioxanthone, isopropyl thioxanthone, and 2,3-bis (4-diethylaminobenzal). ) Cyclopentanone, 2, 6-bis (4-dimethylaminobenzal) cyclohexanone, 2, 6-bis (4-dimethylaminobenzal)-4-methylcyclohexanone, Michler's ketone, 4 , 4-bis (diethylamino) -benzophenone, 4, 4-bis (dimethylamino) chalcone (4, 4-bis (dimethylamino) chalcone), 4, 4-bis (diethylamino) chalcone, p-dimethyl Aminocinnamylidene indanone (p-dimethylaminocinnamylidene indanone), p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonnaphthothiazole, 1, 3-bis (4-dimethylaminobenzal) Acetone, 1, 3-carbonyl-bis (4-diethylaminobenzal) acetone, 3, 3-carbonyl-bis (7-diethylaminocumarin) (3, 3-carbo nyl-bis (7-diethylaminocumarine), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, dimethylamino benzoate isoamyl, Diethylamino benzoic acid isoamyl, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthio tetrazole, etc. are mentioned, These can be used 1 type, or 2 or more types.

Moreover, although a polymerization inhibitor is added in order to improve the thermal stability at the time of storage, as a specific example, hydroquinone, the monoester compound of hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-t -Butyl catechol, N-phenylnaphthylamine, 2, 6-di-t-butyl- p-methylphenol, chloranil, pyrogallol, etc. are mentioned.

Moreover, as a plasticizer for improving the followability to a board | substrate, a dibutyl phthalate (DBP), a dioctyl phthalate (DOP), a dicyclohexyl phthalate, polyethyleneglycol, glycerin, dibutyl tartrate, etc. are mentioned specifically ,.

Specific examples of the antifoaming agent include alkylene glycol-based, silicone-based, and higher alcohol-based antifoaming agents such as polyethylene glycol (molecular weight 400 to 800), and the voids after firing can be reduced by reducing bubbles in the paste or film. .

In addition, the photocurable resin composition of this invention may contain (C) glass powder as a binder. The glass powder (C) is not particularly limited as long as it satisfies the necessary transparency to the exposure light source. Specific examples of the (C) glass powder include PbO-SiO ₂ -based, PbO-B ₂ O ₃ -SiO ₂ -based, ZnO-SiO ₂ -based, ZnO-B ₂ O ₃ -SiO ₂ -based, and BiO-SiO. _And glass powders such as lead borosilicate glass, zinc borosilicate glass, bismuth borosilicate glass, and the like of the bisystem and the BiO-B ₂ O ₃ -SiO ₂ system.

Although the particle diameter of (C) glass powder is based on the shape of the pattern to produce, average particle diameter is 0.5-10 micrometers, Preferably 1-8 micrometers is used suitably. If the average particle diameter exceeds 10 µm, surface irregularities occur at the time of forming a high-precision pattern, which is not preferable. If the average particle diameter is less than 1 µm, fine cavities are formed during firing, which is not preferable because it causes insulation failure. As a shape of this (C) glass powder, spherical shape, a block shape, a flake shape, a dendrite shape, etc. are mentioned, It can be used individually or in combination of 2 or more types.

In the photocurable resin composition of the present invention, the ratio of the powder of the metal having two or more ionic valences to be blackened by oxidation (A) and (B) the organic component is based on 100 parts by mass of the total of the photocurable resin composition (A). 60 to 90 parts by mass of a powder of a metal having two or more ionic valences blackened by oxidation, and 10 to 40 parts by mass of an organic component (B), preferably two or more ionic valences blackened by oxidation (A) 65-85 mass parts of metal powders, 35-15 mass parts of (B) organic components, More preferably, 70-80 mass parts of powders of the metal whose ionic valence to blacken by (A) oxidation are two or more, (B) The organic component is 30-20 mass parts. (B) Since the organic component is 10 mass parts or more, practically sufficient photopolymerization is obtained and sufficient image formation can be performed. On the other hand, since (B) organic component is 40 mass parts or less, generation | occurrence | production of the pattern peeling after baking can be suppressed and it is preferable.

The photocurable resin composition of this invention is prepared by melt | dissolving or disperse | distributing in a solvent. As a solvent to be used, the affinity with the powder of the metal whose ionic valence blackening by (A) oxidation is two or more, and the solubility of (B) organic component are favorable, and moderate viscosity can be provided to curable resin composition, and it is dried It will not specifically limit, if it becomes easy to carry out evaporation removal by becoming. Specific examples of such a solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; n-pentanol and 4-methyl-2-pentanol (4-methyl-2-pentanol) Alcohols such as cyclohexanol and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene Ether alcohols such as glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; n-butyl acetate, amyl acetate Saturated aliphatic monocarboxylic acid alkyl esters such as; lactic acid esters such as ethyl lactate and lactic acid-n-butyl; methylcellosol Acetate (methylcellosolve acetate), ethyl cellosolve acetate, propyleneglycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 2-methoxybutyl acetate, 3 -Methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate (2-methyl-3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, 3-ethyl-3 Ether esters such as -methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, and 2-methoxypentyl acetate; and the like can be exemplified. These can be used individually or in combination of 2 or more types.

In order to keep the viscosity of curable resin composition in a preferable range, the said content rate of the said solvent is 300 with respect to 100 mass parts of total of the powder of the metal whose (A) ionizing blackening is two or more, and (B) organic component. Mass parts or less are preferable, More preferably, 10-70 mass parts and 25-35 mass parts are the most preferable.

The photosensitive film of this invention is produced as follows.

First, the said photocurable resin composition is formed into a film on a support film so that a dry film thickness may be set to 10-50 micrometers (coating and drying), and a photosensitive paste film is formed. As a support film to be used, the flexible film which consists of synthetic resin films, such as polyethylene terephthalate of 15-125 micrometers of thickness, polyethylene, polypropylene, polycarbonate, polyvinyl chloride, etc. is mentioned, for example. Can be. You may perform a mold release process to this support film so that transfer may become easy as needed. In application, it is preferable to use an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like. In particular, the roll coater is preferable because the film thickness is excellent in uniformity and a thick film can be formed efficiently.

Next, in order to stably protect the photosensitive paste film when the photosensitive paste film is not in use, a protective film is attached to obtain a photosensitive film. As this protective film, the polyethylene terephthalate film, the polypropylene film, the polyethylene film, etc. which are about 15-125 micrometers in thickness which coated or baked the silicon | silicone are suitable, for example. .

Next, the formation method of the black matrix using the curable resin composition of this invention is demonstrated. Image exposure is performed by irradiating curable resin composition layer formed by application | coating or transcription | transfer on a board | substrate through actinic light, such as an ultraviolet-ray, an excimer laser, an X-ray, an electron beam, through a mask. Next, development is carried out using water, and the unilluminated portion is dissolved and removed to form a pattern on the substrate and fire. Alternatively, a pattern is formed without exposing the entire surface without a mask and developing. Then, the pattern is baked and blackened in the presence of oxygen to form a black matrix.

When forming a higher precision pattern, a protective film is first removed from the photosensitive film using the said photosensitive film, a photosensitive paste film is transferred to a board | substrate, an image exposure or a whole surface exposure, and a support film is removed. Next, in the case of the photosensitive paste film | membrane image-exposed, it provides to a developing process and forms a pattern. In the case of the photosensitive paste film exposed to the entire surface, a cured film is formed without developing, and baked in the presence of oxygen.

As said board | substrate, the board | substrate which provided electrodes, such as a bus electrode, on the glass substrate, the board | substrate, a ceramic board | substrate, etc. are mentioned, for example. In the transfer of the photosensitive paste film, it is preferable that the photosensitive paste film is polymerized on the substrate surface and thermally compressed by a hot roll laminator or the like. In the thermocompression bonding, the surface temperature of the substrate is heated to 80 to 140 ° C, and the roll pressure is preferably in the range of 1 to 5 kg / cm ² and a moving speed of 0.1 to 10.0 m / min. The said board | substrate may be preheated, and a range of 40-100 degreeC is selected as a preheating temperature, for example. Moreover, as a radiation irradiation apparatus used by exposure, the ultraviolet irradiation apparatus generally used by the photolithography method, the exposure apparatus used when manufacturing a semiconductor, and a liquid crystal display device, etc. can be used.

As described above, the developing treatment (i) has a water-soluble cellulose derivative component and can be performed with water. 10-50 degreeC is preferable and, as for the temperature of water, 20-40 degreeC is more preferable. It is because developability will fall and developing residue will arise out of this range. In the development treatment, the development time, the development temperature, the development method (for example, the immersion method, the rocking method, the shower method, the spray method, the paddle method, etc.) and the development depending on the characteristics of the photosensitive paste film. The device etc. can be selected suitably. The photocurable resin composition of this invention can be easily developed with water, and can form the black matrix which does not have an environmental problem by an organic solvent or an aqueous alkali solution, or a bad influence to a human body, and has sufficient black.

As temperature used for the said baking, what is necessary is just the temperature which blackens the powder of the metal whose ionic valence blackens by blackening by (A) oxidation fully 2, and loses (B) organic component. Specifically, it is 400-1000 degreeC, Preferably it is 500-1000 degreeC, More preferably, it is the temperature range of 500-600 degreeC. It is because if it is less than 400 degreeC, the organic component (B) will not lose | disappear and if it exceeds 1000 degreeC, depending on a metal (for example, copper etc.), once the black metal turns into another color. Although baking time changes with temperature, it is 10 to 120 minutes, for example, when heating at normal temperature from 10 degree-C / min and heating at 500-600 degreeC.

The black matrix of the present invention obtained by the above method is characterized by having an optical density (OD value) of 3.0 or more.

Although the black matrix of the present invention is used as a material for manufacturing various displays such as plasma display panels, organic ELs, inorganic ELs, field emission displays, and the like, it is particularly suitable for use in PDPs. Can be.

The PDP of this invention contains the black matrix obtained by the black matrix formation method which consists of said photocurable resin composition. The PDP of this invention is manufactured by the conventional PDP manufacturing method. Specifically, components selected from barrier ribs, electrodes, resistors, dielectric layers, phosphors, and color filters are formed on a substrate such as a glass substrate by a known method, and the black matrix is a black matrix composed of the photocurable resin composition. PDP is manufactured by forming by a formation method.

<Example>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example. In addition, this invention is not limited to the following Example.

EXAMPLE 1

(1) Adjustment of Water Developing Resist Composition

(i) 22 parts by mass of hydroxypropylcellulose as the water-soluble cellulose derivative, 14 parts by mass of styrene / hydroxyethyl methacrylate = 55/45 (mass%) copolymer (Mw = 40000) as the acrylic resin, and a photopolymerization monomer As a 2-methacryloyloxyethyl 2-hydroxypropyl phthalate (brand name: HO-MPP, the Kyoi Chemical Co., Ltd. product) 63 mass parts, as a photoinitiator, 2, 2- dimethoxy- 2-phenylacetophenone (Product name IR-651, manufactured by Chiba Co., Ltd.) The water-developing resist composition was adjusted by mixing 1.0 parts by mass and 100 parts by mass of 3-methoxy 3-methylbutanol as a solvent by mixing with a mixing machine.

(2) Adjustment of photocurable resin composition

The photocurable resin composition was adjusted by kneading 50 mass parts of water developable resist compositions (solid content 50%) and 75 mass parts of copper powders (average particle diameter 1 micrometer) adjusted by said (1).

(3) Preparation of Photosensitive Film

The photocurable resin composition adjusted in the above (2) is applied onto a support film made of polyethylene terephthalate using a lip coater, and the coating film is dried at 100 ° C. for 6 minutes to completely remove the solvent. It removed and the 16-micrometer-thick photosensitive paste film | membrane was formed on the support film. Next, a 25 μm-thick polyethylene film was abutted on the photosensitive paste film to prepare a photosensitive film.

(4) Evaluation of the photosensitive film

The polyethylene film of the photosensitive film prepared in the above (3) was peeled off and laminated at 105 ° C by a hot roll laminator on a glass substrate previously heated to 80 ° C. The air pressure was 3 kg / cm ² , and the lamination speed was 1.0 m / min.

Next, the polyethylene terephthalate which is a support film was peeled off, and the ultraviolet-ray exposure was carried out with the irradiation amount of 500mJ / cm <^{2> with} an ultrahigh pressure mercury lamp through the test angle pattern mask on the photosensitive paste film. A pattern was formed by spraying for 30 seconds at a spray pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesiveness was evaluated, the minimum line width remaining was 30 μm. Moreover, when the pattern shape was observed by SEM, the trapezoidal pattern shape was obtained.

In order to evaluate the shape stability and blackness after pattern baking, the baking process heated at 1.0 degreeC / min in temperature rise speed, and hold | maintained at 580 degreeC for 30 minutes was performed. As a result, a black matrix having a good rectangular shape and having a sufficient black color with an OD value of 3.5 was formed.

EXAMPLE 2

A photosensitive film was produced in the same manner as in Example 1 except that the copper powder was changed to an iron powder (average particle size 1 μm). The polyethylene film of the prepared photosensitive film was peeled off and laminated at 105 ° C by a hot roll laminator on a glass substrate previously heated to 80 ° C. The air pressure was 3 kg / cm ² , and the lamination speed was 1.0 m / min.

Next, the polyethylene terephthalate which is a support film was peeled off, and the ultraviolet-ray exposure was carried out with the irradiation amount of 500mJ / cm <^{2> with} an ultrahigh pressure mercury lamp through the test angle pattern mask on the photosensitive paste film. A pattern was formed by spraying for 30 seconds at a spray pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesiveness was evaluated, the minimum line width remaining was 30 μm. Moreover, when the pattern shape was observed by SEM, the trapezoidal pattern shape was obtained.

In order to evaluate the shape stability and blackness after pattern baking, the baking process heated at 1.0 degreeC / min in temperature rise speed, and hold | maintained at 580 degreeC for 30 minutes was performed. As a result, a black matrix having a good rectangular shape and having a sufficient black color with an OD value of 3.5 was formed.

EXAMPLE 3

A photosensitive film was produced in the same manner as in Example 1 except that the copper powder was changed to cobalt powder (average particle size 1 μm). The polyethylene film of the prepared photosensitive film was peeled off and laminated at 105 ° C by a hot roll laminator on a glass substrate previously heated to 80 ° C. The air pressure was 3 kg / cm ² , and the lamination speed was 1.0 m / min. Subsequently, the polyethylene terephthalate which is a support film was peeled off, and the ultraviolet-ray exposure was carried out with the irradiation amount of 500mJ / cm <^2> by the ultrahigh pressure mercury lamp through the test pattern mask on the photosensitive paste film. The pattern was formed by spraying for 30 seconds at a spray pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesiveness was evaluated, the minimum line width remaining was 30 μm. Moreover, when the pattern shape was observed by SEM, the trapezoidal pattern shape was obtained.

In order to evaluate the shape stability and blackness after pattern baking, the baking process heated at 1.0 degreeC / min in temperature rise speed, and hold | maintained at 580 degreeC for 30 minutes was performed. As a result, a black matrix having a good rectangular shape and having a sufficient black color with an OD value of 3.5 was formed.

EXAMPLE 4

A photosensitive film was produced in the same manner as in Example 1 except that isobutyl methacrylate / hydroxyethyl acrylate = 90/10 (mass%) copolymer (Mw = 70000) was used as the acrylic resin. While peeling the polyethylene film of the produced photosensitive film, it laminated at 105 degreeC with the hot roll laminate on the glass substrate previously heated at 80 degreeC. The air pressure was 3 kg / cm ² , and the lamination speed was 1.0 m / min. Subsequently, polyethylene terephthalate as a support film was peeled off, and ultraviolet exposure was carried out with an irradiation amount of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp through a test pattern mask on a photosensitive paste film. The pattern was formed by spraying for 30 seconds using the injection pressure of 3 kg / cm <^2> using water of 30 degreeC of liquid temperature. When the adhesiveness was evaluated, the minimum line width remaining was 30 μm. Moreover, when the pattern shape was observed by SEM, the trapezoidal pattern shape was obtained.

In order to evaluate the shape stability and blackness after pattern baking, the baking process heated at 1.0 degreeC / min in temperature rise speed, and hold | maintained at 580 degreeC for 30 minutes was performed. As a result, a black matrix having a good rectangular shape and having a sufficient black color with an OD value of 3.5 was formed.

[Example 5]

The photocurable resin composition was kneaded by mixing 50 parts by mass of the water-developed resist composition (solid content 50%), 75 parts by mass of copper powder (average particle size 1 μm) and 10 parts by weight of glass frit, adjusted in Example 1 (1). Except having adjusted, it carried out similarly to Example 1, and manufactured the photosensitive film. It peeled at 105 degreeC with the hot roll laminator on the glass substrate previously heated at 80 degreeC, peeling the polyethylene film of the manufactured photosensitive film. The air pressure was 3 kg / cm ² , and the lamination speed was 1.0 m / min. Next, the polyethylene terephthalate which is a support film was peeled off, and the ultraviolet-ray exposure was carried out with the irradiation amount of 500mJ / cm <^{2> with} an ultrahigh pressure mercury lamp through the test pattern mask on the photosensitive paste film. The pattern was formed by spraying for 30 seconds using the injection pressure of 3 kg / cm <^2> using water of 30 degreeC of liquid temperature. When the adhesiveness was evaluated, the minimum line width remaining was 30 μm. Moreover, when the pattern shape was observed by SEM, the trapezoidal pattern shape was obtained.

In order to evaluate the shape stability and blackness after pattern baking, the baking process heated at 1.0 degreeC / min in temperature rise speed, and hold | maintained at 580 degreeC for 30 minutes was performed. As a result, a black matrix having a good rectangular shape and having a sufficient black color with an OD value of 3.5 was formed.

[Comparative Example 1]

(1) Adjustment of the water developing resist composition

22 parts by mass of hydroxypropyl cellulose as a water-soluble cellulose derivative, 14 parts by mass of styrene / hydroxyethyl methacrylate = 55/45 (mass%) copolymer (Mw = 40000) as an acrylic resin, and 2-methacryl as a photopolymerization monomer. As a oxyethyl 2-hydroxypropyl phthalate (brand name HO-MPP, the Kyoi Chemical Co., Ltd.) 63 mass parts, a photoinitiator, 2, 2- dimethoxy- 2-phenylacetophenone (brand name IR-651, Chiba) The water-developing resist composition was adjusted by mixing 1.0 mass part of Gaiji Co., Ltd.) and 100 mass parts of 3-methoxy 3-methylbutanol with a mixing machine for 3 hours as a solvent.

(2) Adjustment of Photosensitive Black Paste Composition

The photosensitive black paste composition was kneaded by kneading 50 parts by mass of the water-developed resist composition (solid content 50%) and 75 parts by mass of cobalt trioxide (Co ₃ O ₄ ) (average particle size 1 μm) as adjusted in the above (1). Adjusted.

(3) Preparation of Photosensitive Film

The photosensitive black paste composition adjusted in the above (2) was applied onto a support film made of polyethylene terephthalate using a lip coater, and the coating film was dried at 100 ° C. for 6 minutes to completely remove the solvent, and the thickness was 16 μm. A photosensitive black paste film was formed on the supporting film. Next, a 25 μm-thick polyethylene film was pressed on the photosensitive black paste film to prepare a photosensitive film.

(4) Evaluation of the photosensitive film

It peeled at 105 degreeC with the hot roll laminator on the glass substrate previously heated at 80 degreeC, peeling the polyethylene film of the photosensitive film manufactured by said (3). The air pressure was 3 kg / cm ² , and the lamination speed was 1.0 m / min.

Next, the polyethylene terephthalate which is a support film was peeled off, and the ultraviolet-ray exposure was carried out with the irradiation amount of 500mJ / cm <^{2> with} the ultrahigh pressure mercury lamp through the test pattern mask on the photosensitive black matrix film | membrane. The pattern was formed by spraying for 30 second by the injection pressure of 3 kg / cm <^2> using water of 30 degreeC of liquid temperature. When the adhesiveness was evaluated, the minimum line width remaining was 200 m. Moreover, when the pattern shape was observed by SEM, the pattern shape of the undercut inverted trapezoid was obtained.

In order to evaluate the shape stability and blackness after baking of a pattern, the baking process heated at 1.0 degreeC / min in temperature rise speed, and hold | maintained at 580 degreeC for 30 minutes was performed. As a result, although sufficient black was obtained by OD value 3.5, when the pattern shape after baking was observed by SEM, the pattern edge part peeled partially and could not form a fine pattern.

[Comparative Example 2]

(1) Adjustment of the water developing resist composition

0.4 equivalents to the carboxyl group of the copolymer consisting of 40% methacrylic acid, 30% methyl methacrylate and 30% styrene as a photosensitive polymer having a carboxyl group in the side chain instead of (i) a water-soluble cellulose derivative and (iii) an acrylic resin. A resist composition was adjusted in the same manner as in Example 1 except that 36 parts by mass of a polymer (weight average molecular weight 40,000 acid value 95) to which the glycidyl methacrylate was reacted was added.

(2) Adjustment of Photosensitive Black Paste Composition

The photosensitive black paste composition was adjusted by kneading 50 parts by mass of the resist composition (solid content 50%) and 75 parts by mass of copper powder (average particle size 1 μm) adjusted in the above (1), but the paste composition gelled and could not be applied. It was.

As mentioned above, since the photocurable resin composition of this invention is water developable, a fine pattern can be formed, and the black matrix which has sufficient black can be formed, it can be used for various displays. It is particularly useful for black matrices for PDPs.

Claims (6)

As a photocurable resin composition used for formation of a black matrix, (A) a metal powder having two or more ionic valences blackened by oxidation, (B) The photocurable resin composition for forming a black matrix containing the organic component which consists of (i) a water-soluble cellulose derivative, (ii) a photopolymerizable monomer, (v) an acrylic resin which has a hydroxyl group, and (v) a photoinitiator. The method of claim 1, A photocurable resin composition for forming a black matrix, wherein a metal powder having two or more ionic valences blackened by the oxidation is copper. The photosensitive film for black matrix formation which consists of a photosensitive paste film obtained by forming into a film the photocurable resin composition for black matrix formation of Claim 1, and the protective film which protects this photosensitive paste film. A photosensitive paste film forming step of forming a photosensitive paste film on a substrate using the photocurable resin composition for forming a black matrix according to claim 1, A pattern forming step of exposing the photosensitive paste film and then developing with water to form a predetermined pattern on the substrate; The black matrix formation method which has a pattern baking and blackening process which hardens, oxidizes, and blackens by baking at the temperature of 1000 degrees C or less in presence of oxygen, by baking the pattern obtained by the said pattern formation process. The black matrix whose optical density (OD) obtained by the black matrix formation method of Claim 4 is 3.0 or more. A plasma display panel having a black matrix formed using the method of forming a black matrix according to claim 4.