JP2007012415A - Manufacturing method for panel display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a panel display member capable of shrinkage control in a X-Y plane generated in baking and maintaining the shape of a partition wall by a simple method. <P>SOLUTION: This manufacturing method for the panel display member comprises a process applying a paste A comprising an inorganic component containing at least glass particles and an organic component containing a binder resin on a substrate, a process applying a paste B comprising at least a inorganic component containing glass particles and an organic component containing at least the binder resin on a layer of the paste A, a process forming a desired pattern if necessary, and a sintering process. When a panel display member is manufactured, a relation T<SB>CA</SB><T<SB>CB</SB>is satisfied when T<SB>CA</SB>is crystallizing temperature of the glass particles contained in the paste A, and T<SB>CB</SB>is crystallizing temperature of the glass particles contained in the paste B. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a panel display, and more particularly to a method for manufacturing a panel display that can be suitably used for an electroluminescent display or the like.

As an image forming apparatus that replaces a cathode ray tube, an image forming apparatus using an electron-emitting device that is a self-luminous discharge type display has been proposed. This is because the contrast between light and dark is much larger than that of a liquid crystal display, the viewing angle is wide, and the demand for larger screens and higher definition can be met. There are two known types of electron-emitting devices, a hot cathode electron-emitting device and a cold cathode electron-emitting device. Hot cathode electron-emitting devices include field emission type (referred to as FE type), metal / insulating layer / metal type (referred to as MIM type), and surface conduction type electron emitting device. An image forming apparatus using a cold cathode electron-emitting device displays an image by generating fluorescence by irradiating a phosphor with an electron beam emitted from the electron-emitting device. What is required here is to prevent electrons generated from these electron-emitting devices from radiating to the adjacent unit. When electrons jump over the barrier rib, the adjacent unit emits light, resulting in a decrease in contrast. Therefore, it is important to make the partition shape of each unit sharp and adjust the height of the partition appropriately. For example, a method of obtaining a partition wall necessary for improving contrast and improving brightness by forming a two-layer partition wall using at least two kinds of partition wall materials on a substrate and changing a difference in refractive index thereof (for example, Patent Document 1) There is a method in which barrier ribs having different heights are formed by only one development and baking by combining the steps of application, exposure, and drying using a photosensitive paste. (For example, Patent Document 2)
The barrier structure of the electron-emitting device member is formed by a manufacturing method such as a sandblast method, an intaglio transfer method, a photolithography method, a press method, or a screen printing method. For example, a technique for forming a partition wall having a uniform shape without a defect at the edge portion of the partition wall top portion using a sandblast method has been proposed. (For example, Patent Document 3)
The barrier ribs can be obtained by forming a barrier rib pattern using a paste mainly made of a material such as a low-melting glass, a resin binder, a solvent, an additive, and the like, and firing it. In firing the partition walls, first, after the solvent is evaporated, organic substances such as a resin binder react with the air in the firing furnace and are removed by heat and oxidative decomposition. The partition walls become porous due to the release of the decomposition gas at this time, but as the temperature rises further, the low melting point glass becomes soft and fluid, and sinters to fill the porous part, and the entire partition pattern Heat shrinkage occurs. Since the heat shrinkage of the barrier rib pattern occurs uniformly over the entire wall, the barrier ribs to be erected are slanted due to the tensile force caused by the heat shrinkage, and after firing the barrier rib structure before firing, electrons are transferred to the adjacent unit. There was a concern that the structure would be easy to radiate and as a result the contrast would deteriorate. That is, if the glass is baked at the softening point temperature or higher, the desired glass shape may not be obtained. For this problem, for example, by forming a pattern with a high melting point glass powder having a softening point higher than the firing temperature and a low melting point glass component having a softening point lower than the firing temperature, and then coating with the low melting point glass component, firing There has been proposed a method capable of improving the dimensional deviation due to thermal deformation at the time. However (for example, Patent Document 4), since this method includes a step of mixing high-melting glass and low-melting glass to form a pattern and a step of coating low-melting glass thereafter, the process of partition configuration becomes complicated. In addition, a method has also been proposed in which shape deformation of the partition wall pattern can be reduced by firing with the filling material filled in the partition wall pattern. (For example, Patent Document 5) However, even in this method, it is necessary to physically or chemically remove the filling material after firing, and a separate removal step is necessary after firing.
JP 2000-133139 A JP 2002-216618 A JP 2001-043793 A JP 2005-135682 A JP 2001-332178 A

  Accordingly, an object of the present invention is to provide a method for manufacturing a panel display member, which can suppress shrinkage in the XY plane generated during firing and maintain the shape of the partition wall by a simpler method.

The gist of the present invention for solving the above-mentioned problems is to apply a paste A consisting of an inorganic component containing at least glass particles and an organic component containing at least a binder resin on a substrate, and a layer made of the paste A. A method for producing a panel display member, comprising: applying a paste B comprising an inorganic component containing at least glass particles and an organic component containing at least a binder resin; forming a desired pattern if necessary; and sintering step a is, when the crystallization temperature T _CA of the glass particles contained in the paste _a, the crystallization temperature of the glass particles contained in the paste B was T _CB, panel and satisfies the T _{CA <T CB} It is a manufacturing method of a display member.

  According to the present invention, it is possible to manufacture a panel display member that can easily suppress shrinkage in the X and Y directions and maintain the shape of the partition wall, which is easily generated during firing, without requiring a coating step and a post-baking process that have been conventionally performed. A method can be provided.

  Hereinafter, the pattern formation method using the inorganic particle containing paste composition of this invention and the manufacturing method of the panel display member produced by it are demonstrated.

  The substrate used in the method for producing a panel display member of the present invention is not particularly limited as long as it has a certain rigidity and flatness and can withstand firing, but a glass substrate is used because it is easy to handle. It is preferable. As the glass substrate, soda lime glass or heat-resistant glass (PD200 manufactured by Asahi Glass Co., Ltd., PP8 manufactured by Nippon Electric Glass Co., Ltd., CS25 manufactured by Saint-Gobain Co., Ltd.) can be preferably used. In consideration of heat dissipation, ceramic substrates, metal substrates, and semiconductor substrates (AiN, CuW, CuMo, SiC substrates, etc.) can also be used.

  On these substrates, if necessary, one or more insulators, semiconductors, conductors, etc., or a combination thereof may be formed. In this case, the insulator, semiconductor, conductor, etc. should be able to withstand the sintering temperature.

The glass powder used in the paste A and paste B used in the present invention has SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , ZnO, PbO, Bi ₂ O ₃ , ZrO ₃ , alkaline earth metal oxide as glass components. These include metal oxides such as alkali metal oxides, and examples thereof include borosilicate glass, alkali silicate glass, Pb glass, and Bi glass. As these glasses, those in which at least one kind of crystallized glass (mullite, spinel, garnite, etc.) is precipitated by firing treatment are preferably used.

  The glass composition is preferably non-lead oxide or low lead oxide. Thereby, environmental pollution and workability can be improved. Further, it is desirable to use a glass having a crystallization temperature of 600 ° C. or lower. When the crystallization temperature is 600 ° C. or lower, there is an advantage that an inexpensive glass substrate can be used as well as cost reduction and productivity improvement due to the fact that firing at a low temperature is possible. Furthermore, it is desirable that it is an alkali free glass. As described above, specifically, Ba—Bi or Bi—Zr glass is preferable, but it is not limited thereto.

In the glass component, SiO ₂ is desirably contained in a range of 3 to 60% by weight, and more preferably 20 to 60% by weight. When the amount is less than 3% by weight, the density, strength and stability of the inorganic component are lowered during sintering, and the inorganic component is easily peeled off from the substrate. On the other hand, if it exceeds 60% by weight, the heat softening point becomes high, and baking on the glass substrate becomes difficult.

  In general, amorphous glass has a property of crystallizing when heated to a crystallization temperature. In the crystallized glass, glass crystals are formed from several tens to about 90 vol%, so that the strength and the coefficient of thermal expansion can be improved. Using this, it is possible to suppress shrinkage during firing. It is also possible to use already crystallized glass. In this case, since the glass crystallizes as it approaches the crystallization peak temperature, it has the property of consolidating the glass. In the present invention, both amorphous glass and crystallized glass can be used.

  It is known that the crystallization temperature of glass varies depending on the composition (type and amount of constituent components), and a glass having a target crystallization temperature can be obtained by manipulating the composition. The crystallization temperature of the glass can be specified by DTA (differential thermal analysis). Since the crystallization temperature of the glass powder to be contained in the paste can be designed using this apparatus, it becomes possible to apply a paste containing glass powder having a low crystallization temperature in the lower layer relative to the upper layer.

The present invention has a process of using two types of pastes, paste A and paste B, and applying them in layers. Here, when the crystallization temperature of the glass particles contained in the paste A T _CA, the crystallization temperature of the glass particles contained in the paste B was T _CB, to require that satisfy T _{CA <T CB} is When the pattern of paste A that crystallizes on the low temperature side and the pattern of paste B that crystallizes on the higher temperature side than the pattern of paste A are directly applied on the pattern of paste A in the temperature rising process of firing. Before the paste A pattern crystallizes, the paste B pattern suppresses the shrinkage of the paste A pattern in the XY direction, and after the paste A pattern crystallizes, the paste B pattern X- This is because by utilizing the fact that the shrinkage in the Y direction is suppressed by the paste A, it is considered that the shrinkage in the XY direction during sintering can be suppressed. The relationship between T _CA and T _CB is preferably T _CB −T _CA ≧ 5 ° C. If the difference between T _CB and T _CA is less than 5 ° C., the effect of suppressing shrinkage in the XY direction may be small. More preferably, _TCB - _TCA ≧ 10 ° C. More preferably, T _CB −T _CA ≧ 20 ° C. Is 0.99 ° C. or less as a T _CB -T _CA because is not particularly limited but the T _CB is large becomes difficult to obtain the benefits as previously described as the upper limit. Further, a filler may be further used as an inorganic component. As the filler, SiO ₂ , Al ₂ O ₃ , ZrO ₂ , mullite, spinel, magnesia, ZnO and the like are preferably used. Here, the filler is a component that does not dissolve in the glass component even during sintering. By adding a filler, the strength of the partition wall can be improved, but the filler content is preferably less than 10 vol% with respect to the total paste volume. When it contains more than it, there exists a possibility that a crack may generate | occur | produce at the time of sintering.

  In paste A and / or paste B, the amount of the inorganic component contained therein is preferably 30 to 60 vol% with respect to the total volume of the paste. If it is less than 30 vol%, the paste may be in a liquid state and the shape retention may be impaired. If it exceeds 60 vol%, pattern omission will be worse when there is a development step.

  The binder resin used for the organic components of paste A and paste B is not particularly limited as long as it has an action of maintaining its shape when the paste is applied and dried, and generates tar and gas during sintering. It is desirable that there is no adverse effect due to the above. For example, an acrylic resin, an epoxy resin, a polyurethane resin, a silicon resin, a melamine resin, a phenol resin, and the like can be given. More preferred are polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, α-methylstyrene polymer, butyl methacrylate, and the like.

  Addition of plasticizer, thickener, organic solvent, antioxidant, dispersant, organic or inorganic suspending agent or leveling agent as necessary in addition to binder resin as organic components of pastes A and B Agent components can be used. The organic component is preferably 40 to 70 vol% with respect to the total paste volume.

  Further, preferably, a photosensitive component can be used as the organic component. Examples of the photosensitive component include a photosensitive monomer, a photopolymerization initiator, an ultraviolet absorber, and a sensitizer.

  Examples of photosensitive monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, Benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, Isobonyl acrylate, 2-hydroxypropyl acrylate , Isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy Pentaacryle Ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate , Phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, thiophenol Acrylate, benzyl merca Butane acrylate, a monomer in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorination Styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene, vinylcarbazole, and the above compounds In this molecule, acrylate in the molecule is partially or entirely changed to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. In the present invention, one or more of these can be used.

  In addition to these, the development property after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

  Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl- 4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, ben Inmethyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (P-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propane Dione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile , Diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide and eosin, methylene blue and other reducing agents such as ascorbic acid and triethanolamine The combination etc. are given. In the present invention, one or more of these can be used. A photoinitiator is used in 0.05-10 weight% with respect to the photosensitive component, More preferably, it is 0.1-5 weight%. If the amount of the photopolymerization initiator is too small, the photosensitivity becomes poor. If the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small.

  Ultraviolet absorbers are preferably used because they provide high aspect ratio, high definition, and high resolution. As the ultraviolet absorber, an organic dye, particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like can be used. . Even when an organic dye is added as an ultraviolet absorber, it is preferable because it does not remain in the partition walls after firing and the deterioration of the insulating film characteristics due to the ultraviolet absorber can be reduced. Of these, azo dyes and benzophenone dyes are preferable. The content of the ultraviolet absorber in the paste is preferably 0.05 to 5% by weight. If it is less than 0.05% by weight, the effect of adding an ultraviolet absorber is reduced, and if it exceeds 5% by weight, the insulating film properties after firing are deteriorated. More preferably, it is 0.1 to 1 weight%.

  Sensitizers are used to improve sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 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 (diethylamino) ) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone 1,3-carbonyl-bis (4-diethylamino) Benzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, Examples thereof include 3-phenyl-5-benzoylthiotetrazole and 1-phenyl-5-ethoxycarbonylthiotetrazole. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer to paste A and B, the content is 0.05-30 weight% with respect to the photosensitive component, More preferably, it is 0.1-20 weight%. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

  The paste A and paste B used in the present invention may further contain a polymerization inhibitor, a plasticizer, an antioxidant, a solvent and the like as organic components. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol. When using a polymerization inhibitor, the content is preferably 0.001 to 1% by weight based on the paste.

  Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

  Antioxidants can be used to prevent oxidation of organic components such as acrylic copolymers during storage. Specifically, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol), 2,2-methylene-bis- (4-ethyl-6-t) -Butylphenol), 4,4-bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-Methyl-4-hydroxy-t-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, dilaurylthiodipro Onato, triphenyl phosphite. When using an antioxidant, the content is preferably 0.001 to 1% by weight based on the paste.

  The paste used in the present invention can use an organic solvent for the purpose of adjusting the viscosity. Examples of the organic solvent include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, Dichlorobenzene, bromobenzoic acid, chlorobenzoic acid and the like and organic solvent mixtures containing one or more of these are used. Further, water may be used as necessary.

  The viscosity of the paste is appropriately adjusted depending on the addition ratio of the inorganic component, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is usually 2 to 200 Pa · s (Pascal · second). For example, when applying to a glass substrate by a spin coat method, 2-5 Pa.s is preferable. In order to obtain a film thickness of 10 to 20 μm by applying it once by the screen printing method, 50 to 200 Pa · s is preferable. In the case of using a blade coater method or a die coater method, 2 to 20 Pa · s is preferable.

  Next, the pattern processing method for the partition of the panel display will be described in more detail with an example. However, the present invention is not limited to this.

  As a coating method for coating the paste A on the entire surface or a part thereof, a general method such as screen printing, bar coater, roll coater, or the like can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste. However, in consideration of shrinkage due to drying or baking, it is preferable that the coating thickness is 10 to 30 μm after drying.

  Next, the paste B is applied to the entire surface or a part of the layer made of the paste A. As a coating method, general methods such as screen printing, bar coater, and roll coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste. However, in consideration of shrinkage due to drying or baking, it is preferable that the coating thickness is about 5 to 30 μm after drying.

  Before applying the paste B onto the paste A, it is preferable to bake the film made of the paste A. By doing so, the paste A dries and hardens, and when the paste B is applied, a reduction in paste thickness can be prevented. The baking temperature and time can be appropriately set according to the paste composition to be constituted, and it is preferable to apply the baking at 50 to 100 ° C. for about 5 to 30 minutes. The baking is preferably performed in a convection baking furnace or an infrared baking furnace, but there is no particular limitation.

  In the case of coating, if the thickness is insufficient by one coating, there is no problem in overcoating. Thus, the layer applied many times with the same paste can be viewed as a whole.

  When a photosensitive component is used for paste A and / or paste B, a pattern can be formed by exposing and developing after applying the paste entirely or partially.

  For the exposure, a mask exposure method using a photomask and a direct drawing exposure method using a laser beam or the like can be used. However, exposure using a photomask can shorten the exposure time and is excellent in productivity. . As an exposure apparatus in this case, a stepper exposure machine, a proximity exposure machine, or the like can be used.

Examples of the actinic rays used at this time include visible rays, near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are preferable. Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, germicidal lamp, etc. can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, for example, exposure may be performed for 0.5 to 30 minutes using an ultrahigh pressure mercury lamp with an output of 0.5 to 100 mW / cm ² . In particular, it is preferable to perform exposure with an exposure amount of about 0.05 to 1.0 J / cm ² .

  After the exposure, development is performed using a developer. As the development method, a known method such as an immersion method, a spray method, or a brush method can be employed. As the developer, an organic solvent or an aqueous solution in which an organic component in the paste can be dissolved or dispersed can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the paste, it can be developed even with an alkaline aqueous solution. A metal alkali aqueous solution such as sodium hydroxide, calcium hydroxide, sodium carbonate aqueous solution or the like can be used as the alkaline aqueous solution. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound or ammonium salt can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkali component contained in the alkaline aqueous solution is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, it is difficult to remove the unexposed portion. If the alkali concentration is too high, the pattern portion may be peeled off and the exposed portion may be corroded. Moreover, it is preferable on process control that the temperature of a developing solution is 20-50 degreeC.

  In the present invention, at least two types of pastes are used, but the patterns of paste A and paste B (in the case of three layers or more, the pattern of all layers using the paste according to the present invention) are preferably the same. This is because if the patterns of the upper layer and the lower layer are different, shrinkage in the XY direction of the pattern of the paste A may not be suppressed.

  Further, the relationship between the thickness ta of the lower layer paste and the thickness tb of the upper layer paste is preferably 0.5 × ta ≦ tb ≦ ta. This is because if the thickness of the upper layer paste is too thin than the thickness of the lower layer paste, shrinkage in the XY direction may not be suppressed in firing the glass contained in the lower layer paste, and the upper layer is thick. This is because the glass contained in the upper layer is softened during sintering and the upper part of the partition may be curved.

  In the production method of the present invention, in addition to the layers of pastes A and B, a layer of paste C composed of an inorganic component containing at least glass particles and an organic component containing at least a binder resin other than pastes A and B. It can apply | coat on the layer by the paste B. FIG. Thus, in the present invention, it is possible to form a multilayer with three or more types of paste. The larger the number of layers, the more the glass is bent during heat shrinkage, but the number of layers is appropriately determined in consideration of the overall thickness and the like.

  The details of what can be used for the inorganic component and the organic component of the paste C are as described in the description of the pastes A and B. The crystallization temperature Tcc of the glass particles contained in the paste C is preferably in a relationship of Tcb <Tcc. In this case, the relationship between the paste thickness tb and the paste thickness tc is preferably 0.5 × tb ≦ tc ≦ tb.

  The paste coating film is introduced into the firing step after forming a desired pattern as necessary. The atmosphere and temperature in firing can be appropriately selected depending on the type of paste or substrate, and an atmosphere of air, nitrogen, hydrogen or the like is used. The firing temperature is usually 400 to 610 ° C. When the paste film is patterned, firing is generally performed by holding at a temperature of 520 to 610 ° C. for 10 to 60 minutes. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. Moreover, you may heat at 50-300 degreeC in the above each process for the purpose of drying and a preliminary reaction.

  A substrate for a panel display can be obtained by forming an electron-emitting device between the side wall of the partition formed by the above steps and between the partitions.

  In addition, by using the substrate as a back plate, for example, and sealing with a separately manufactured front plate, and then mounting the wiring, a panel display with high brightness and high contrast can be obtained.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this. The concentration in Examples and Comparative Examples is% by weight unless otherwise specified.

  The materials used for the pastes A, B, and C are as follows.

(Organic component)
Binder resin: 0.4 equivalent of glycidyl methacrylate (GMA) with respect to the carboxyl group of a copolymer comprising 40% methacrylic acid (MMA), 30% methyl methacrylate (MMA), and 30% methacrylic acid. A weight average molecular weight of 19000 and an acid value of 107 were used.

Photosensitive monomer: Nippon Kayaku Co., Ltd. Karayad TPA-330
Photopolymerization initiator: 2,4-dimethyl oxanthone (manufactured by Nippon Kayaku Co., Ltd.) and Irgacure 369 (manufactured by Ciba Specialty Chemicals) 1: 2 (weight ratio) mixture UV absorber: Sudan (chemical formula C ₂₄ H ₂₀ N ₄ O, azo organic dye having a molecular weight of 380.45)
Dispersant: Noop Cosperth manufactured by Kao Corporation Polymerization inhibitor: p-methoxyphenol,
Solvent: 3-methyl-3-methoxybutanol (inorganic component)
Glass powder A: SiO ₂ 25%, Al ₂ O ₃ 19%, B ₂ O ₃ 33%, ZnO 12%, MgO 6%, CaO 2%, BaO 2%, LiO ₂ 1%
The glass powder was made into a fine powder with an attractor in advance and used with an average particle size of 1.5 μm. The crystallization temperature was 510 ° C.

Glass powder B: SiO ₂ 19%, Al ₂ O ₃ 35%, B ₂ O ₃ 28%, ZnO 10%, MgO 3%, CaO 2%, BaO 1.5%, LiO ₂ 1.5%
The glass powder was made into a fine powder with an attractor in advance and used with an average particle size of 1.8 μm. The crystallization temperature was 515 ° C.

Glass powder C: SiO ₂ 22%, Al ₂ O ₃ 42%, B ₂ O ₃ 28%, ZnO 5%, MgO 1%, CaO 1%, BaO 1%
The glass powder was made into a fine powder with an attractor in advance and used with an average particle size of 1.7 um. The crystallization temperature was 540 ° C.

  Paste A consists of 3.7% by weight of the binder resin, 10% by weight of the photosensitive monomer, 5% by weight of the photopolymerization initiator, 0.1% by weight of the ultraviolet light absorber, 0.2% by weight of the dispersant, and 0% of the polymerization inhibitor. It was prepared by adding 5% by weight, 3.5% by weight of solvent, and 77% by weight of the above glass powder A, and was used after being filtered using a 400 mesh filter. Paste B and Paste C were prepared in the same manner as Paste A, except that the glass components in Paste A were replaced with Glass Powder B and Glass Powder C, respectively.

(Measurement of shrinkage rate)
Using a scanning electron microscope (SEM), the pore diameter before firing and the pore diameter after firing were determined and determined by the following formula.

Shrinkage rate = (pore diameter after firing) / (pore diameter before firing)
In addition, the hole diameter measured the diameter in an opening surface (uppermost surface of a partition).

Example 1
Paste A was uniformly applied on a glass substrate using a screen printing method. Thereafter, it was kept at 80 ° C. for 5 minutes and dried. Next, paste B was uniformly applied thereon using screen printing. Thereafter, it was kept at 80 ° C. for 10 minutes and dried. Subsequently, using a negative chrome mask having a circular pattern with a diameter of 20 μm at a pitch of 40 μm, the surface was exposed to ultraviolet rays from an upper surface with an ultrahigh pressure mercury lamp having an output of 0.5 kW. The exposure amount was 1.0 J / cm ² .

  Next, a 0.1% by weight aqueous solution of potassium hydroxide maintained at 25 ° C. is applied by showering, developed for 30 seconds, then washed with water using a shower spray, and a partition wall pattern having a pore size of about 20 μm on a glass substrate. Formed. The glass substrate on which the partition pattern was formed was baked and crystallized in air at 540 ° C. for 40 minutes to form the partition. When the film thickness after drying was observed with a scanning electron microscope (SEM), the paste A layer was 14 μm and the paste B layer was 9 μm. The film thickness after firing was 15 μm.

Example 2
After paste-printing paste A and paste B in the same manner as in Example 1, paste C is further applied onto the paste B layer by screen printing, followed by drying in the same manner as in Example 1, followed by exposure, development, and baking. A partition wall was formed. The thickness of the paste A layer after drying was 12 μm, the thickness of the paste B layer was 8 μm, and the thickness of the paste C layer was 5 μm. The film thickness after firing was 17 μm.

Example 3
A partition wall was formed in the same manner as in Example 1 except that the paste A was used for the lower layer and the paste C was used for the upper layer. The thickness of the paste A layer after drying was 12 μm, and the thickness of the paste C layer was 8 μm. The film thickness after firing was 14 μm.

Comparative Example 1
A partition wall was formed in the same manner as in Example 1 except that paste B was used for the lower layer and paste A was used for the upper layer. The thickness of the paste B layer after drying was 12 μm, and the thickness of the paste A layer was 10 μm. The film thickness after firing was 15 μm.

Comparative Example 2
A partition wall was formed in the same manner as in Example 1 except that the paste A was applied twice. The film thickness of the lower paste A layer after drying was 12 μm, and the film thickness of the upper paste A layer was 10 μm. The film thickness after firing was 14 μm.

Example 4
A partition wall was formed in the same manner as in Example 1 except that the viscosity of the paste B was lowered and the film thickness of the upper paste B layer was changed to 3 μm. The film thickness of the lower paste A layer after drying was 14 μm. The film thickness after firing was 9 μm.

  The results of Examples 1 to 4 and Comparative Examples 1 and 2 are summarized in Table 1. The first to third layers in Table 1 are in order from the substrate surface side, and the symbols A, B, and C correspond to the types of paste, respectively.

Claims (8)

A step of applying a paste A composed of an inorganic component including at least glass particles and an organic component including at least a binder resin on the substrate; and an inorganic component including at least the glass particles and at least a binder resin on the layer of the paste A. A method for manufacturing a panel display member comprising a step of applying a paste B comprising an organic component, a step of forming a desired pattern as necessary, and a sintering step, wherein the crystallization temperature of the glass particles contained in the paste A is determined. T _CA, when the crystallization temperature of the glass particles contained in the paste B was _{T CB,} the manufacturing method of the panel display member characterized by satisfying _T CA _{<T CB.} The method for producing a panel display member according to claim 1, wherein the organic component includes a photosensitive component. Method for producing a panel display member according to claim 1 or 2 T _CB may be higher 5 ° C. or higher than T _CA. The method for producing a panel display member according to any one of claims 1 to 3, wherein the crystallization temperature of the glass particles contained in the paste A and the paste B is 600 ° C or lower. The method for manufacturing a panel display member according to any one of claims 1 to 4, wherein the amount of the inorganic component in the paste A is 30 to 60 vol% with respect to the total volume of the paste A. The method for manufacturing a panel display member according to any one of claims 1 to 5, wherein the amount of the inorganic component in the paste B is 30 to 60 vol% with respect to the total volume of the paste B. The method for producing a panel display member according to claim 1, wherein the particle size of the glass particles contained in the paste A or paste B is 2 μm or less. The thickness after sintering is 40 micrometers or less, The manufacturing method of the panel display member in any one of Claims 1-7 characterized by the above-mentioned.