KR100868550B1 - Photosensitive insulative paste composition and photosensitive film using the same - Google Patents

Abstract

Photosensitive insulating paste compositions that can be developed in alkaline developer or water can be used to form thick but still high photosensitive layers, thus high precision patterns. The photosensitive insulating paste composition contains an organic component and an inorganic powder, and the organic component includes (A) a water-soluble cellulose derivative, (B) a hydroxyl group-containing acrylic resin having a molecular weight of 20000 or less, (C) a photopolymerizable monomer, and (D) a photopolymerization. It includes an initiator.

Photosensitive Insulation Paste Composition, Photosensitive Film

Description

Photosensitive insulative paste composition and photosensitive film using the same

The present invention relates to a photosensitive insulating paste composition and a photosensitive film using the same. More specifically, the present invention relates to a photosensitive insulating paste composition comprising an organic component having a sufficiently high sensitivity to form a high precision pattern even in thick layers and having a very high resistance to an inorganic powder and a developer. The present invention also relates to a photosensitive film using the photosensitive insulating paste composition.

Techniques such as screen printing and photolithography are traditionally used in thick multilayer circuits and various display panels. In screen printing, the desired pattern is screen printed onto the substrate using a photocurable insulating paste containing inorganic particles. In photolithography, the photocurable insulating paste composition used for the substrate is irradiated with actinic light such as ultraviolet light through a photomask to develop a desired pattern on the substrate.

Other forms of display panels, plasma display panels (hereinafter simply referred to as "PDPs") are relatively simple structures and are suitable for large displays. PDPs are not only high quality images, but light emitting devices capable of displaying high quality images. Because of these advantageous features, PDPs have received considerable attention and several proposals have been made to develop larger plasma displays capable of displaying more sophisticated images.

PDPs include two facing substrates, between which display cells are formed by insulating barrier ribs. Each cell contains a fluorescent substance that acts as a photographic element and emits light upon exposure to UV radiation emitted by the plasma. The electrodes, resistors, dielectrics and other components needed to generate the plasma are placed on the substrate or inside the cell. In order to produce high precision PDPs, components including bulkheads, electrodes, resistors, dielectrics, fluorescent materials, color filters and black matrices need to be produced precisely (these components are later collectively referred to as "bulk walls"). Is called). For this purpose, the patterns forming the partition wall or the like must also be formed accurately.

In conventional screen printing techniques, certain patterns of the paste composition are patterns printed on top of others to form a multilayer pattern. It is difficult to arrange these patterns accurately to form a high precision pattern. Photolithography techniques also have the disadvantage that the sensitivity of thick layers of film material to form barrier ribs and the like decreases with depth. This also makes it difficult to form high precision patterns. Photolithography also requires expensive organic solvents such as trichloroethane as developer. This increases the production cost. These organic solvents also cause environmental pollution and are harmful to the body.

In order to solve these problems associated with the developing process using organic solvents, a photocurable insulating paste composition that can be developed in an aqueous solution has been proposed. This composition contains a water-soluble cellulose such as methyl cellulose, a photopolymerizable monomer, a photopolymerization initiator and an inorganic powder (see, for example, Patent Document 1 (Japanese Patent Laid-Open No. 63-265238)). However, this composition does not have sufficient resistance to the developer. Therefore, a development photosensitive insulating paste composition has been proposed that can solve not only this problem but also the problem of incorrect formation of partition walls in screen printing caused by dissolution and misalignment of the image area. This composition contains a water-soluble cellulose derivative, a photopolymerizable monomer, a hydroxyl group containing acrylic resin, a photoinitiator, and an inorganic powder (for example, refer patent document 2 (Unexamined-Japanese-Patent No. 2002-328470)).

However, if the photosensitive insulating paste composition disclosed in Patent Document 2 contains a hydroxyl group-containing hydrophilic acrylic resin in an amount of 50 parts by weight or more relative to the mixed amount (= 100 parts by weight) of the water-soluble cellulose derivative and the hydroxyl group-containing hydrophilic acrylic resin, Form residue. Acrylic resin is added to make the present composition more resistant to the developer. This residue interferes with the development process.

Given the current state of the art, the inventors are making considerable efforts to find ways to solve the above problems. Through this effort, as long as the hydroxyl group-containing acrylic resin has a molecular weight not exceeding 20000, the composition of the hydroxyl group-containing acrylic resin (relative to the mixed amount (= 100 parts by weight) of the water-soluble cellulose derivative and the hydroxyl group-containing acrylic resin) Even if it contains 90 to 50 parts by weight, the composition does not delay the development process, and the developer resistance of the composition is equal to the amount of hydroxyl group-containing acrylic resin (to a mixed amount of water-soluble cellulose derivative and hydroxyl group-containing acrylic resin (= 100 parts by weight)). It has been found that it can be improved by adjusting the amount to 50 parts by weight or more. The present invention is based on this finding.

It is therefore an object of the present invention that, although the composition of the present invention may contain a significant amount of hydrophilic resin component and can be developed in alkaline developer or water and is thick, it can still form a highly sensitive layer of membrane material, suitable for high precision patterns. It is to provide an insulation paste composition. Another object of the present invention is to provide a photosensitive film using such a photosensitive insulating paste composition.

The photosensitive insulating paste composition according to the present invention contains an organic component and an inorganic powder. The said organic component contains (A) water-soluble cellulose derivative, (B) hydroxyl-containing acrylic resin which has a molecular weight of 20000 or less, (C) photopolymerizable monomer, and (D) photoinitiator. Preferably, the photosensitive insulating paste composition comprises 10 to 50 parts by weight and 90 to 50 parts by weight relative to the mixed amount (= 100 parts by weight) of component (A) and component (B) as organic components, respectively. Component (B) is contained.

Preferably, the inorganic powder for use in the photosensitive insulating paste composition of the present invention is an organic powder and the composition is 10 to 10 parts by weight, respectively, with respect to the mixed amount of components (A) and (C) as organic components (= 100 parts by weight). 50 parts by weight and 90 to 50 parts by weight of component (A) and component (C).

Preferably, the photosensitive insulating paste composition of the present invention contains the organic component and the inorganic powder in amounts of 5 to 35 parts by weight and 95 to 65 parts by weight, respectively, relative to the mixed amount (= 100 parts by weight) of the organic component and the inorganic powder. do.

The photosensitive film of the present invention is characterized in that the above-mentioned photosensitive insulating paste composition is formed on a supporting film.

The photosensitive insulating paste composition of the present invention shows excellent performance when used to develop high precision patterns in water or alkaline developer: The composition can be used to form thick but still highly sensitive high precision insulating patterns. Therefore, the photosensitive insulating paste composition of the present invention can produce high precision PDPs at low cost and thus has important industrial value.

Exemplary embodiments of the invention will be described.

The photosensitive insulating paste composition of this invention contains an organic component and an inorganic component. The organic component includes (A) a water-soluble cellulose derivative, (B) a hydroxyl group-containing acrylic resin having a molecular weight of 20000 or less, (C) a photopolymerizable monomer and (D) a photopolymerization initiator.

Since it contains a water-soluble cellulose derivative which acts as a binder resin, the photosensitive insulating paste composition of the present invention exhibits high transmittance to ultraviolet rays, excimer lasers, X-rays, electron beams, and other active rays, and is a conventional acrylic resin photosensitive insulating paste. It exhibits higher developer resistance than the composition. For this reason, the composition of the present invention can form very accurate patterns.

The photosensitive insulating paste composition of the present invention uses a hydroxyl group-containing acrylic resin having a molecular weight of 20000 or less, which acts as component (B), so that the composition contains a mixed amount of water-soluble cellulose derivative and hydroxyl group-containing acrylic resin (= 100 parts by weight, Thereafter, even if it contains more than 50 parts by weight of component (B), referred to as "the total amount of resin components", it does not interfere with the development process. In addition, the present paste composition can exhibit improved developability by adjusting the amount of component (B), which is a hydrophilic resin, to an amount of 50 parts by weight or more relative to the total amount of resin components (= 100 parts by weight).

Water-soluble cellulose derivatives which act as component (A) include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, ethylhydroxy ethyl cellulose, carboxymethyl ethyl cellulose and hydroxypropyl methyl cellulose It may be any known water soluble cellulose derivative. These cellulose derivatives can be used individually or in mixtures of two or more derivatives.

The hydroxyl group-containing acrylic resin serving as component (B) usually has a molecular weight of 20000 or less, preferably 5000 to 15000, and more preferably 8000 to 12000. If the molecular weight of component (B) exceeds 20000 and the amount of hydroxyl-containing acrylic resin is 50 parts by weight or more based on the mixed amount (= 100 parts by weight) of the water-soluble cellulose derivative and the hydroxyl-containing acrylic resin, the developability of the composition is It can be reduced and unwanted residue can be formed.

The hydroxyl group-containing acrylic resin may be a copolymer obtained by polymerization of a hydroxyl group-containing monomer serving as a main copolymerizable monomer. If necessary, other monomers capable of copolymerizing with hydroxyl group containing monomers can be used.

Preferred examples of hydroxyl group-containing monomers are hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxy Monoesters formed by the reaction of acrylic acid or methacrylic acid, including butyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate with monohydric alcohols having 1 to 20 carbon atoms.

Other preferred examples of hydroxyl group containing monomers are glycerol acrylate, glycerol methacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate, ε-caprolactone-modified hydroxyethyl acrylate, ε-caprolactone Monoesters formed by the reaction of modified hydroxyethyl methacrylate, and acrylic or methacrylic acid, including 2-hydroxy-3-phenoxypropyl acrylate, with glycols having from 1 to 10 carbon atoms.

Preferred examples of other monomers that can be copolymerized with hydroxyl group containing monomers are, for example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, itaconic acid, maleic acid and fumaric acid, and their Anhydride or semi-ester product; 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 meta Methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, 2,2,2-trifluoromethyl acrylate, and 2,2,2-trifluoromethyl methacrylate Α, β-unsaturated carboxylates such as the like; And styrene such as styrene and α-methyl styrene, p-vinyl toluene and the like. Other examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, glycidyl acrylate, and glycidyl methacrylate. These compounds may be used alone or in mixture of two or more.

The photosensitive insulating paste composition of the present invention has a hydroxyl group in an amount of 50 to 90 parts by weight, more preferably 60 to 80 parts by weight, still more preferably 65 to 75 parts by weight based on the total amount of resin components (= 100 parts by weight). It is preferable to contain a containing acrylic resin.

If the amount of hydroxyl-containing acrylic resin component does not fall within a certain range, the required accuracy may not be achieved in the final pattern: up to 50 parts by weight of hydroxyl-containing acrylic resin reduces developer resistance, while at least 90 parts by weight of resin Can reduce developability and form unwanted residues during the development process. For example, up to 50 parts by weight of the photopolymerizable monomer may lead to poor photopolymerization, resulting in image area dissolve during development, which may cause image formation to fail. In comparison, more than 90 parts by weight of the photopolymerizable monomer may degrade the resolution of a sophisticated image.

Photopolymerizable monomers which act as component (C) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylol propane triacrylate, trimethyl All propane trimethacrylate, trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta Methacrylate, dipenta Lithitol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol acrylate, glycerol methacrylate, cardoepoxy diacrylate, as well as (meth) acrylate salts of the above compounds, respectively, fumarate and itaconate And any known photopolymerizable monomers including but not limited to fumaric acid esters, itaconic acid esters, and maleic acid esters obtained by exchange with maleate.

Photopolymerization initiators acting as component (D) are any conventional, including benzophenone, benzoin, benzoin alkyl ether, acetophenone, aminoacetophenone, benzyl, benzyl alkyl ketal, anthraquinone, ketal, and thioxanthone It may be a photopolymerization initiator. 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-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, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, 1- [4- (2- Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, 2-chlorothione Oxanthone, 1-chloro-4-propoxyoxyoxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid , Methyl 4-dimethylaminobenzo Salt, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-die Oxyacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethylacetal, 1-phenyl-1,2-propaneionone 2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4'-bisdiethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzoin isobutyl ether, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropyl Thioxanthone, dibenzosuberon, α, α-dichloro-4-phenoxyacetophenone, pentyl 4-dimethylaminobenzoate, and 2- (o-chlorofe ) -4,5-diphenyl may already include jolil dimer. These compounds may be used alone or in mixture of two or more.

The photopolymerization initiator is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on the mixed amount (= 100 parts by weight) of the water-soluble cellulose derivative and the photopolymerizable monomer. 0.1 part by weight or less of the photopolymerization initiator can reduce the curability, while when 10 parts by weight or more are contained, the photopolymerization initiator absorbs the light before it reaches the bottom, so that curing is not sufficiently performed.

In addition to components (A) to (D), the photosensitive insulating paste composition of the present invention may contain optional additives such as UV absorbers, photosensitizers, polymerization initiators, plasticizers, thickeners, organic solvents, dispersants, antifoaming agents and organic or inorganic suspending agents. Can be.

A photosensitizer is added for the purpose of increasing photosensitivity. Specific examples of the photosensitizer include 2,4-diethyl thioxanthone, isopropyl thioxanthone, 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) chacon, 4,4-bis (diethylamino) chacon, p-dimethylaminocinamidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinyl Den) -isonaphthiothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis ( 7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylamino Ben Crude acid salts, 3-phenyl-5-benzoylthiotetrazole and 1-phenyl-5-ethoxycarbonylthiotetrazole. Such photosensitizers may be used alone or in a mixture of two or more.

Polymerization inhibitors may be added for the purpose of increasing thermal stability during storage. Specific examples of polymerization inhibitors include hydroquinone, hydroquinone monoester, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechin, N-phenylnaphthylamine, 2,6-di-t-butyl-p -Methylphenol, chloranyl, and pyrogallol.

Plasticizers may be added to improve the suitability for the substrate. Specific examples of plasticizers may include esters of phthalates such as polyethylene glycol, glycerol, and dibutyl tartarate, as well as dibutyl phthalate (DBP), dioctyl phthalate (DOP), and dicyclohexyl phthalate.

Defoamers serve to prevent the formation of air bubbles in the paste or film that can form pores after baking. Specific examples of antifoaming agents may include those based on alkylene glycols, silicones or higher alcohols such as polyethylene glycol (molecular weight = 400 to 800).

The inorganic powder for use in the photosensitive insulating paste composition of the present invention may be any inorganic powder that is sufficiently transparent to the light source used. Examples thereof may include glass, ceramics (eg cordierite), and metal powders. More specific examples thereof include PbO-SiO ₂ glass, PbO-B ₂ O ₃ -SiO ₂ Glass, ZnO-SiO ₂ Glass, ZnO-B ₂ O ₃ -SiO ₂ Glass, Bio-SiO ₂ Glass, Bio-B ₂ O ₃ -SiO ₂ Glass powders such as borosilicate lead glass, such as glass, borosilicate zinc glass, borosilicate bismuth glass; Na, K, Mg, Ca, such as cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, neodymium oxide, vanadium oxide, cerium oxide, cadmium oxide, ruthenium oxide, silica, magnesia, spinel, etc. Oxides such as Ba, Ti, Zr, Al; ZnO: Zn, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ SiO ₅ : Ce, CaWO ₄ : Pb, BaMgAl ₁₄ O ₂₃ : Eu, ZnS: (Ag, Cd), Y ₂ O ₃ : Eu, Y ₂ SiO ₅ : Eu, Y ₃ Al ₅ O ₁₂ : Eu, YBO ₃ : Eu, (Y, Gd) BO ₃ : Eu, GdBO ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu, Zn ₂ SiO ₄ : Mn , BaAl ₁₂ O ₁₉ : Mn, SrAl ₁₂ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ , YBO ₃ : Tb, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdBO: Tb, ScBO ₃ Tb, Sr ₆ Si ₃ O Fluorescent material such as ₃ Cl ₄ : Eu, ZnS: (Cu, Al), ZnS: Ag, Y ₂ O ₂ S: Eu, ZnS: Zn, (Y, Cd) BO ₃ : Eu, BaMaAl ₁₂ O ₂₃ : Eu Field powder; And metal powders such as iron, nickel, palladium, aluminum, silver, platinum and the like. Among them, glass powder and ceramic powder are particularly preferable because of the excellent transparency. Glass powder (glass frit) provides the most significant effect. Since silicon oxide, aluminum oxide or titanium oxide makes the inorganic powder opaque and reduces the light transmittance of the inorganic powder, it is preferable that the inorganic powders do not contain these components.

The particle size of the inorganic powder is determined according to the shape of the pattern to be formed but it is preferable to use inorganic powders having an average particle size of 0.5 to 10 μm, more preferably an average particle size of 1 to 8 μm. Inorganic powders with an average particle size of 10 µm or more can form rough surfaces as soon as they form a very accurate pattern, while inorganic powders with an average particle size of 0.5 µm or less scatter light and prevent light from penetrating downwards towards the bottom. . The inorganic powder may be spheres, blocks, fragments and dendritic crystals, and one or a combination of two or more of three forms may be used.

The inorganic powder may contain not only black powder but also inorganic dyes of other colors such as red, blue and green dyes. Photosensitive insulating paste compositions containing such dyes can be used to form patterns of various colors and are suitable for the production of color filters or other parts of plasma display panels. The inorganic powders may be a mixture of several kinds of fine particles, each of which has different physical properties. By using glass powder or ceramic powder with different thermal softening points, shrinkage during baking can be minimized. These inorganic powders may be mixed in any suitable combination of shape and physical properties suitable for the required properties such as partition walls.

Since it has an average particle size of 10 μm or less (0.5 to 10 μm), the inorganic powder may be organic acid, inorganic acid, It may be surface treated with a silane-binder, titanate-based binder, aluminum-based binder, surfactant, or other surface treatment agent. Specifically, the surface treatment is treated as follows. First, the surface treatment agent is dissolved in an organic solvent or water. Inorganic powder is then added to the solution and the mixture is stirred. The solvent is then evaporated and the residue is heated to approximately 50-200 ° C. for 2 hours. Optionally, a surface treating agent may be added when the photosensitive composition is formed into a paste.

Each ratio of the organic component and the inorganic powder in the photosensitive insulating paste composition of the present invention is usually 5 to 35 parts by weight and 95 to 65 parts by weight, preferably based on the total amount of the photosensitive insulating paste composition (= 100 parts by weight). 10 to 30 parts by weight and 90 to 70 parts by weight, and more preferably 15 to 25 parts by weight and 85 to 75 parts by weight. If the amount of the organic component is 5 parts by weight or less, photopolymerization may be insufficient. This causes dissolution of the image area during development, causing image formation to fail. In comparison, if the amount of the inorganic component is 35 parts by weight or more, the final pattern may be peeled off as soon as it is baked.

The photosensitive insulating paste composition may be produced by dissolving or dispersing the above components in a solvent. The solvent used for this purpose shows high affinity for the inorganic powder, dissolves the organic component well, imparts suitable viscosity to the photosensitive insulating paste composition, and any solvent is possible as long as it can be easily evaporated. Specific examples of such solvents include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, cyclohexaneone; alcohols such as n-pentaneol, 4-methyl-2-pentaneol, cyclohexaneol, diacetone alcohol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether Ethers such as diethylene glycol diethyl ether; saturated alkyl aliphatic monocarboxylic acid salts such as n-butyl acetate, and amyl acetate; Lactates such as ethyl lactate, n-butyl lactate; And methyl cellosolve acetate, ethyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 2-methoxybutyl acetate Salt, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxy Butyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate and 2-methoxypentyl acetate. These solvents may be used alone or in a mixture of two or more.

In order to maintain the viscosity of the photosensitive insulating paste composition in a preferred range, the amount of the solvent used is preferably 300 parts by weight or less, more preferably 10 to 10 parts by weight based on the total amount of the organic component and the inorganic powder (= 100 parts by weight). 70 parts by weight, and most preferably 25 to 35 parts by weight.

Depending on the intended use, the photosensitive insulating paste composition of the present invention may be used in the substrate as a liquid or by screen printing or various other techniques. In applications requiring a high precision process, such as bulkheads of PDPs, the composition is preferably used as a photosensitive film. In this way, the accuracy of the formed patterns can be significantly improved, whereby a bulkhead or the like with high accuracy can be obtained. The photosensitive film can be formed by applying the photosensitive paste composition of the present invention to a supporting film and drying the film to obtain a film having a thickness of 10 to 100 mu m. For example, the support membrane used for this purpose may be a 15 to 125 μm thick flexible membrane made of synthetic resins such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride. If necessary, the support membrane may be treated with a release agent to facilitate the mobility of the membrane. The composition may be applied to the support membrane by an applicator, bar coater, wire bar coater, roll coater or curtain flow coater. In particular, roll coaters are preferred because they can be used to effectively form a uniform and thick film. The protective film can be applied to the photosensitive film to protect the photosensitive paste composition when the photosensitive film is not used. The protective film used for this purpose may be a silicon coating or silicon-baked film of approximately 15 to 125 μm thickness made of polyethylene terephthalate, polypropylene or polyethylene.

Subsequently, a method of forming desired patterns using the photosensitive insulating paste composition of the present invention will be described. The photosensitive insulating paste composition is applied to the substrate by coating or transfer techniques to form a layer. Thereafter, actinic rays such as ultraviolet light, excimer laser, X-rays and electron beams are irradiated to the composition layer through a mask to expose the image. The exposed image is then developed in alkaline developer or water. Unexposed areas will dissolve in the developer and leave a pattern on the substrate. If necessary, the patterned layer is baked. Optionally, the entire surface of the photosensitive insulating paste composition layer can be exposed without masking. In this case, the pattern is formed without performing the developing process. If necessary, the substrate is then baked. When it is desirable to form high precision patterns, the photosensitive film is first peeled from the protective film and the photosensitive insulating paste composition is moved to the substrate to form a layer. The layer is exposed with or without masking. The layer exposed with masking is developed to form a pattern, while the layer exposed without masking is cured without going through the developing process. The substrate may be a glass substrate, a glass substrate having a electrode, such as a bus electrode formed thereon, or a ceramic substrate. In moving the photosensitive insulative paste composition layer, the composition layer is heat compressed using, for example, a hot roll thinner while in contact with the substrate surface. Heat compression is preferably carried out at a roll pressure of 1 to 5 kg / cm ² and a compression rate of 0.1 to 10.0 m / min while raising the surface temperature of the substrate to 80 to 140 ° C. The substrate may be preheated to a temperature of 40-100 ° C. The radiation emitter used to expose the paste composition may be a UV-emitter commonly used in photolithography or an exposure apparatus used in the production of semiconductors and liquid crystal displays (LCDs).

Alkali components of the alkaline developer used in the developing process include hydroxides, carbonates, bicarbonates, phosphates and pyrophosphates of alkali metals such as lithium, sodium, potassium; Primary amines such as benzyl amine, butyl amine, secondary amines such as dimethyl amine, dibenzyl amine, diethanol amine; Tertiary amines such as trimethylamine, triethylamine, triethanolamine; Cyclic amines such as morpholine, piperazine, pyridine; Polyamines such as ethylenediamine and hexamethylenediamine; Ammonium hydroxides such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, and trimethyl phenyl benzyl ammonium hydroxide; Sulfonium hydroxides such as trimethyl sulfonium hydroxide, diethylmethyl sulfonium hydroxide, dimethylbenzyl sulfonium hydroxide; Choline; And silicate-containing buffers. The type, composition and concentration of the developer as well as the time, temperature, mode of development (eg, dipping, stirring, showering, spraying and paddling) and the apparatus used for the developing process are based on the characteristics of the photosensitive insulating paste composition. Can be appropriately selected.

The baking process may be carried out at any temperature sufficient to burn off any organic materials present in the photosensitive insulating paste composition. For example, the process may be performed at 400 to 600 ° C. for 10 to 90 minutes.

The photosensitive insulating paste composition of the present invention can be widely used for the production of thick multilayer circuits as well as for the production of plasma displays, plasma address liquid crystal displays, and various other displays, and especially for the production of bulkheads and the like used for high-precision PDPs and specifically for PDPs. It is particularly suitable for the production of dielectrics used.

The invention will be described with reference to various embodiments which are not intended to limit the scope of the invention.

Example 1

(Production of Photosensitive Insulation Paste Composition)

The following organic components were mixed together on a stirrer for 3 hours to form a solution (solid component = 50%): 15 parts by weight of hydroxypropyl cellulose as a water-soluble cellulose derivative, 33 parts by weight of styrene / hydro as a hydroxyl-containing acrylic resin Hydroxyethyl methacrylate copolymer (styrene / hydroxyethyl methacrylate = 55/45 (wt%), MW = 8500), 39 parts by weight of 2-hydroxy-3-phenoxypropylacrylate as photopolymerization initiator (Product name: M-600A, Kyoeisha Chemical), 1.0 part by weight of 2,2-dimethoxy-2-phenylacetophenone (product name: IR-651, Ciba gauge) as a photopolymerization initiator, 12 parts by weight of dichloro as a plasticizer 100 parts by weight of 3-methoxy-3-methylbutanol as hexyl phthalate and solvent. 35 parts by weight of this solution (solid component = 50%) was mixed / doughed with 82.5 parts by weight of glass frit as an inorganic powder to form a photosensitive insulating paste composition.

(Production of Photosensitive Film)

Using a lip coater, the photosensitive insulating paste composition thus obtained was applied to a polyethylene terephthalate support film. The coating was dried at 100 ° C. for 6 minutes to completely remove the solvent. This left a 27 탆 thick photosensitive insulating paste film formed on the supporting film. Thereafter, the coating layer of the photosensitive insulating paste was covered with a 25 μm thick polyethylene film. Thus, the photosensitive film was completed.

(Evaluation of the photosensitive film)

Using a hot roll laminator set at 105 ° C., the glass substrate preheated to 80 ° C. was laminated with the resulting photosensitive film and the polyethylene film was peeled off from the glass substrate. The air pressure and laminar velocities used were 3 kg / cm ² and 1.0 m / min, respectively. Subsequently, the polyethylene terephthalate support membrane was stripped off. Using a high pressure mercury lamp as the light source, ultraviolet light was irradiated to the photosensitive coating in an amount of 500 mJ / cm ² through a mask with a square test pattern. To develop the pattern, 30 ° C. water was sprayed onto the exposed coating at a pressure of 3 kg / cm ² over five times to allow the film to reach the break point. The term " break point " as used above means the time taken until the material in the exposed area is completely removed.

The minimum line width remaining was determined by the size of the adhesion of the formed pattern and was determined by 40 μm. The formed pattern was observed by SEM and a trapezoidal pattern was found. The pattern formed in this way was baked to evaluate morphological stability. The baking process was first performed by heating the membrane at a rate of 1.0 ° C./min and maintaining it at 580 ° C. for 30 minutes. The baked pattern was satisfactory.

Comparative Example 1

(Production of Photosensitive Insulation Paste Composition)

The following organic components were mixed together on a stirrer for 3 hours to form a solution: 15 parts by weight of hydroxypropyl cellulose as a water-soluble cellulose derivative, 33 parts by weight of styrene / hydroxyethyl methacrylate copolymer as a hydroxyl-containing acrylic resin (Styrene / hydroxyethyl methacrylate = 55/45 (wt%), MW = 25000), 39 parts by weight of 2-hydroxy-3-phenoxypropylacrylate (product name: M-600A, as a photopolymerization initiator) Kyoeisha Chemical), 1.0 part by weight of 2,2-dimethoxy-2-phenylacetophenone (product name: IR-651, Ciba gauge) as a photopolymerization initiator, 12 parts by weight of dichlorohexyl phthalate as a plasticizer and 100 as a solvent. Parts by weight of 3-methoxy-3-methylbutanol. 35 parts by weight of this solution was mixed / doughed with 82.5 parts by weight of glass frit as an inorganic powder to form a photosensitive insulating paste composition.

(Production of Photosensitive Film)

Using a lip coater, the photosensitive insulating paste composition was applied to a polyethylene terephthalate support film. The coating was dried at 100 ° C. for 6 minutes to completely remove the solvent. This left a 27 탆 thick photosensitive insulating paste film formed on the supporting film. Thereafter, the coating layer of the photosensitive insulating paste was covered with a 25 μm thick polyethylene film. Thus, the photosensitive film was completed.

(Evaluation of the photosensitive film)

Using a hot roll laminator set at 105 ° C., the glass substrate preheated to 80 ° C. was laminated with the resulting photosensitive film and the polyethylene film was peeled off from the glass substrate. The air pressure and laminar velocities used were 3 kg / cm ² and 1.0 m / min, respectively. Subsequently, the polyethylene terephthalate support membrane was stripped off. Using a high pressure mercury lamp as the light source, ultraviolet light was irradiated to the photosensitive coating in an amount of 500 mJ / cm ² through a mask with a square test pattern. To develop the pattern, 30 ° C. water was sprayed onto the exposed coating at a pressure of 3 kg / cm ² over five times to allow the film to reach the break point.

The minimum line width remaining was determined by the size of the adhesion of the formed pattern and was determined by 40 μm. The formed pattern was observed by SEM and a trapezoidal pattern was found. However, the development of the pattern was not fully accomplished and a residue was found.

As mentioned above, the photosensitive insulating paste composition of the present invention containing an organic component that imparts excellent developer resistance to the composition is suitable for forming a thick but still high photosensitive layer, thus a high precision pattern. The photosensitive insulating paste composition of the present invention is suitable for the production of a photosensitive film.

Claims (6)

In the photosensitive insulating paste composition containing an organic component and an inorganic powder, The organic component comprises (A) a water-soluble cellulose derivative, (B) a hydroxyl group-containing acrylic resin having a molecular weight of 5000 to 20000, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator, A component (A) is 10 to 50 parts by weight and component (B) is 90 to 50 parts by weight based on 100 parts by weight of the total of the components (A) and (B) in the organic component. delete The method of claim 1, The inorganic powder is a glass powder, the photosensitive insulating paste composition. The method of claim 1, A photosensitive insulating paste composition containing 10 to 50 parts by weight of component (A) and 90 to 50 parts by weight of component (C) with respect to the total amount of components (A) and 100 parts by weight of component (C) as organic components. The method of claim 1, A photosensitive insulating paste composition containing 5 to 35 parts by weight of an organic component and 95 to 65 parts by weight of an inorganic powder with respect to a total amount of 100 parts by weight of an organic component and an inorganic powder. A photosensitive film comprising a support film and a layer of the photosensitive insulating paste composition according to any one of claims 1 to 3 formed on the support film.