JP2007230804A - Inorganic material paste, method of manufacturing member for flat display and flat display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier rib for a flat display free from the occurrence of problems such as tip part chipping due to projecting and recessed part of a tip part of the barrier rib or defective sintering in the formation of the barrier rib for the high precision high aspect ratio flat display. <P>SOLUTION: The inorganic material paste contains an inorganic component and an organic component. The inorganic component contains glass frit L<SB>1</SB>having a softening point expressed by Ts<SB>L1</SB>(°C) and an average particle diameter expressed by D<SB>L1</SB>, glass frit L<SB>2</SB>having a softening point expressed by Ts<SB>L2</SB>(°C) and an average particle diameter expressed by D<SB>L2</SB>and inorganic powder H having an average particle diameter expressed by D<SB>H</SB>and no softening point of ≤600°C wherein a volume concentration of the glass frit L<SB>1</SB>to total inorganic component in the inorganic material paste is V<SB>L1</SB>(%), a volume concentration of the inorganic powder H to total inorganic component in the inorganic material paste is V<SB>H</SB>(%) and the softening temperature, the average particle diameter and the volume concentration of the inorganic component satisfies following relation (1)-(3), where relation (1) is Ts<SB>L1</SB>≤Ts<SB>L2</SB>≤600, relation (2) is D<SB>L1</SB>≤D<SB>H</SB><D<SB>L2</SB>and relation (3) is V<SB>H</SB>≤V<SB>L1</SB>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an inorganic material paste suitable for manufacturing a flat display such as a plasma display, a field emission display, and a fluorescent display tube, a method for manufacturing a flat display member, and a flat display.

  In recent years, development of flat displays such as a plasma display, a field emission display, a fluorescent display tube, a liquid crystal display device, an electroluminescence display, and a light emitting diode has been rapidly advanced. Among these, a gas discharge type display such as a plasma display or a fluorescent display tube requires an insulating partition for partitioning the discharge space. A field emission display such as a field emission display requires an insulating partition for isolating the gate electrode from the cathode electrode. In the formation of insulating partition walls such as these plasma displays and field emission displays, materials and processing methods capable of patterning inorganic materials such as glass fine particles with high accuracy are required.

  In particular, in a plasma display (hereinafter referred to as PDP), it is an indispensable technique for increasing the brightness of a plasma display by forming high-definition and high-aspect-ratio barrier ribs to ensure a wider discharge space. Conventionally, a method of forming a pattern using a photosensitive paste has been proposed as a method for performing fine pattern processing of an inorganic material (for example, Patent Document 1).

The top of the partition for plasma display is preferably flat for the purpose of preventing charge leakage to adjacent cells and chipping of the top of the partition when the panel is dropped. Conventionally, for flattening the top, there is a method in which a high melting point glass that does not melt during firing and a low melting point glass that melts during firing are used in combination, and the average particle size of the high melting point glass is smaller than the average particle size of the low melting point glass. It has been proposed (for example, Patent Document 2). However, if the average particle size of the high melting point glass is simply reduced, the high melting point glass tends to agglomerate at the time of firing, and there is a problem that a raised product is formed at the top of the partition wall or a sintering failure due to the aggregate occurs inside the partition wall. It was.
JP-A-5-342992 JP-A-8-050811

  The present invention pays attention to the above-mentioned problems of the prior art, and for forming a high-definition and high-aspect-ratio flat display partition wall, it does not cause problems such as chipping due to irregularities at the top of the partition wall or defective sintering. An object of the present invention is to provide an inorganic material paste used for forming a partition wall, a method for producing a flat display member using the same, and a flat display.

  In order to solve the above problems, the present invention has the following configuration.

That is, an inorganic material paste containing an inorganic component and an organic component, the glass frit L _{1 having} a softening temperature Ts _L1 (° C.) and an average particle diameter of D _L1 as the inorganic component, and the softening temperature Ts _L2 (° C.). Glass frit L ₂ having an average particle diameter of D _L2 and inorganic powder H having an average particle diameter of _DH and having no softening temperature at 600 ° C. or less, and the glass frit L _{1 in} the inorganic material paste The volume concentration with respect to the inorganic component is V _L1 (%), the volume concentration with respect to all the inorganic components in the inorganic material paste of the inorganic powder H is V _H (%), and the softening temperature, average particle diameter, and volume concentration of the inorganic component Satisfies the following formulas (1) to (3).
Ts _L1 ≦ Ts _L2 ≦ 600 (1)
D _L1 ≦ D _H <D _L2 (2)
V _H ≦ V _L1 (3)

  According to the present invention, when a high-definition and high-aspect-ratio flat display partition is formed, it is possible to provide a flat display partition that does not suffer from problems such as chipping due to irregularities at the top of the partition and poor sintering.

As a result of intensive studies on a method for producing an inorganic material paste used for a partition wall of a flat display capable of solving the above-mentioned problems, the inventors have found that this can be achieved by a method for producing an inorganic material paste as described below. That is, an inorganic material paste containing an inorganic component and an organic component, wherein the inorganic component is a glass frit L ₁ having a softening temperature of Ts _L1 (° C.), an average particle diameter of D _L1 , and a softening temperature of Ts _L2 (° C.). A glass frit L ₂ having an average particle diameter of D _L2 and an inorganic powder H having an average particle diameter of _DH and not having a softening temperature at 600 ° C. or less, including all inorganic substances in the inorganic material paste of the glass frit L ₁ The volume concentration with respect to the component is V _L1 (%), the volume concentration with respect to all inorganic components in the inorganic material paste of the inorganic powder H is V _H (%), and the softening temperature, average particle diameter, and volume concentration of the inorganic component are An inorganic material paste characterized by satisfying the following formulas (1) to (3).
Ts _L1 ≦ Ts _L2 ≦ 600 (1)
D _L1 ≦ D _H <D _L2 (2)
V _H ≦ V _L1 (3)
The glass frit used in the present invention is not particularly limited and can be selected in consideration of the electrical characteristics, optical characteristics, mechanical characteristics, sinterability, etc. of the pattern, but when used for plasma display partition walls and front plate dielectric patterns, The softening temperatures Ts _L1 and Ts _L2 of the glass frit L ₁ and L ₂ are preferably in the range of 400 ° C. to 600 ° C. When glass frit is used as the inorganic powder H, the softening temperature of the inorganic powder H is preferably 600 ° C to 800 ° C. A more preferable range of Ts _L1 and Ts _L2 is 400 to 530 ° C.
In the present invention, the softening temperatures Ts _L1 and Ts _L2 of the glass frit satisfy the above formula (1). It as glass frit L ₁ and the glass frit L ₂ by using a glass frit identical composition softening temperature Ts _L1, Ts _L2 may be used the same, the softening temperature Ts _L1 using a glass frit having different compositions It may be lower than Ts _L2 .
When the glass frit having the same composition is used as the glass frit L ₁ and the glass frit L ₂ , among the glass frits having a softening temperature Ts _L1 (= Ts _L2 ), those having a particle diameter smaller than _DH are the glass frit L ₁ , D _L1 , D _L2 , V _L1 , V _L1 (volume concentration with respect to all inorganic components in the inorganic material paste of the glass frit L ₁ ) is determined with a glass frit L ₂ having a particle size larger than _DH .

The glass frit of the present invention is preferably used in a method for forming an inorganic material pattern by firing at a temperature higher than Ts _L2 and at which the inorganic powder H does not soften. Glass frit L ₁ and glass frit L ₂ forms a strong inorganic material pattern softened during the firing. By including the inorganic powder H that does not soften during firing, shape retention during firing and mechanical strength of the inorganic material pattern after firing can be ensured.

  The softening temperature Ts of the glass frit can be measured using a differential thermal analyzer DTA (for example, Thermo Plus2: manufactured by Rigaku Corporation). A sample is filled in a dedicated sample holder, the temperature is raised at 10 ° C./min, and the endothermic amount is measured. The temperature at which the endotherm reaches the lowest point is read as the softening temperature.

  The particle size of the glass frit can be measured using a laser diffraction scattering method (for example, Microtrack particle size distribution measuring device MT3000, manufactured by Nikkiso Co., Ltd.). The average particle diameter is read as the particle diameter at which the accumulation (%) of the frequency (%) of each particle diameter becomes 50%. The maximum particle size is read as the particle size with a frequency (%) of 100%.

The maximum particle size of the inorganic powder H used in the present invention is preferably 10 μm or less. When the maximum particle size is 10 μm or more, the unevenness at the top of the inorganic material pattern obtained after firing becomes large. For example, when it is used for a PDP partition wall, if the unevenness of the top of the partition wall becomes large, a problem that the partition wall is missing when it comes into contact with the opposing substrate, so-called chipping occurs. Further, _DH is preferably 5 μm or less, more preferably 2 μm or less. This is because when _DH is 5 μm or more, many particles having a particle diameter exceeding 10 μm are included, which causes chipping. When chipping occurs, it causes a display defect due to a glass piece generated by chipping.

In the present invention the mean particle diameter D _L1 of the glass frit L ₁ is characterized in that either the same as the average particle diameter D _H of the inorganic powder H small.

When D _L1 is the same as or smaller than _DH , when the inorganic material paste is applied, the glass frit L ₁ is arranged between the inorganic powders H, and the glass frit L ₁ functions as a binder that connects the inorganic powder H. has, inorganic powder H is covered in glass frit L ₁ which is melted during firing, it can be inorganic powder H is prevented from aggregation. The probability that conversely D _L1 inorganic powder H is placed in the large and the gap of the glass frit L ₁ than D _H is increased, the inorganic powder H are agglomerated during calcination, in the surface of the inorganic material pattern coarse protrusions appear. In the internal inorganic material pattern glass frit L ₁ melted in the gap made by agglomeration remains sintering defect arises that is generated as a void can not penetrate. When used in the PDP barrier ribs, or coarse protrusions on the partition wall top occurs and the sintered defect occurs in the partition wall, it will cause the display defect due to chipping and chipping mentioned above, D _L1 is a D _H Must be the same or smaller.

Also in the present invention, wherein the average particle diameter D _L2 of the glass frit L ₂ is greater than the average particle diameter D _H of the inorganic powder H.

When D _L2 is larger than _DH, the specific surface area of the glass frit L ₂ is reduced, and the dispersibility of the inorganic material paste is improved.

It is preferred maximum particle size of the glass frit L ₂ is 15μm or less. This is because when the maximum particle size is 15 μm or more, even if the softening temperature is reached, it does not melt sufficiently and irregularities are formed at the top of the partition walls.

In the present invention, the volume concentration V _L1 (%) with respect to all inorganic components in the inorganic material paste of the glass frit L _{1 and} the volume concentration V _H (%) with respect to all inorganic components in the paste of the inorganic powder H are expressed by the following formulas. It is necessary to satisfy (3).
V _H ≦ V _L1 (3)
Same or V _L1 is a V _H, by greater than V _H, glass frit L ₁ is securely disposed on the periphery of the inorganic powder H when applied to inorganic materials paste, an inorganic powder H glass frit L ₁ is melted It is covered with, and aggregation of the inorganic powder H can be suppressed.

In the present invention, when the volume concentration for total inorganic component in the inorganic material of the glass frit L ₂ paste and V _{L2 (%),} it V _L2 is greater than V _L1 it is preferable. By making V _L2 larger than V _L1 and V _H , dispersibility in the paste can be improved.

Volume content _{V H} of the glass frit _{L 1} and the sum of the volume content of _{L 2 V L (= V L1} + V L2) and the inorganic powder H is 5: 95 to 40: is preferably in the range of 60. When _VH is less than the above range, shape retention and mechanical strength may be reduced. This is because when V _H is larger than the above range, display failure due to sintering failure or generation of coarse protrusions due to aggregation occurs.

The composition of the glass frit L ₁ and glass frit L ₂ used in the present invention is not particularly limited, the firing temperature or electrical, can be appropriately selected by the optical properties. For example, known PbO—B ₂ O ₃ series, PbO—ZnO—B ₂ O ₃ —SiO ₂ series, PbO—ZnO—B ₂ O ₃ series, ZnO—BaO—B ₂ O ₃ series, Bi ₂ O ₃ series Glass, phosphate glass, and ZnO—B ₂ O ₃ glass are preferably used. Thermal expansion coefficient, preferably a material showing a value close to the glass substrate to be used, (the difference between the glass substrate in thermal expansion coefficient at eg 30 ° C. to 400 ° C.) the difference in thermal expansion coefficient 10 × 10 ^-7 ℃ ^-1 It is as follows. More preferably, it is 5 × 10 ⁻⁷ ° C. ⁻¹ or less.

  The composition of the inorganic powder H used in the present invention is not particularly limited, and oxides such as alumina, silica, titania, cordierite, and magnesia, composite oxides thereof, and high softening temperature glass having a softening temperature higher than 600 ° C. are preferable. It is. A white pigment or a black pigment may be added for the purpose of controlling the object color after firing.

Further, when producing a photosensitive paste using the present invention, the densities R _L1 , R _L2 and R _H of the glass frit L ₁ , the glass frit L ₂ and the inorganic powder H satisfy the following expressions (4) and (5). It is preferable.
0 ≦ R _L2 −R _L1 <1 (4)
0 ≦ R _H −R _L1 <1 (5)
When the density of the glass frit L ₁ , the glass frit L ₂ and the inorganic powder H is within the above range, each component is separated in the paste particularly during the production, storage and use of the inorganic powder paste. It is possible to prevent H from aggregating.

  As an organic component contained in the inorganic material paste, for example, as described later, for example, a resin, a solvent, a monomer, an oligomer, a polymerization initiator, or the like can be used as necessary.

  The organic material is not particularly limited and can be appropriately selected depending on the pattern forming method. For example, when pattern formation is performed by a sandblasting method or a screen printing method, a cellulose compound such as methyl cellulose or ethyl cellulose, a high molecular weight polyether, an acrylic resin, or the like can be used as the resin. Acrylic resins can be preferably used as a polymer because there are few firing residues after firing. For example, it is an acrylic resin made of a polymer or copolymer such as methyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopril methacrylate, isobutyl acrylate, and isobutyl methacrylate.

  The solvent is not particularly limited, and known solvents can be used. For example, alcohols, terpenes, ketones, ketone esters, ethers, esters, ether esters, amides, amide esters, lactams, lactones And hydrocarbons can be used. For example, methanol, ethanol, isopropanol, benzyl alcohol, propylene glycol, terpineol, acetone, methyl ethyl ketone, cyclohexane, diethyl ketone, carbitol, methyl carbyl tol, propylene glycol monoethyl ether, ethyl acetate, butyl acetate, carbitol acetate, γ- Examples include butyrolactone, toluene, xylene, and tetramethylbenzene.

  In addition, the inorganic material paste of the present invention is preferably a photosensitive paste containing a photosensitive component in an organic component because a pattern with high definition and a high aspect ratio can be obtained. Hereinafter, an organic component when the inorganic material paste of the present invention is a photosensitive paste will be described.

  As the resin used for the photosensitive paste, a known material can be applied, but it preferably has a function of controlling the developability of the unexposed portion. In particular, a polymer having a weight average molecular weight of 2000 to 60,000, more preferably 5000 to 40,000 having a carboxyl group in the molecular side chain is used. The acid value of the polymer is preferably from 50 to 160, particularly preferably from 70 to 140, from the viewpoint of development tolerance and solubility in the unexposed area developer.

  Moreover, it is preferable to contain a photoinitiator. In some cases, a sensitizer may be added to assist the effect of the photopolymerization initiator.

  As the photopolymerization initiator, those that generate radical species are preferably used. For example, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, di Benzyl 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, benzoin methyl ether, Zoin 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-propanedione-2 -(O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2- Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole Examples include combinations of disulfide, triphenylformine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, methylene blue and other photoreductive dyes and reducing agents such as ascorbic acid and triethanolamine. It is done.

  Moreover, when making the inorganic material paste of this invention into a photosensitive paste, it is preferable to contain a crosslinking agent. By forming a three-dimensional network structure with radicals generated from the polymerization initiator as a starting point, the cross-linking agent improves developer resistance during development, and defects such as cracks and disconnection even when firing stress occurs during firing Can be suppressed. Specific examples of the compound containing a carbon-carbon unsaturated bond as a crosslinking agent include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl 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, isobo Acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoro Ethyl 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, Pentaerythritol monohydroxypentaacrylate, 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, bisphenol A-propylene oxide adduct Jiacri Rate, thiophenol acrylate, benzyl mercaptan 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, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene , Vinyl carbazole, and those obtained by changing some or all of the acrylates in the molecule of the above compounds to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like.

  When the inorganic material paste of the present invention is a photosensitive paste, it is preferable to use an ultraviolet absorber.

  The ultraviolet absorber here refers to a substance that absorbs a wavelength of 300 to 500 nm and emits the absorbed light energy as an inactive radiation (thermal energy). Usually, an ultra-high pressure mercury lamp used in photolithography technology. It is particularly effective if it has excellent absorbance at wavelengths in the vicinity of g-line (436 nm), h-line (405 nm), and i-line (365 nm), but absorbs ultraviolet rays to distinguish it from the photo-fading compound described later. This means that the total light transmittance of ultraviolet rays does not change with time.

  Specific examples include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, inorganic fine-particle metal oxides, and the like. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective.

  Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-. Dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2'-G Roxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-ethylhexyl- 2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, BONASORB UA-3901 (manufactured by Orient Chemical Co., Ltd.), BONASORB UA-3902 (indole UV absorber) Orient Chemical Co., Ltd.), BONASORB UA-3911 (Orient Chemical Co., Ltd.), SOM-2-0008 (Orient Chemical Co., Ltd.), Basic Blue, Sudan Blue, Sudan R, Sudan I, Sudan II, Sudan III, Sudan IV, Oil Orange SS, Oil Violet, Oil Yellow OB (above, Aldrich) are limited to these. Not. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  When the inorganic material paste of the present invention is used as a photosensitive paste, the addition of a silane coupling agent or a titanium coupling agent (hereinafter referred to as a coupling agent) can increase the exposure margin when forming a high-definition pattern. More preferred above. From the viewpoint of ease of use and cost, a silane coupling agent is particularly preferable. A silane coupling agent is a structure in which an organic functional group having affinity or reactivity for organic substances is chemically bonded to a hydrolyzable silyl group having affinity or reactivity for inorganic materials. The titanium coupling agent has a structure in which the silane portion of the silane coupling agent is replaced with titanium. By adding a coupling agent to the paste, adhesion between a substrate containing a glass substrate and a material containing an inorganic substance and a pattern containing an organic component is improved. Usually, a pattern with a width of 60 μm or less is easily peeled off during development, but the addition of a silane coupling agent or a titanium coupling agent makes peeling during development difficult even when a high-definition pattern with a width of 50 μm or less is formed. The amount margin can be expanded.

  In the silane coupling agent, examples of the hydrolyzable group bonded to silicon include an alkoxy group, a halogen, and an acetoxy group. Usually, an alkoxy group, particularly a methoxy group and an ethoxy group are preferably used.

  Examples of the organic functional group include amino group, methacryl group, acrylic group, vinyl group, epoxy group, mercapto group, alkyl group, and allyl group. Specifically, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-dibutylaminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminomethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyeth Xy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-decyl Examples include trimethoxysilane, n-hexadecyltrimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. In the present invention, these coupling agents may be used alone or in combination of two or more. Moreover, you may use the self-condensate of one type of coupling agent, and the heterocondensate which combined 2 or more types.

  The weight average molecular weight of the coupling agent is preferably 200 to 1000, and more preferably 250 to 500. When the weight average molecular weight is 200 or more, the effect reduction due to evaporation of the coupling agent during drying of the paste coating film can be suppressed, and when it is 1000 or less, the thermal decomposability during firing is improved. Can keep.

  The organic functional group of the coupling agent is preferably a photosensitive functional group, and is preferably an ethylenically unsaturated group. Specific examples include a methacryl group, an acryl group, and a vinyl group. Coupling agents having these organic functional groups also act as monomers during photocuring of the photosensitive paste, and insolubility progresses near the boundary between the inorganic fine particles and the organic components during exposure, and the pattern meanders due to the infiltration of the developer. Can be suppressed.

  In the case where the inorganic material paste of the present invention is a photosensitive paste, the organic component may be a photosensitive oligomer, a photosensitive agent, in addition to the ultraviolet absorber, antioxidant, photosensitive monomer, silane coupling agent or titanium coupling agent. Photosensitive organic component, organic dye, photopolymerization initiator, sensitizer, sensitizer, plasticizer, thickener, dispersant, organic solvent, precipitation inhibitor, etc. It is comprised by adding the additive component of as needed.

  It is also a preferred practical form of the present invention to use a glass frit that has been surface-treated with the above coupling agent or titanium coupling agent. By using the surface-treated glass frit, the affinity between the glass frit and the organic component can be increased, and the development resistance of the exposed portion can be improved. The surface treatment method is arbitrary. For example, an aqueous solution method in which a dilute aqueous solution containing a coupling agent is prepared to impregnate glass frit, an organic solvent method in which an organic solvent containing a coupling agent is applied, and a direct coupling agent The spray method etc. which spray can be mentioned.

  When the inorganic material paste of the present invention is used as a photosensitive paste, each component such as an ultraviolet absorber, a silane coupling agent, an antioxidant, inorganic fine particles, a photosensitive organic component, an organic dye, a dispersant, and a solvent is predetermined. It is preferable to carry out the main kneading after pre-kneading after preparing the composition so as to have the following composition. The preliminary mixing can be preferably applied by hand stirring, a magnetic stirrer, or a mechanical stirrer. Further, when adding a photosensitive polymer, it may be added directly to the dispersion, but adding a photosensitive polymer solution in which a photosensitive polymer is dissolved in advance in an organic solvent provides a uniform photosensitive paste. This is preferable. Next, main kneading is performed using a kneading apparatus such as a three-roller, and the mixture is uniformly dispersed to produce a glass paste. Moreover, it is also preferable to filter the glass paste after this kneading using a filter having an opening of 1 to 20 μm. Furthermore, it is also preferable to defoam the glass paste using a kneading and defoaming machine or a vacuum stirrer.

  Moreover, the manufacturing method of the member for flat displays of this invention is a manufacturing method of the member for flat displays including the process of forming the inorganic material pattern by apply | coating the above-mentioned inorganic material paste to a base material, patterning, and baking. It is. The present invention is suitable when the inorganic material pattern to be formed is a partition, and is particularly suitable for the production of a PDP member, particularly a PDP back plate.

  Hereinafter, the manufacturing method of the member for flat displays using the inorganic material paste of this invention, especially the manufacturing method of the backplate of PDP is demonstrated.

  As the glass substrate of the present invention, “PD200” manufactured by Asahi Glass or “PP8” manufactured by Nippon Electric Glass, which is a heat-resistant glass, can be used in addition to soda glass.

  When used as a member for a plasma display, an electrode pattern is formed on a glass substrate with a metal such as silver, aluminum, chromium or nickel. As a method for forming an electrode, a metal paste mainly composed of these metal fine particles and an organic binder is subjected to pattern printing and baking by screen printing, or a photosensitive metal paste using a photosensitive organic component as an organic binder. After coating, a photosensitive paste method can be used in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development step, and further, heated and baked at 350 to 600 ° C. to form an electrode pattern. . Further, an etching method can be used in which after chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, and after the resist is subjected to pattern exposure and development, unnecessary portions are removed by etching.

  When used as a back plate for a plasma display, it is preferable to provide a dielectric layer after the electrodes are formed. By providing the dielectric layer, it is possible to improve the stability of discharge and to prevent the partition wall formed on the upper layer of the dielectric layer from falling or peeling off. As a method of forming the dielectric layer, a dielectric paste mainly composed of inorganic fine particles such as glass and high-melting glass fine particles and an organic binder is applied on the entire surface with a screen printer, a slit die coater, or a release film. There is a method in which a front surface is printed or coated and then transferred onto a substrate on which an electrode is formed.

  Next, a method for forming partition walls by photolithography using a photosensitive paste will be described. The partition pattern is not particularly limited, but a lattice shape, a waffle shape, a via hole shape, and the like are preferable.

  In the present invention, a barrier rib paste made of a photosensitive paste is applied on a substrate on which an electrode or a dielectric is formed. For coating, an apparatus such as a bar coater, a roll coater, a slit die coater, a blade coater, or a screen printing machine can be used. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage rate due to baking of the paste. The coating thickness can be adjusted by the number of coatings, screen mesh, paste viscosity, and the like. For field emission displays and fluorescent display tubes, the thickness after firing is preferably 5 to 50 μm, and for plasma displays, it is preferably applied to 50 to 200 μm.

  The exposure is generally carried out through a photomask, as is done by ordinary photolithography, but a method of drawing directly with a laser beam or the like may be used.

As the exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. Moreover, when performing exposure of a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate such as a glass substrate and then performing exposure while transporting. it can. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is usually performed for 0.01 to 30 minutes using an ultrahigh pressure mercury lamp having an output of 1 to 100 mW / cm ² .

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the non-exposed portion in the developer. Usually, the immersion method, the spray method, the brush method, and the like are performed. As the developer, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. However, when a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used. 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 can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine.

  The density | concentration of aqueous alkali solution is 0.05-5 mass% normally, More preferably, it is 0.1-1 mass%. If the alkali concentration is too low, it is difficult to remove the soluble part, and if the alkali concentration is too high, the pattern may be peeled off or corroded, which is not preferable. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  In the present invention, patterning after applying the inorganic material paste is particularly preferably performed by a photolithography method using a photosensitive paste as described above in order to obtain a high-definition pattern. An inexpensive clean printing method or the like may be used.

  Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of inorganic material paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Usually, when an acrylic resin is used, baking is performed at 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked. Through the above process, the partition for a flat display of the present invention is formed.

  Next, a method for manufacturing a display using this partition will be described.

In the case of forming a back plate for a plasma display, after forming electrodes, dielectrics and barrier ribs on a glass substrate, a phosphor is formed between the barrier ribs using a phosphor paste. It can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. The thickness of the phosphor is not particularly limited, but is 0.01 to 0.03 mm, more preferably 0.015 to 0.025 mm. The phosphor fine particles are not particularly limited, but the following phosphors are preferable from the viewpoints of light emission intensity, chromaticity, color balance, lifetime, and the like. Blue is an aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ activated with divalent europium. In the case of green, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl ₁₂ O ₁₉ : Mn, and BaMgAl ₁₄ O ₂₃ : Mn are preferable in terms of panel luminance. More preferably _Zn 2 _SiO 4: is Mn. In red, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, YPVO: Eu, and YVO ₄ : Eu are also preferable. More preferred is (Y, Gd) BO ₃ : Eu.

  Next, a method for producing a front plate for plasma display will be described. As the substrate, in addition to soda glass, “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) or “PD200” (manufactured by Asahi Glass Co., Ltd.), which is a heat resistant glass for plasma display, can be used. The size of the glass substrate is not particularly limited, and a glass substrate having a thickness of 1 to 5 mm can be used.

  First, indium-tin oxide (ITO) is sputtered on a glass substrate, and a pattern is formed by a photoetching method. Subsequently, the black electrode paste for black electrodes is printed. The black electrode paste is composed mainly of an organic binder, a black pigment, conductive fine particles, and a photosensitive component when used in a photolithography method. As the black pigment, a metal oxide is preferably used. Examples of metal oxides include titanium black, copper, iron, manganese oxides and their composite oxides, and cobalt oxides. Cobalt oxides are less susceptible to fading when mixed with glass and fired. Is excellent. Examples of the conductive fine particles include metal fine particles or metal oxide fine particles. As the metal fine particles, gold, silver, copper, nickel and the like which are usually used as electrode materials can be used without particular limitation. Since this black electrode has a high resistivity, an electrode paste having a high conductivity (for example, a material containing silver as a main component) is printed on the black electrode paste in order to produce a bus electrode by producing an electrode with a low resistivity. Print on the side. As this conductive paste, an electrode paste used for an address electrode can also be suitably used. Then, batch exposure / development is performed to produce a bus electrode pattern. In order to ensure the conductivity, a highly conductive electrode paste may be printed again before development, and may be collectively developed after re-exposure. After the bus electrode pattern is formed, baking is performed. Thereafter, it is preferable to form a black stripe or a black matrix in order to improve contrast. Next, a transparent dielectric layer is formed using a transparent dielectric paste. The transparent dielectric paste is mainly composed of an organic binder, an organic solvent, and glass, but an additive such as a plasticizer may be appropriately added. The method for forming the transparent dielectric layer is not particularly limited. For example, the transparent dielectric paste is applied to the entire surface of the substrate on which the electrode is formed by screen printing, bar coater, roll coater, die coater, blade coater, spin coater, etc. Or after apply | coating partially, it can dry using arbitrary things, such as ventilation oven, a hotplate, an infrared drying furnace, and vacuum drying, and a thick film can be formed. It is also possible to make the transparent dielectric paste into a green sheet and laminate it on the electrode forming substrate. The thickness is preferably 0.01 to 0.03 mm.

  Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Usually, when an acrylic resin is used, baking is performed at 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked.

Further, a protective film is formed. As the protective film, MgO, MgGd ₂ O ₄ , BaGd ₂ O ₄ , Sr _0.6 Ca _0.4 Gd ₂ O ₄ , Ba _0.6 Sr _0.4 Gd ₂ O ₄ , SiO ₂ , TiO ₂ , Al ₂ O ₃ and at least one kind from the above-mentioned group of low softening point glasses are preferably used, and MgO is particularly preferable. As a method for producing the protective film, a known technique such as electron beam evaporation or ion plating is suitable.

  Next, a method for manufacturing a plasma display panel will be described. After sealing the back plate and the front plate of the present invention, evacuating while heating the space formed in the gap between the two substrates, and then enclosing a discharge composed of He, Ne, Xe, etc. Seal. From the viewpoint of both discharge voltage and luminance, a Xe-Ne mixed gas having .Xe of 5 to 15% by volume is preferable. In order to increase the generation efficiency of ultraviolet rays, Xe may be further increased to about 30% by volume.

  Finally, a plasma display panel can be manufactured by mounting and aging the drive circuit.

  When manufacturing a cathode substrate for field emission display using the manufacturing method of the present invention, after forming electrodes and partition walls on a glass substrate, after depositing nickel or aluminum, a resist is applied, and the resist is subjected to pattern exposure and development. After that, unnecessary portions are removed by etching, and a gate electrode is formed on the partition wall. Next, an electrode pattern is formed on the gate electrode with a metal such as silver, aluminum, chromium, or nickel. As a method of forming, after applying a metal paste mainly composed of these metal fine particles and an organic binder by screen printing, or after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, It is possible to use a photosensitive paste method in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development step, and further heated and baked at 350 to 600 ° C. to form an electrode pattern. Further, an etching method can be used in which after silver or aluminum is vapor-deposited on a glass substrate, a resist is applied, an unnecessary portion is removed by etching after pattern exposure / development of the resist. After the electrodes are formed, the cathode substrate can be formed by forming an emitter between the partition walls by a rotary evaporation method or CNT paste.

  Next, a method for producing an anode substrate for a field emission display will be described. First, indium-tin oxide (ITO) is sputtered on a glass substrate, and a pattern is formed by a photoetching method. Next, a black resin paste for black matrix (BM) is printed. The black resin paste contains an organic binder, a black pigment, and a photosensitive component as a main component when used in a photolithography method. As the black pigment, carbon black or metal oxide is preferably used. Examples of the metal oxide include titanium black, copper, iron, manganese oxides, composite oxides thereof, and cobalt oxides. Next, a phosphor layer is formed on the transparent electrode. The phosphor layer can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. Next, an aluminum back film is formed by vapor deposition, and an anode substrate can be formed by disposing a spacer.

  Next, a method for manufacturing a field emission display will be described. After sealing the cathode substrate and the anode substrate of the present invention, the space formed between the two substrates is evacuated while being heated and then sealed. Finally, a field emission display can be manufactured by attaching a drive circuit and aging.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this.

A. Measurement of glass softening point The glass softening temperature Ts was measured using a differential thermal analyzer DTA (Thermo Plus 2: manufactured by Rigaku Corporation). A sample is filled in a dedicated sample holder, the temperature is raised at 10 ° C./min, and the endotherm is measured. The point at which the endothermic curve first bends (first endothermic point) is read as the glass transition temperature, and the temperature at which the endothermic amount reaches the lowest point is read as the softening point.

B. Classification of glass frit and inorganic powder Classification of glass frit and inorganic powder was carried out using an air classifier MDS-1 manufactured by Nippon New Match Industrial Co., Ltd.

C. Measurement of Particle Size Distribution The particle size of glass can be measured using a laser diffraction scattering method (Microtrack particle size distribution measuring device MT3000, manufactured by Nikkiso Co., Ltd.). The average particle diameter is read as the particle diameter at which the accumulation (%) of the frequency (%) of each particle diameter becomes 50%. The maximum particle size is read as the particle size with a frequency (%) of 100%.
Measurement conditions were as follows.
Sample amount: 100mg
Dispersion conditions: Ultrasonic dispersion in purified water for 5 minutes. If dispersion is difficult, perform in 0.2% sodium hexametaphosphate aqueous solution.

D. Manufacturing method of barrier rib paste As the barrier rib paste, a photosensitive paste was prepared as follows.

Photosensitive polymer: a product obtained by adding 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer of methacrylic acid / methyl methacrylate / styrene = 40/40/30 (weight average molecular weight 43,000, acid value) 100) 40% by mass γ-butyrolactone solution (30 parts by mass), photosensitive monomer 1: trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.) (3 parts by mass), photosensitive monomer 2: tetrapropylene glycol dimethacrylate (Nippon Yushi Co., Ltd.) (3 parts by mass), photopolymerization initiator: IC369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, Ciba Specialty Chemicals) ( 3 parts by mass), antioxidant: 1,6-hexanediol-bis [(3,5-di-t-butyl) -4-hydroxyphenyl) propionate]) (0.01 parts by mass), UV absorber: Sudan IV (manufactured by Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm) (0.3 parts by mass), silane coupling agent : Γ-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) (3 parts by mass), γ-butyrolactone was appropriately added as a solvent to adjust the viscosity, and an organic component was prepared. Then the glass frit L ₁ and the glass frit L ₂ and the inorganic powder H selected from the following inorganic components were added.
Glass frit 1: lithium oxide 7% by mass, silicon oxide 23% by mass, boron oxide 50% by mass, zinc oxide 1% by mass, aluminum oxide 13% by mass, magnesium oxide 1% by mass, barium oxide 2% by mass, calcium oxide 1% by mass %, Other 2%. Glass transition point 480 ° C., glass softening point 530 ° C., coefficient of thermal expansion 75 × 10 ⁻⁷ ° C. ⁻¹ , density 2.54 g / cm ³ , average refractive index 1.586.
Glass frit 2: Alumina borosilicate glass, glass transition point 455 ° C., glass softening point 495 ° C., thermal expansion coefficient 85 × 10 ⁻⁷ ° C. ⁻¹ , density 2.56 g / cm ³ .
Glass frit 3: alumina borosilicate glass, glass transition point 428 ° C., glass softening point 458 ° C., coefficient of thermal expansion 95 × 10 ⁻⁷ ° C. ⁻¹ , density 2.55 g / cm ³ .
Inorganic powder 1 (high softening temperature glass frit): sodium oxide 1%, silicon oxide 40%, boron oxide 10%, aluminum oxide 33%, zinc oxide 4%, calcium oxide 9%, titanium oxide 3%. Glass transition point 652 ° C., glass softening point 720 ° C., thermal expansion coefficient 42 × 10 ⁻⁷ ° C. ⁻¹ , density 2.59 g / cm ³ .

  In addition to the organic components at a volume ratio shown in Table 1 so that the total mass of the glass frit and inorganic powder was 50% by mass of the entire partition wall paste, the photosensitive paste was prepared by kneading with a three-roller kneader.

  Glass frit and inorganic powder were classified by the above method, and those having an average particle diameter shown in Table 1 were used.

D. Preparation of electrode paste The electrode paste is composed of the photosensitive polymer (7 parts by mass), the photosensitive monomer 1 (3 parts by mass), the photopolymerization initiator (1 part by mass), and the urethane compound UA-5348PE (1 part by mass). ) And dipropylene glycol monomethyl ether (7 parts by mass) while being heated to 50 ° C., and then silver fine particles (average particle size 1.5 μm, specific surface area 0.80 m ² / g, 80 parts by mass) are added. And kneading using a kneader.

E. Preparation of Dielectric Paste Dielectric paste is composed of polymer solution: ethyl cellulose (number average molecular weight 80000) 5% by mass terpineol solution (20% by mass), photosensitive monomer 1 (10% by mass), polymerization initiator (1,1- Azobiscyclohexane-1-carbonitrile (5% by mass) and urethane compound (5% by mass) are dissolved while heating to 50 ° C., and inorganic components (low melting point glass powder: 38% by mass of bismuth oxide, 6% by mass of silicon oxide) %, Boron oxide 20 mass%, zinc oxide 20 mass%, aluminum oxide mass 4%, glass transition point 475 ° C., softening point 515 ° C., thermal expansion coefficient 75 × 10 ⁻⁷ / ° C., density 4.61 g / cm ³ ) (40% by mass), filler (silicon oxide: manufactured by Nippon Aerosil Co., Ltd., “Aerosil 200” 5% by mass), conductor powder (titanium oxide, 10% by mass), TE A mixture composed of lupineol (5% by mass) was prepared by kneading with a three-roller kneader. In addition, the titanium oxide mixed as conductive powder also has a role as a filler component.

F. Manufacturing method of display member First, a plasma display front plate was prepared by the following procedure. An ITO electrode having a thickness of 1 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by a photoetching method, and then a bus electrode pattern was formed by a photolithography method using a photosensitive silver paste. . Thereafter, a transparent dielectric layer was formed to a thickness of 30 μm by screen printing. Finally, a 500 nm thick MgO film was formed by electron beam evaporation to obtain a front plate.

The plasma display back plate was prepared by the following procedure. On the “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd., an electrode paste was used to form a coating film having a thickness of 8 μm by screen printing, and then an address electrode pattern was formed by photolithography. Next, a dielectric layer having a thickness of 20 μm was formed on the glass substrate on which the address electrodes were formed by screen printing. Thereafter, the photosensitive paste was repeatedly applied and dried several times or more on the back plate glass substrate on which the address electrode pattern and the dielectric layer were formed by screen printing so that the thickness after drying was 100 μm. Drying during printing was performed at 100 ° C. for 10 minutes. Next, exposure was performed through an exposure mask. The exposure mask is a negative chrome mask designed to enable the formation of a stripe-shaped auxiliary barrier rib pattern in a plasma display with a pitch of 700 μm and a line width of 40 μm. In the exposure, 250 mJ / cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² . Next, the photosensitive paste was printed several times by screen printing so that the thickness after drying was 150 μm including the lower layer. Drying during printing was performed at 100 ° C. for 10 minutes. As the exposure mask, a negative chrome mask having a pitch of 300 μm and a line width of 40 μm was used, and ultraviolet exposure was performed from the top surface with an ultrahigh pressure mercury lamp with 50 mW / cm ² output.

  Next, a 0.3% by mass aqueous solution of monoethanolamine kept at 35 ° C. was developed by applying it for 150 seconds in a shower, and was washed with water using a shower spray to remove the uncured space portion. Furthermore, the partition was formed by hold | maintaining for 30 minutes and baking at 560 degreeC. Next, a phosphor layer was formed to a thickness of 20 μm by a dispenser method and fired to obtain a back plate.

G. Surface roughness measurement Using an ultra-deep shape measurement microscope VK-8500 (manufactured by KEYENCE), align with a 50x lens on the top of the partition wall of a 42-inch back plate, and in a color ultra-deep mode, DISTANCE ± 20 μm, PITCH 0.1 μm 30 points were measured randomly under the conditions, and evaluated as an average value of 10-point average roughness (Rz) in the line roughness in the longitudinal direction of the partition walls.

H. Display manufacturing method After sealing the prepared front plate and back plate, a xenon-neon mixed gas noble gas containing 5% by volume of xenon is sealed at a pressure of 450 mmHg in the space formed between the front and back substrates. Thus, a panel portion of the plasma display was produced. Further, a plasma display was manufactured by mounting a driver IC for driving.

I. Evaluation method of display characteristics The panels were turned on every other row along the partition wall direction, and visually evaluated for lighting, non-lighting, or flickering due to erroneous discharge. When the inorganic particles H aggregate and coarse protrusions or firing defects occur on the partition walls of the back plate, five discharges are generated by chipping. The evaluation is that the display characteristics are AA if the number of lit cells or non-lighted cells due to erroneous discharge is 1 or less, and the display characteristics are A if 2-4, and unsuitable as a display if 5-7. Yes, B, 8 or more, not possible as a display panel, and C.

Example 1
Average equal inorganic powder H and the glass frit L ₁ of particle size was added the same volume, further averaging the glass frit L ₂ larger particle size was added to prepare a barrier rib. When the surface roughness of the top of the partition wall was measured, Rz was a low value. The plasma display was manufactured by pasting the front plate prepared in advance and enclosing the discharge gas. When the drive circuit was mounted and displayed, the display characteristics were good.
(Example 2)
The average particle diameter of the glass frit L ₁ smaller than the inorganic powder H, inorganic powders H and the same volume was added, further the average glass frit L ₂ larger particle size was added to prepare a barrier rib. Improved denseness by decreasing the average particle diameter of the glass frit L _1, the surface roughness of the partition wall top is further improved. Furthermore, there was almost no aggregate of inorganic powder H, chipping did not occur in pasting with the front plate, and the display characteristics were good.
(Example 3)
The average particle diameter of the glass frit L ₁ and the inorganic powder H of Example 1 together small, was added the same volume. By reducing the particle size of the inorganic powder H, the surface top roughness was further improved. Chipping did not occur in pasting with the front plate, and the display characteristics were good.
Example 4
The average particle diameters of the glass frit L ₁ and the inorganic powder H of Example 1 were both reduced, and the addition amount of the glass frit L ₁ was increased. Since there was no aggregation due to the inorganic powder H inside the partition walls and the partition wall strength was improved, no chipping occurred in pasting with the front plate, and the display characteristics were good.
(Examples 5 and 6)
The amount of inorganic powder H added in Example 3 was increased or decreased at the rate shown in Table 1, and the amount of glass frit L _{2 was} relatively increased or decreased. There was a change in the surface roughness, but there was no problem in display characteristics.
(Examples 7 and 8)
A glass with different softening point of the glass frit L _1. The low softening point of the glass increased the binder effect on the inorganic powder H, and the surface roughness was good. There was no problem with the display characteristics.
(Comparative Example 1)
The average particle diameter of the glass frits L ₁ and L ₂ was made larger than the average particle diameter of the inorganic powder H. When the top of the partition wall was observed, there were many aggregates of the inorganic powder H, and the surface roughness Rz was large. Even inside the partition walls, there were many unsintered parts due to aggregates, and the partition wall strength was small. In pasting with the front plate, chipping occurred frequently and display evaluation characteristics were not possible (Comparative Example 2)
When the average particle size of the glass frit was the same as that in Comparative Example 1 and the addition amount of the glass frit L ₁ was further reduced, aggregates of the inorganic powder H further increased and the surface roughness Rz further deteriorated. There were many unsintered parts inside the partition walls, and chipping occurred frequently in pasting with the front plate, and display evaluation characteristics were not possible.

(Comparative Example 3)
The average particle size of the inorganic powder H was increased. Reduces the binder effect of the glass frit L _1, sintered agglomeration of the inorganic powder H is generated, the surface roughness Rz of the partition wall top was large. Similar agglomerates were observed inside the partition walls, the partition wall strength was low, chipping occurred frequently in pasting with the front plate, and display evaluation characteristics were not possible.

(Comparative Example 4)
The average particle diameter of the glass frit remains Comparative Example 3, further reducing the amount of glass frit L ₁ surface roughness of the partition wall top is a maximum value. In pasting with the front plate, the most chipping occurred, and the display evaluation characteristics were not possible.

Claims (5)

An inorganic material paste containing an inorganic component and an organic component, the glass frit L ₁ having a softening temperature of Ts _L1 (° C.) and an average particle diameter of D _L1 as the inorganic component, a softening temperature of Ts _L2 (° C.), an average A glass frit L ₂ having a particle size of D _L2 and an inorganic powder H having an average particle size of _DH and having no softening temperature of 600 ° C. or less, and all inorganic components in the inorganic material paste of the glass frit L ₁ Is a volume concentration of V _L1 (%), the volume concentration of all inorganic components in the inorganic material paste of the inorganic powder H is V _H (%), and the softening temperature, average particle diameter and volume concentration of the inorganic component are lower. An inorganic material paste characterized by satisfying the formulas (1) to (3).
Ts _L1 ≦ Ts _L2 ≦ 600 (1)
D _L1 ≦ D _H <D _L2 (2)
V _H ≦ V _L1 (3) The inorganic material paste according to claim 1, wherein the organic component contains a photosensitive component. Claim to satisfy the density of the glass frit ^{_{L 1 R L1 (g / cm}} 3), the density of the glass frit _{L 2 R L2 (g / cm} 3) , and _{R H} is the formula of the inorganic powder H (4) and (5) The inorganic material paste according to 1 or 2.
0 ≦ R _L2 −R _L1 <1 (4)
0 ≦ R _H −R _L1 <1 (5) The manufacturing method of the member for flat display including the process of apply | coating the inorganic material paste in any one of Claims 1-3 to a base material, forming an inorganic material pattern by baking after patterning. The flat display containing the flat display member manufactured by the manufacturing method of the member for flat displays of Claim 4.