WO2006100825A1

WO2006100825A1 - 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

Info

Publication number: WO2006100825A1
Application number: PCT/JP2006/301149
Authority: WO
Inventors: Kiminori Oshio; Akira Kumazawa; Ryuma Mizusawa; Hitoshi Setsuda; Hiroyuki Obiya
Original assignee: Tokyo Ohka Kogyo Co., Ltd.
Priority date: 2005-03-18
Filing date: 2006-01-25
Publication date: 2006-09-28
Also published as: JP2006259421A; JP4197177B2; KR20070095425A; CN101142526A

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

Specification

Photo-curable resin composition for forming black matrix, photosensitive film using the same, method for forming black matrix,

Technical field

[0001] The present invention relates to a photocurable resin composition for forming a black matrix. The present invention also relates to a photosensitive film using the composition, a method for forming a black matrix, a black matrix, and a plasma display panel having the black matrix.

Background art

[0002] Currently, flat panel displays include liquid crystal displays, electroluminescence, light emitting diodes (LEDs), fluorescent display tubes (VFD), plasma displays (PDP), field emission displays (FED), and digital micromirror devices (DMD). ) Etc. are known.

[0003] A color display obtained by colorizing these displays produces three primary colors of red, blue, and green light for each pixel and expresses a change in color by controlling the brightness of each pixel. In such a color display, a black matrix is formed to prevent a decrease in contrast and color purity. Naturally, this black matrix is required to have excellent light shielding properties.

[0004] In particular, PDPs have attracted a great deal of attention because they are relatively simple in structure and easy to increase in size, are self-luminous, have high display quality, and are capable of color display. Therefore, many proposals have been made. Such PDPs are generally divided into a large number of display cells by providing partition walls made of an insulating material on the surface of a substrate arranged oppositely, and a phosphor layer is formed in the cells so as to surround each cell. Is provided with a pattern electrode. The screen display is realized by generating plasma discharge by applying a voltage to the pattern electrode, and causing each of the light emitting layers to emit light by the action of ultraviolet rays by the plasma discharge. For this purpose, electrodes, resistors, dielectrics, etc. for generating plasma are provided in the substrate or cell. To make this PDP highly precise, The partition walls, electrodes, resistors, dielectrics, phosphors, color filters, and black matrix that make up these components must be made with high precision.

[0005] Conventionally, a photosensitive resin composition for forming a light shielding film used for forming a black matrix such as a CRT display or a liquid crystal display panel has been used for forming the black matrix. However, in the production of PDP, there is a high-temperature baking step, and in this process, the carbon black contained in the photosensitive resin composition for forming a light-shielding film is decomposed and it is difficult to form a satisfactory black matrix. Therefore, a light-shielding film-forming photosensitive resin composition in which copper oxide and another metal oxide such as iron are blended as a light-shielding material has been proposed (for example, see Patent Document 1).

[0006] A photosensitive paste that is not intended for forming a black matrix, but that contains a low-melting glass and changes to black after firing has also been disclosed (for example, (See Patent Document 2).

Patent Document 1: Japanese Patent Laid-Open No. 9 160243

Patent Document 2: JP 2000-347394

Disclosure of the invention

Problems to be solved by the invention

[0008] However, it is necessary to form a fine black matrix pattern due to the advancement of technical requirements. When a black matrix is formed using a resin composition such as Patent Document 1, it already contains black fine particles. Therefore, it is difficult to form a fine black matrix pattern that requires low light transmission.

[0009] Further, in Patent Document 2, the property of changing to black is achieved by using a compound that is converted into a black oxide by firing, such as an organometallic compound nickel acetyl cintonate, which is expensive and cheaper. Was demanded. In addition, when these bivalent or higher metals such as copper, iron and cobalt are used as metal powder, they will gel with a polymer having a carboxyl group in the side chain, so that coating patterning is not possible. I got it.

Means for solving the problem

[0010] In order to solve the above problems, the present inventors first have transparency during patterning. However, investigations have been made on substances that can form fine patterning and are available at low cost. Instead of using the above organometallic compounds, it is not sufficient to use metal powder that becomes black by oxidation. I got a discussion of heels. Therefore, when actually carried out, metal powders having an ionic valence of 2 or more, such as copper, iron, cobalt, etc., which have the property of becoming black when oxidized, are carboxyl groups used as photosensitive components in the composition. A problem arises in that coating patterning becomes impossible due to gelation with oligomers or polymers having a side chain. Therefore, the inventors examined a photosensitive resin having a characteristic that it does not gel even when a metal powder having an ionic valence of 2 or more is used, and further development with water is possible. We also examined the characteristic of being. As a result, the inventors have found that the above problem can be solved by combining a powder of a metal having an ionic valence of 2 or more, which is blackened by oxidation, and a specific resin component.

[0011] The present invention has been made on the basis of strong knowledge, and the photocurable resin composition of the present invention is a photocurable resin composition used for forming a black matrix, and comprises (A) oxidation. (B) (i) a water-soluble cellulose derivative, (ii) a photopolymerizable monomer, and (iii) an acrylic resin having a hydroxy group And (iv) a photocurable resin composition for forming a black matrix, which comprises an organic component comprising a photopolymerization initiator.

[0012] The photosensitive film of the present invention comprises a photosensitive paste film obtained by forming the photo-curable resin composition into a film, and a protective film for protecting the photosensitive paste film.

[0013] In addition, the black matrix of the present invention has an optical density (OD) of 3.0 or more obtained by curing the photosensitive paste film by baking after patterning.

[0014] In addition, the black matrix forming method of the present invention includes a photosensitive paste film forming step of forming a photosensitive paste film on a substrate using the photocurable resin composition, and exposing the photosensitive paste film. Then, a development process is performed with water to form a predetermined pattern on the substrate, and the pattern obtained in the pattern formation process is baked at a temperature of 1000 ° C. or less in the presence of oxygen. A black matrix forming method having a pattern baking and blackening step of curing and oxidizing to blacken [0015] In addition, the plasma display of the present invention has a black matrix formed by using the above black matrix forming method.

The invention's effect

[0016] According to the present invention, a photocurable resin composition for forming a black matrix capable of forming a fine black pattern that can be developed with water and capable of forming a black matrix at low cost is provided. can do.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] Hereinafter, embodiments of the present invention will be described.

The photocurable resin composition of the present invention is a photocurable resin composition used for forming a black matrix, and (A) a powder of a metal having an ionic valence of 2 or more that is blackened by oxidation; B) (i) a water-soluble cellulose derivative, (ii) a photopolymerizable monomer, (iii) an acrylic resin having a hydroxy group, and (iv) an organic component comprising a photopolymerization initiator .

[0018] The metal having an ionic valence of 2 or more that is blackened by oxidation used in the present invention is not particularly limited as long as it is blackened by oxidation by baking treatment after pattern formation. Among iron and cobalt, copper is more preferable. When copper that is preferably insulated is used for the black matrix, copper oxide obtained by oxidation is more preferable because it is insulative. Also, copper is preferable because it is inexpensive and easy to purchase. These (A) metals having an ionic valence of 2 or more that are blackened by oxidation may be used alone or in combination.

[0019] Specific examples of the shape of the metal powder include forces such as a granular shape, a spherical shape, and a flake shape. The shape is not particularly limited to these, and other shapes may be used. As the metal powder, a metal powder having a single shape may be used, or a mixture of two or more types of metal powder may be used. The average particle size of the metal powder is in the range of 0.01 to 100 μΐη, preferably in the range of 0.0 :! to 30 zm, more preferably in the range of 0.5 to 10 to 111. If the average particle size exceeds 100 111, it becomes difficult to form a fine and highly accurate pattern, and if the average particle size is less than 0.01 × m, the light is irregularly reflected and the pattern light cannot be transmitted.

[0020] The organic component used in the present invention includes (i) a water-soluble cellulose derivative, (ii) a photopolymerizable monomer, (iii) an acrylic resin having a hydroxy group, and (iv) initiation of photopolymerization. It consists of an agent. [0021] As the above-mentioned (i) water-soluble cellulose derivative, known ones can be used, and are not particularly limited, and examples thereof include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxy chineno metheno resenorelose, and hydroxypropino rescenole. Examples thereof include rosin, ethinorehydroxyethinorenorose, canoleboxymethinoreethinoresenorelose, hydroxypropinoremethinoresenorelose and the like. These may be used alone or in admixture of two or more.

[0022] The above (ii) photopolymerizable monomer may be a known photopolymerizable monomer, and is not particularly limited. For example, ethylene glycol ditalinate, ethylene glycol dimethacrylate, Ethylene glycol diatalylate, triethylene glycol dimetatalylate, trimethylol propane tritalylate, trimethylol propane trimethalylate, trimethylol ethane tritalylate, trimethylol ethane trimethacrylate, pentaerythritol diattalylate, pentaerythritol dimethylate Tatalylate, Pentaerythritol Tritalylate, Pentaerythritol Trimetatalylate, Pentaerythritol Tetratalylate, Pentaerythritol Tetrametatalylate, Dipentaerythritol Tet Laatalylate, Dipentaerythritol tetrametatalylate, Dipentaerythritol pentaatalylate, Dipentaerythritol Monopentamethacrylate, Dipentaerythritol Hexaatalylate, Dipentaerythritol Hexametatalylate, Glycerol Atallate, Glycerol metatalylate, hardened epoxy diatalylate, fumaric acid ester in which (meth) atalylate of these exemplified compounds is replaced with fumarate, itaconic acid ester in place of itaconate, maleic acid ester in place of maleate, etc. .

(Iii) The acrylic resin having a hydroxy group is obtained by polymerizing a monomer having a hydroxyl group as a main copolymerizable monomer and further copolymerizing with other monomers as necessary. And copolymers. The monomer having a hydroxyl group is preferably a monoester product of acrylic acid or methacrylic acid and a monoalcohol having 1 to 20 carbon atoms, such as hydroxymethyl acrylate, hydroxymethyl methacrylate, 2 —Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Butyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl Examples include chinoremethacrylate, 4-hydroxybutynoleatelate, 4-hydroxybutinoacrylate, and monoesterolates of acrylic acid or methacrylic acid with 1- to 10-carbon glycolate. Glycerololeatalylate, Glycellonoremetatalylate, Dipentaerythritolol monoatalylate, Dipentaerythritololmonometatalylate, _ε — Force Pro Lataton Modified Hydroxyethyl Atylate, ε — Force Prolatatone Examples thereof include epoxy ester compounds such as modified hydroxyl ether methacrylate and 2-hydroxy-3phenoxypropyl acrylate.

[0024] Other monomers copolymerizable with the monomer having a hydroxyl group include, for example, methyl acrylate, ethyl acetate, η-propyl acrylate, isopropyl acrylate, η butyl acrylate, isobutyl acrylate, sec Butyl Atylate, Cyclohexyl Atylate, 2-Ethylhexyl Atylate, Stearyl Atylate, Methyl Metatalylate, Ethyl Metatalylate, n-Propyl Metatalylate, Isopropyl Metatalylate, sec Propyl Metatalyl , N-butyl methacrylate, sec-butyl methacrylate, sec butyl methacrylate, cyclohexyl methacrylate, 2-ethyl hexyl methacrylate, sterol methacrylate, 2, 2, 2-trifanolate romethinolate , 2 Preferred examples include α, β unsaturated carboxylic acid esters such as 1,2,2-trifluoromethyl metatalylate, styrenes such as styrene, α-methyl styrene, and ρ butyltoluene. Further, acrylonitrile, methacrylonitrile, attalinoleamide, methacrylolamide, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, and the like can also be used. These may be used alone or in combination of two or more.

[0025] The photocurable resin composition of the present invention contains the above (iii) acrylic resin having a hydroxyl group, whereby the development resistance is improved and a highly accurate image can be formed.

[0026] The ratio of (i) the water-soluble cellulose derivative and (ii) the photopolymerizable monomer in the photocurable resin composition of the present invention is as follows: 10 to 50 parts by weight of the cellulose derivative, (ii) 90 to 50 parts by weight of the photopolymerizable monomer, preferably (i) 20 to 40 parts by weight of the water-soluble cellulose derivative, (ii) the photopolymerizable monomer It is preferable that the monomer is 80 to 60 parts by mass, more preferably (i) 25 to 35 parts by mass of the water-soluble cellulose derivative, and (ii) 75 to 65 parts by mass of the photopolymerizable monomer. Necessary pattern formation precision by each component being within the above range. Degree and sufficient permeability to actinic rays. For example, when (ii) the photopolymerizable monomer is 50 parts by mass or more, the photopolymerization necessary for development can be obtained, and practically sufficient image forming ability can be obtained. Further, when the photopolymerizable monomer is 90 parts by mass or less, resolution of a fine image is improved.

[0027] The ratio of (i) the water-soluble cellulose derivative and (iii) the hydroxyl group-containing acrylic resin is such that (i) the water-soluble cellulose derivative is 30 to 90 parts by mass with respect to 100 parts by mass of the total of the two components. Parts (iii) 70 to 10 parts by mass of an acrylic resin having a hydroxyl group, preferably (i) 40 to 80 parts by mass of a water-soluble cellulose derivative, and (iii) 60 to 80 parts of an acrylic resin having a hydroxyl group. 20 parts by mass, more preferably (i) 50 to 70 parts by mass of the water-soluble cellulose derivative and (iii) 50 to 30 parts by mass of the acrylic resin having a hydroxyl group. When each component is within the above range, the necessary pattern formation accuracy can be obtained, and sufficient transparency to actinic rays can be obtained. For example, (iii) Acrylic resin having a hydroxyl group When the strength is S10 parts by mass or more, development resistance is improved. In the case of 90 parts by mass or less, developability is improved and development residue can be prevented.

[0028] (iv) As the photopolymerization initiator, generally known photoinitiators can be used. For example, benzophenones, benzoins, benzoin alkyl ethers, acetophenones, aminoacetophenones, benzyl Benzoin alkyl ethers, benzylalkylketals, anthraquinones, ketals, thixanthones and the like. Specific examples are 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2,4_bis-trichloromethyl-6_ (2-bromo_4 —Methoxy) phenyl-1-s-triazine, 2,4-bis-trichloromethyl-1-6- (3-bromo-1-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2— Bromo-4-methoxy) styrylphenyl _ s-triazine, 2, 4, 6 _Trimethylbenzoyldiphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -1-2-hydroxy-2- _Methyl _ 1 _Propane _ 1 _one, 2, 4 _Jetylthioxanthone, 2, 4 _Dimethinorethioxanthone, 2 _Chroochi thioxanthone, 1 _Croca _4 _Propoxy thioxanthone, 3, 3— Dimethyl mono 4-methoxybenzo Enone, benzophenone, 1- (4-isopropylidene Rufue sulfonyl) Single hydroxy one 2-methylpropan-one 1-one, 1- (4-Dodeshirufe 1) 2-hydroxy-1 2_methylpropane_1_one, 4_benzoyl_4'_methyl dimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylmethylaminobenzoic acid, 4_dimethylaminobenzoic acid ethyl, 4 _Butyl dimethylaminobenzoate, 4 _Dimethylaminobenzoic acid-2-ethylhexyl, 4-dimethylaminobenzoic acid _2 _Isamyl, 2,2-jetoxyacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl cetylacetal, 1 _Finole 1, 2 _Propanedione _ 2 _ (ο _Ethoxycarbonyl) oxime, ο _Methyl benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4, 4'-bisger Tyramino benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzine Inisopropyl ether, benzoin η butyl ether, benzoin isobutyl ether, ρ dimethylaminoacetophenone, p-tert butyltrichloroacetophenone, p-tert butyldichloroacetophenone, thixanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, Examples include dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentinore-4 dimethylaminobenzoate, 2- (ο-clophenyl) 1,4,5 diphenylimidazolyl dimer, and the like. These can be used alone or in combination of two or more.

[0029] The above (iv) photopolymerization initiator comprises (i) a water-soluble cellulose derivative and (iv) a total of 100 parts by mass of the photopolymerizable monomer. A range of 0.2 to 5 parts by mass is preferably used. (Iv) When the photopolymerization initiator is 0.1 part by mass or more, sufficient curability for practical use can be obtained. In addition, (iv) when the photopolymerization initiator is 10 parts by mass or less, poor bottom curing due to excessive absorption of the initiator can be prevented.

[0030] The photo-curable resin composition of the present invention does not have an oligomer or a polymer having a carboxyl group in the side chain. Therefore, even if a metal powder having an ionic valence of 2 or more is used, gelation does not occur. In addition, because it can be developed with water, it has little impact on the environment. Furthermore, it is excellent in storage stability as compared with an alkali development type photocurable resin composition. This is probably because the acid component contained in the composition is small.

[0031] In addition to the above, the photocurable resin composition of the present invention may contain an ultraviolet absorber, a sensitizer, a sensitizer, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, if necessary. , Dispersant, antifoaming agent, yes Or additive components such as inorganic precipitation inhibitors can be added.

[0032] The above sensitizer is a force added to improve the sensitivity. Specific examples thereof include 2, 4 -jetylthioxanthone, isopropyl thixanthone, 2,3_bis (4-jetylamino benzal) cyclopenta Non, 2, 6_bis (4-dimethylaminobenzal) cyclohexanone, 2, 6_bis (4-dimethylaminobenzal) _4 Methylcyclohexanone, Michler's ketone, 4, 4_bis (jetylamino) ) One benzophenone, 4, 4_bis (dimethylamino) force rucon, 4, 4_bis (jetylamino) chalcone, p-dimethylaminocinnamylidene indanone, p dimethylaminobenzylidene indanone, 2- (p dimethylamino) Minophenyl rubiylene) Isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carborubibis (4 Jetylaminobenzal) Acetone, 3, 3-Carbonyl loops (7-Jetylaminocoumarin), N-Phenolux N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine , N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl dimethylaminobenzoate, 3-phenenole 5-benzoylthiotetrazole, 1-phenolinole 5-ethoxycarbonylthiotetrazole, and the like. Two or more types can be used.

[0033] In addition, a polymerization inhibitor is added to improve thermal stability during storage. Specific examples thereof include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, p_t-butyl. Catechol, N-phenylnaphthylamine, 2,6-di_t_butyl_p_methylphenol, chloranil, pyrogallol and the like.

[0034] Further, as plasticizers for improving the followability to the substrate, specifically, dibutyl phthalate (HDBP), dioctyl phthalate (DOP), dicyclohexyl phthalate, polyethylene glycol, glycerin, dibutyl tartrate Etc.

[0035] 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 bubbles in the paste or film It is possible to reduce vacancies after firing.

[0036] Further, the photocurable resin composition of the present invention contains (C) glass powder as a binder. Moyore. (C) The glass powder is not particularly limited as long as it satisfies the transparency required for the exposure light source. (C) Specific examples of the glass powder include PbO_SiO, PbO

— B〇Si 〇 series, Zn〇1 Si〇 series, Zn〇1 B〇1 Si〇 series, Bi〇1 Si〇 series, Bi〇1 B

Examples thereof include glass powders such as O—SiO-based lead borosilicate glass, zinc borosilicate glass, and bismuth borosilicate glass.

[0037] (C) As the particle size of the glass powder, a force average particle size of 0.5 to 10 x m, preferably 1 to 8 z m, is suitably used depending on the shape of the pattern to be produced. If the average particle size exceeds 10 μm, surface irregularities occur when forming a highly accurate pattern, and if the average particle size is less than 1 μm, fine cavities are formed during firing, which may cause insulation failure. . Examples of the shape of the (C) glass powder include a spherical shape, a block shape, a flake shape, a dendrite shape, and the like, and these can be used alone or in combination of two or more.

[0038] In the photocurable resin composition of the present invention, the ratio of (A) a metal powder having an ionic valence of 2 or more, which is blackened by oxidation, and (B) the organic component is the ratio of the photocurable resin composition. To 100 parts by mass of total, (A) 60-90 parts by mass of metal powder having an ionic valence of 2 or more that is blackened by oxidation, (B) 10-40 parts by mass of organic component, preferably (A) oxidation 65 to 85 parts by mass of metal powder having an ionic valence of 2 or more due to oxidization, (B) 35 to 15 parts by mass of organic component, more preferably (A) ionic valence to be blackened by oxidation Is 70-80 parts by mass of metal powder of 2 or more, and (B) the organic component is 30-20 parts by mass. (B) When the organic component is 10 parts by mass or more, a practically sufficient photopolymerizability can be obtained, and a sufficient image can be formed. On the other hand, since the organic component (B) is 40 parts by mass or less, the occurrence of pattern peeling after firing can be suppressed, which is preferable.

[0039] The photocurable resin composition of the present invention is prepared by dissolving or dispersing in a solvent. As the solvent to be used, (A) Affinity with a metal powder having an ionic valence of 2 or more, which is blackened by oxidation, and (B) Solubility of organic components are good. There is no particular limitation as long as it can impart an appropriate viscosity and can be easily evaporated and removed by drying. Specific examples of powerful solvents include ketones such as jetyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methylol 2-pentanol, cyclohexanol, and diacetone alcohol. ; Ethylene glycol monomethino ethenore, ethylene glycol mono methino ree noate, ethylene glycol mono chineno ethenore, propylene glyco no mono mono chineno ethenore, propylene glycol mono methino eno enoenore, diethylene Ether-based alcohols such as glyconolemonomethinoreethenole, diethyleneglycolenomonotinoreatenore, diethyleneglycolenoresinetinoreethenole, diethyleneglycol-l-deethylether; acetic acid _ n-butyl, amyl acetate Saturated aliphatic monocarboxylic acid alkyl esters such as lactic acid ethyl ester, lactic acid _n_butyl lactic acid esters, etc .; methyl cetyl sorb acetate, ethyl cetyl sorb acetate, propylene glycol monomethyl ether acetate, propylene N-glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 2-methybutynoacetate, 3-methoxybutynoacetate, 4-methoxybutynoacetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3 —Methoxybutyl acetate, 3-ethynoleate 3-Methoxybutynoleacetate, 2-ethoxybutynoleacetate, 4 ethoxy butyl / acetate, 4 propoxybutynoleacetate, ethers such as 2-methoxypentinorea acetate Examples thereof include esters. These can be used alone or in combination of two or more.

[0040] In order to maintain the viscosity of the curable resin composition within a suitable range, the content of the solvent is as follows: (A) a metal powder having an ionic valence of 2 or more that is blackened by oxidation and (B) an organic component More preferably, 300 parts by mass or less is more preferable, with 10 to 70 parts by mass and 25 to 35 parts by mass being most preferable with respect to 100 parts by mass.

[0041] The photosensitive film of the present invention is produced as follows.

First, a photosensitive paste film is prepared by forming (applying and drying) the photocurable resin composition on a support film so as to have a dry film thickness of 10 to 50 μm. Examples of the supporting film to be used include a flexible film made of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polychlorinated butyl having a film thickness of 15 to 125 zm. If necessary, this support film may be subjected to a release treatment so that transfer is easy. Also, when applying, applicator, bar ¹ ~ ¹ ~ wire ¹ ~ wire "~ ¹ ~ ¹ ~ ¹ ~ mouth" ~ Nore ¹ ~ ¹ ~ force '~ Tenflo ¹ ~ ¹ ~ ¹ ~ ¹ ~ In particular, the roll coater has excellent film thickness uniformity, and a thick film is effective. Since it can form efficiently, it is preferable.

Next, in order to stably protect the photosensitive paste film when the photosensitive paste film is not used, a protective film is attached to obtain a photosensitive film. As this protective film, for example, a polyethylene terephthalate film, a polypropylene film, a polyethylene film having a thickness of about 15 to 125 zm coated or baked with silicone is suitable.

[0043] Next, a method for forming a black matrix using the curable resin composition of the present invention will be described. The curable resin composition layer formed on the substrate by coating or transfer is exposed to an image by irradiating an active ray such as ultraviolet ray, excimer laser, _χ ray, electron beam through a mask. Next, development processing is performed using water, and unirradiated portions are dissolved and removed to form a pattern on the substrate, followed by baking. Alternatively, the entire surface is exposed without a mask and a pattern is formed without developing, and it is baked and blackened in the presence of oxygen to form a black matrix.

[0044] In the case of forming a pattern with higher accuracy, the above-mentioned photosensitive film is used. First, the protective film is removed from the photosensitive film, the photosensitive paste film is transferred to the substrate, and image exposure or overall exposure is performed. Remove the support film. Next, in the case of the photosensitive paste film subjected to image exposure, it is subjected to a development process to form a pattern. In the case of a photosensitive paste film that has been exposed to the entire surface, a cured film is formed without developing, and is fired in the presence of oxygen.

[0045] Examples of the substrate include a glass substrate, a substrate in which an electrode such as a bus electrode is provided on the glass substrate, and a ceramic substrate. In the transfer of the photosensitive paste film, it is preferable that the photosensitive paste film is superposed on the substrate surface and thermocompression bonded with a hot roll laminator or the like. Thermocompression bonding is preferably performed at a substrate surface temperature of 80 to 140 ° C, roll pressure:! To 5 kg / cm ² , and moving speed of 0.1 to 10 OmZ. . The substrate may be preheated. As the preheating temperature, for example, a range of 40 to 100 ° C. is selected. Furthermore, as a radiation irradiation apparatus used for exposure, an ultraviolet irradiation apparatus generally used in a photolithography method, an exposure apparatus used when manufacturing semiconductors and liquid crystal display devices, and the like are used. be able to.

[0046] As described above, the development processing is carried out with water because (i) it has a water-soluble cellulose derivative component. Can be. The water temperature is preferably 10-50 ° C force S, more preferably 20-40 ° C force S. If it is out of this range, developability deteriorates and a development residue is generated. In the development process, depending on the characteristics of the photosensitive paste film, development time, development temperature, development method (eg, dipping method, rocking method, shower method, spray method, paddle method, etc.), development A device or the like can be selected as appropriate. The photocurable resin composition of the present invention can be easily developed with water, and can form a black matrix having sufficient blackness without causing environmental problems or adverse effects on the human body due to organic solvents or aqueous alkali solutions.

[0047] The temperature used for the baking is a temperature at which (A) a metal powder having an ionic valence of 2 or more that is blackened by oxidation is sufficiently blackened, and (B) is a temperature at which the organic component is burned off. That ’s ίmayyo. Specific white birch (ko (boiled, 400 ~: 1000 ^o C, preferably ryoma 500 ~ 1000 ^o C, more preferably ryah 500 ~ 600 ° C. If less than 400 ° C, (B) organic component) This is because some metals (for example, copper, etc.) change the color of the black metal to a different color when the temperature exceeds 1000 ° C. From 10 to 120 minutes when heated at a heating rate of 10 ° C / min and calcined at 500 to 600 ° C.

[0048] The black matrix of the present invention obtained by the above method has an optical density (OD value) of 3.

It is 0 or more.

[0049] The black matrix of the present invention can be suitably used for a power used as a material for producing various displays such as a plasma display panel, an organic EL, an inorganic EL, and a field emission display, particularly for a PDP.

[0050] The PDP of the present invention includes a black matrix obtained by the method for forming a black matrix comprising the photocurable resin composition. The PDP of the present invention is manufactured by a normal PDP manufacturing method. Specifically, a constituent element selected from a partition, an electrode, a resistor, a dielectric layer, a phosphor, and a color filter is formed on a substrate such as a glass substrate by a known method, and the black matrix is the photocurable resin composition. The PDP is manufactured by forming the black matrix using the method.

Example

[0051] Hereinafter, the present invention will be described in more detail based on examples. The present invention is not limited to the following examples. [Example 1]

(1) Preparation of water-developable resist composition

(i) Hydroxypropyl cellulose 22 parts by weight as water-soluble cellulose derivative, Styrene Z hydroxyethyl methacrylate = 55 Z45 (mass%) copolymer (Mw = 40000) 14 parts by weight, photopolymerization monomer 2-Methacryloyloxetyl 2-Hydroxypropyl phthalate (trade name: HO_MPP, manufactured by Kyoeisha Chemical Co., Ltd.) 63 parts by mass, 2,2-dimethoxy-1-2-phenylacetophenone (product) Name IR-651, manufactured by Ciba Gaigi Co., Ltd.) 1. A water-developing resist composition was prepared by mixing 0 parts by mass and 100 parts by mass of 3-methoxy 3-methylbutanol as a solvent with a force stirrer for 3 hours.

[0053] (2) Preparation of photocurable resin composition

A photocurable resin composition obtained by kneading 50 parts by mass of the water-developable resist composition (solid content 50%) prepared in (1) above and 75 parts by mass of copper powder (average particle size 1 μm). Adjusted.

[0054] (3) Production of photosensitive film

The photocurable resin composition prepared in (2) above 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. A photosensitive paste film having a thickness of 16 μΐη was formed on a support film. Next, a 25 μm thick polyethylene film was laminated on the photosensitive paste film to produce a photosensitive film.

[0055] (4) Evaluation of photosensitive film

While peeling the polyethylene film of the photosensitive film produced in (3) above, it was laminated at 105 ° C. with a hot roll laminator on a glass substrate that had been heated to 80 ° C. in advance. The air pressure was 3 kg / cm ² and the laminating speed was 1. Om / min.

Subsequently, polyethylene terephthalate as a support film was peeled off, and ultraviolet light exposure was performed on the photosensitive paste film through a test angle pattern mask with an ultrahigh pressure mercury lamp at an irradiation dose of 500 mj / cm ² . A pattern was formed by performing spray development for 30 seconds at a spraying pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesion was evaluated, the remaining minimum line width was 30 μΐη. Also, when the pattern shape was observed with SEM, the trapezoidal pattern shape was Obtained.

In order to evaluate the shape stability and blackness after pattern firing, a firing process was performed by heating at a heating rate of 1.0 ° C / min and holding at 580 ° C for 30 minutes. As a result, a black matrix having a good rectangular pattern shape and sufficient blackness with a D 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 iron powder (average particle size 1 β m). While peeling off the polyethylene film of the produced photosensitive film, it was laminated at 105 ° C. with a hot roll laminator on a glass substrate that had been heated to 80 ° C. in advance. The air pressure was 3 kg / cm ² and the laminating speed was 1 · Om / min.

Subsequently, polyethylene terephthalate as a support film was peeled off, and ultraviolet light exposure was performed on the photosensitive paste film through a test angle pattern mask with an ultrahigh pressure mercury lamp at an irradiation dose of 500 mj / cm ² . A pattern was formed by performing spray development for 30 seconds at a spraying pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesion was evaluated, the remaining minimum line width was 30 μΐη. When the pattern shape was observed with SEM, a trapezoidal pattern shape was obtained.

[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). While peeling off the polyethylene film of the produced photosensitive film, it was laminated at 105 ° C. with a hot roll laminator on a glass substrate that had been heated to 80 ° C. in advance. The air pressure was 3 kg / cm ² and the laminating speed was 1. Om / min. Subsequently, the polyethylene terephthalate as a support film was peeled off, and the photosensitive paste film was exposed to ultraviolet rays at an irradiation dose of 500 mj / cm ² with a super high pressure mercury lamp through a test angle pattern mask. Spray for 30 seconds at an injection pressure of 3 kg / cm ² using a water solution temperature 30 ° C Development was performed to form a pattern. When the adhesion was evaluated, the remaining minimum line width was 30 μm. When the pattern shape was observed with SEM, a trapezoidal pattern shape was obtained.

[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 off the polyethylene film of the produced photosensitive film, it was laminated at 105 ° C. with a hot roll laminator on a glass substrate that had been heated to 80 ° C. in advance. The air pressure was 3 kg / cm ² and the laminating speed was 1. Om / min. Subsequently, the support film, polyethylene terephthalate, was peeled off, and the photosensitive paste film was exposed to ultraviolet light at a dose of 500 mj / cm ² with a super high pressure mercury lamp through a test angle pattern mask. A pattern was formed by spray development for 30 seconds at a spraying pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesion was evaluated, the minimum remaining line width was 30 / m. In addition, when the pattern shape was observed by SEM, a trapezoidal pattern shape was obtained. To evaluate the shape stability and blackness after pattern firing, the film was heated at a heating rate of 1.0 ° C / min. A baking treatment was performed for 30 minutes at ° C. As a result, a black matrix having a good rectangular pattern shape and sufficient blackness with a D value of 3.5 was formed.

[Example 5]

50 parts by weight of the water-developable resist composition (solid content 50%) prepared in Example 1 (1), 75 parts by weight of copper powder (average particle size 1 μm), and 10 parts by weight of glass frit were mixed. A photosensitive film was produced in the same manner as in Example 1 except that the photocurable resin composition was adjusted by kneading. While peeling off the polyethylene film of the manufactured photosensitive film, preheat it to 80 ° C. It was laminated at 105 ° C. with a hot roll laminator on a heated glass substrate. The air pressure was 3 kg / cm ² and the laminating speed was 1. Om / min. Subsequently, the polyethylene terephthalate as a support film was peeled off, and the photosensitive paste film was exposed to ultraviolet rays at a dose of 500 mj / cm ² with an ultrahigh pressure mercury lamp through a test angle pattern mask. Using water at a liquid temperature of 30 ° C, spray development was performed at a spraying pressure of 3 kg / cm ² for 30 seconds to form a pattern. When the adhesion was evaluated, the remaining minimum line width was 30 zm. When the pattern shape was observed with SEM, a trapezoidal pattern shape was obtained.

In order to evaluate the shape stability and blackness after pattern firing, a firing process was performed by heating at a heating rate of 1.0 ° C / min and holding at 580 ° C for 30 minutes. As a result, a black matrix having a good rectangular pattern shape and sufficient blackness with a D value of 3 and 5 is formed.

[Comparative Example 1]

(1) Preparation of water-developable resist composition

Hydroxypropyl cellulose 22 parts by weight water-soluble cellulose derivatives, styrene / hydroxyethyl E chill meth Tari rate = 55/45 (mass ^_0/0) copolymer acrylic榭fat (Mw = 40000) 14 parts by weight of a photopolymerization monomer 2-Methacryloyloxetyl 2-hydroxypropyl phthalate (trade name HO-MPP, manufactured by Kyoeisha Chemical Co., Ltd.) 63 parts by mass, 2,2-dimethoxy-1-phenylacetofu as a photopolymerization initiator Enon (trade name IR-651, manufactured by Ciba Gaigi Co., Ltd.) 1. Water development resist composition by mixing 0 parts by mass and 100 parts by mass of 3-methoxy 3-methylbutanol as a solvent with a force stirrer for 3 hours. I adjusted things.

[0061] (2) Preparation of photosensitive black paste composition

50 parts by mass of the water-developable resist composition (solid content 50%) prepared in (1) above and 75 parts by mass of black fine particles of cobalt trioxide (Co 2 O 3) (average particle size lxm) were kneaded. To do

3 4

Thus, a photosensitive black paste composition was prepared.

[0062] (3) Production of photosensitive film

The photosensitive black paste composition prepared in (2) above 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. 16 μm thick photosensitive black paste film on support film Formed. Next, a 25 μm thick polyethylene film was laminated on the photosensitive black paste film to produce a photosensitive film.

[0063] (4) Evaluation of photosensitive film

Subsequently, the polyethylene terephthalate as a supporting film was peeled off, and the photosensitive black matrix film was exposed to ultraviolet rays at an irradiation dose of 500 mj / cm ² with a super high pressure mercury lamp through a test angle pattern mask. A pattern was formed by spray development for 30 seconds at a spraying pressure of 3 kg / cm ² using water at a liquid temperature of 30 ° C. When the adhesion was evaluated, the minimum remaining line width was 200 / im. In addition, when the pattern shape was observed by SEM, an inverted trapezoidal pattern shape with an under force was obtained.

In order to evaluate the shape stability and blackness after baking of the pattern, a baking treatment was performed by heating at a heating rate of 1.0 ° C./min and holding at 580 ° C. for 30 minutes. As a result, an OD value of 3.5 and sufficient blackness were obtained, but when the pattern shape after firing was observed by SEM, the pattern edge partly peeled off and a fine pattern could not be formed. It was.

[Comparative Example 2]

(1) Preparation of water-developable resist composition

(i) a water-soluble cellulose derivative and (iii) a photopolymer having a carboxyl group in the side chain instead of an acrylic resin, a copolymer comprising 40% methacrylolic acid, 30% methyl methacrylate and 30% styrene. Resist composition in the same manner as in Example 1 except that a polymer obtained by addition reaction of 0.4 equivalent of glycidyl metatalylate with respect to the carboxyl group of the polymer (weight average molecular weight 40,000 acid value 95) 36 parts by mass was used. I adjusted things.

[0065] (2) Preparation of photosensitive black paste composition

The photosensitive black paste composition was prepared by kneading 50 parts by mass of the resist composition (solid content 50./o) prepared in (1) above and 75 parts by mass of copper powder (average particle size 1 μm). The adjusted force S, paste yarn and composition were gelled and could not be applied. Industrial applicability As described above, the photocurable resin composition of the present invention can be developed with water, can form a fine pattern, and can form a black matrix having a sufficient black color. Therefore, it can be used for various displays. it can. It is particularly useful for black matrix for PDP.

Claims

The scope of the claims

[1] A photocurable resin composition used for forming a black matrix,

(A) a metal powder having an ionic valence of 2 or more that is blackened by oxidation;

(B) (i) a water-soluble cellulose derivative, (ii) a photopolymerizable monomer, (iii) an acrylic resin having a hydroxy group, and (iv) an organic component comprising a photopolymerization initiator,

A photocurable resin composition for forming a black matrix.

2. The photocurable resin composition for forming a black matrix according to claim 1, wherein the metal powder having an ionic valence of 2 or more that is blackened by oxidation is copper.

[3] A photosensitive material for forming a black matrix comprising a photosensitive paste film obtained by forming a film of the photocurable resin composition for forming a black matrix according to claim 1, and a protective film for protecting the photosensitive paste film. Sex film.

[4] Using the photocurable resin composition for forming a black matrix according to claim 1, a photosensitive paste film forming step of forming a photosensitive paste film on a substrate;

A pattern forming step of exposing the photosensitive paste film to a development process with water to form a predetermined pattern on the substrate;

By baking the pattern obtained in the pattern formation step in the presence of oxygen at a temperature of 1000 ° C. or lower, the pattern is fired and oxidized to blacken, a blackening step,

A method for forming a black matrix.

[5] The optical density (OD) obtained by the black matrix forming method according to claim 4 is 3.

Black matrix that is 0 or more.

[6] A plasma display panel having a black matrix formed by using the black matrix forming method according to claim 4.