JP2012158484A - Glass paste, and method for producing plasma display panel using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a power-saving plasma display panel, and glass paste for producing the same.SOLUTION: The glass paste contains glass powder having a low softening point and an organic component, wherein the glass having the low softening point contains FeO and FeOin the range of 1-1,000 ppm in the weight base total, and the content ratio of FeO to the total content of FeO and FeOis in the range of 0.40-0.95 on the weight base.

Description

  The present invention relates to a glass paste and a method for manufacturing a plasma display panel using the same.

  A plasma display panel (hereinafter referred to as PDP) is a flat display that displays images and information using light emission by plasma discharge, and is classified into a DC type and an AC type depending on the panel structure and driving method. The principle of color display by PDP is that plasma discharge is generated in a cell space (discharge space) between opposing electrodes formed on a front glass substrate and a rear glass substrate separated by a partition wall (also called a rib). The phosphor formed on the inner surface of the rear glass substrate is excited by ultraviolet rays generated by the discharge of He, Xe, or other gas sealed in the cell space, and three primary colors of visible light are generated. Each cell space is partitioned by grid-like ribs in the DC type PDP, while it is partitioned by partition walls arranged in parallel to the substrate surface in the AC type PDP. It is made by a partition.

  Hereinafter, it will be briefly described with reference to the accompanying drawings. FIG. 1 partially shows an example of the structure of a surface discharge AC type PDP having a three-electrode structure for full color display. On the lower surface of the front glass substrate 1, a large number of a pair of display electrodes 2a and 2b, each consisting of transparent electrodes 3a and 3b for discharging and bus electrodes 4a and 4b for reducing the line resistance of the transparent electrodes, are formed at a predetermined pitch. It is lined up. On these display electrodes 2a and 2b, a transparent dielectric layer 5 made of low softening point glass for accumulating charges is formed by printing and baking, and a protective layer 6 made of MgO is deposited thereon. Yes. The protective layer 6 has a role of protecting the display electrode, maintaining a discharge state, and the like. On the other hand, on the rear glass substrate 11, a plurality of stripe-shaped barrier ribs 12 partitioning the discharge space and a plurality of address electrodes 13 (data electrodes) arranged in each discharge space are arranged at a predetermined pitch. The address electrode 13 is generally covered with a dielectric layer 15, and the partition wall 12 is generally provided on the dielectric layer 15. Further, on the inner surface of each discharge space, phosphor films of three colors, a red phosphor film 14a, a blue phosphor film 14b, and a green phosphor film 14c, are regularly arranged, and in full color display, as described above. One pixel is composed of phosphor films (14a, 14b, and 14c) of three primary colors of red, blue, and green.

  Further, in some cases, stripe-shaped black patterns 10 are similarly formed on both sides of the pair of display electrodes 2a and 2b forming the discharge space in order to further increase the contrast of the image.

  In the PDP having the above structure, an alternating pulse voltage is applied between the pair of display electrodes 2a and 2b to cause discharge between the electrodes on the same substrate.

  In the PDP having the above structure, the ultraviolet rays generated by the discharge excite the phosphor films (14a, 14b, 14c) of the rear glass substrate 11, and the generated visible light is transmitted through the transparent electrodes 3a, 3b of the front glass substrate 1. It has a structure to see.

  A discharge method of the AC type PDP will be described. First, during the writing period, the potentials of all the sustain electrodes are held at 0, and a positive writing pulse voltage is applied to a predetermined one corresponding to the display content of the first scanning line among the data electrodes. A negative scan pulse voltage is applied to the second scan electrode. As a result, a write discharge occurs at the intersection of the data electrode to which the positive write pulse electrode is applied and the first scan electrode, and negative charges are accumulated on the surface of the back plate dielectric layer at the intersection where the write discharge occurs. The Next, when a positive write pulse voltage is applied to a predetermined data electrode corresponding to the display content of the second scan line and a negative scan pulse voltage is applied to the second scan electrode, Write discharge occurs at the intersection between the data electrode to which the write pulse electrode is applied and the second scan electrode, and negative charges are accumulated on the surface of the back plate dielectric layer at the intersection where the write discharge has occurred. Similarly, the scan driving operation is performed continuously, and a positive write pulse voltage is applied to a predetermined data electrode corresponding to the display content of the last scan line, and a negative scan pulse voltage is applied to the last scan electrode. Is applied, a write discharge occurs at the intersection of the data electrode to which the positive write pulse electrode is applied and the last scan electrode, and negative charges are accumulated on the surface of the back plate dielectric layer at the intersection where the write discharge occurs. The

  Next, in the sustain period, first, when a positive sustain pulse voltage is applied to all the display electrodes, a sustain discharge is started between the scan electrode and the sustain electrode at the intersection where the write discharge has occurred. Immediately after the application of the positive sustain pulse voltage to the sustain electrode, if a positive sustain pulse voltage is applied to all the scan electrodes, the sustain discharge is again generated between the scan electrode and the sustain electrode at the intersection where the write discharge has occurred. Done. As the time length represented by the term “immediately after completion of application”, for example, about 100 nanoseconds is appropriate. In this case, a positive sustain pulse voltage is applied to the scan electrode about 100 nanoseconds after the end of the application of the positive sustain pulse voltage to the sustain electrode. A sufficient erroneous discharge prevention effect can be obtained by setting the time length to about 100 nanoseconds. Further, when a positive sustain pulse voltage is applied to all the sustain electrodes immediately after the application of the positive sustain pulse voltage applied to the scan electrodes, it is again between the scan electrodes and the sustain electrodes at the intersection where the write discharge has occurred. A sustain discharge is performed. Similarly, sustain discharge is continuously performed by alternately applying a positive sustain pulse voltage to all scan electrodes and all sustain electrodes. Light emission by this sustain discharge is used for display.

  In the subsequent erasing period, a positive narrow erasing pulse voltage is applied to all the sustain electrodes to cause erasing discharge and stop the discharge. With the above operation, the display operation of one screen of the AC type plasma display panel is performed.

  In the PDP as described above, a panel made using a glass paste that has been conventionally used generates more oxygen than the partition walls and the dielectric layer during sealing firing or panel discharge. MgO that forms the protective layer is oxidized. For this reason, there is a problem that the secondary electron emission capability of the protective layer is lowered, the absolute value of the sustain pulse voltage necessary for continuing the sustain discharge is increased, and the power consumption is increased (see Patent Document 1). .

JP 2004-342606 A

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a glass paste for producing a power-saving PDP, and also to save power obtained by using the glass paste. To provide a PDP.

In order to achieve the above object, the present invention has the following configuration. That is, a glass paste containing a low softening point glass powder and an organic component, wherein the low softening point glass contains FeO and Fe ₂ O ₃ in a total range of 1 to 1000 ppm on a weight basis, and the content of FeO and Fe ₂ O ₃ The glass paste is characterized in that the ratio of the content of FeO with respect to the total amount is in the range of 0.40 to 0.95 on a weight basis. Further, the present invention is a method for manufacturing a plasma display panel, wherein a dielectric layer or a partition is formed using the glass paste described above.

  According to the present invention, a power-saving PDP and a glass paste for producing the same can be provided.

It is a schematic diagram showing a structural example of a surface discharge AC type PDP having a three-electrode structure for full color display.

The present invention is a glass paste containing a low softening point glass powder and an organic component, wherein the low softening point glass contains FeO and Fe ₂ O ₃ in a total range of 1 to 1000 ppm by weight, and FeO and Fe _2. The present invention relates to a glass paste characterized in that the ratio of the content of FeO to the total content of O ₃ is in the range of 0.40 to 0.95 on a weight basis.

The low softening point glass powder contained in the glass paste of the present invention contains FeO and Fe ₂ O ₃ in a total range of 1-1000 ppm on a weight basis. If it exceeds 1000 ppm, the coloring of the glass becomes too strong, which causes problems such as affecting the display color when used for displays. Further, even when iron oxide is not actively added, the low soft-added glass powder contains a small amount of iron oxide as an impurity, and a general low soft-added glass powder has a weight of FeO and Fe ₂ O ₃ . Contains a total of 1 ppm or more on the basis.

The ratio of the content of FeO to the total content of FeO and Fe ₂ O _{3 in} the low softening point glass powder contained in the glass paste of the present invention has a correlation with the oxygen inclusion amount in the low softening point glass, and is large. The glass is so reducible that the oxygen content tends to decrease. The ratio of the content of FeO to the total content of FeO and Fe ₂ O _{3 in} the low softening point glass powder contained in the glass paste of the present invention is in the range of 0.40 to 0.95, preferably 0. The range is from .65 to 0.95. In order to change the ratio of the content of FeO to the total content of FeO and Fe ₂ O ₃ , the glass melting temperature is changed, an oxidizing agent is added, or a reducing material is used. The higher the melting temperature, the larger the ratio of the content of FeO to the total content of FeO and Fe ₂ O ₃ . The oxidizing agent _{added, CeO 2, Co 2 O 3} , Co 3 O 4, MnO 2, KMnO 4, CuO, Cr 2 O 3, K 2 Cr 2 O 7, NiO, Nd 2 O 3, Er 2 O 3 , Sb ₂ O ₃ , nitrates of raw materials, and the like. Examples of the reducing raw material include a carbonate of the raw material. When the ratio of the content of FeO to the total content of FeO and Fe ₂ O _{3 in} the softening point glass powder is less than 0.40, the amount of oxygen inclusion in the low softening point glass increases, so the dielectric of the PDP When used for forming layers and barrier ribs, there is a problem that the sustain pulse voltage required for sustain discharge is increased, resulting in a PDP with high power consumption. Further, since FeO is relatively unstable, the ratio of the content of FeO to the total content of FeO and Fe ₂ O _{3 in} the softening point glass powder is usually 0.95 or less.

The composition of the low-softening point glass powder contained in the glass paste of the present invention is _Bi 2 _O 3: _5~45 mol%, ZnO: 5 to 60 _mol%, SiO 2: _{0.5~40 mol%,} B 2 _{O 3} : 10 to 60 _{mol%, Al} 2 O 3: _{0~10 mol%,} ZrO 2: 0 _{mol%, Li 2 O, Na 2} O, the sum of _{K 2} O: 0 to 15 mol%, MgO, CaO , SrO, the sum of the BaO: within the scope of 0 to 15 mol%, or ZnO: 0 to 20 _mol%, SiO 2: 3 to 50 _{mol%, B} 2 O 3: _10~60 mol%, _Al 2 O _3: 0 to 40 _mol%, ZrO 2: 0 _{mol%, Li 2 O, Na 2} O, the sum of _{K 2} O: 0 to 30 mol%, MgO, CaO, SrO, the sum of the BaO: 0 to 30 Those within the range of mol% are preferred.

In the former glass powder having the composition, Bi ₂ O ₃ is an oxide that forms a network, and is preferably contained in a range of 5 to 45 mol%. When Bi ₂ O ₃ is less than 5 mol%, the softening point of the low softening point glass tends to be high, and it tends to be difficult to form a dielectric layer or partition walls. When it exceeds 45 mol%, vitrification tends to be difficult and the thermal expansion coefficient tends to increase. ZnO is a component that lowers the thermal expansion coefficient and lowers the thermal softening point, and is preferably contained in the range of 5 to 60 mol%. If ZnO is less than 5 mol%, vitrification is difficult, and if it exceeds 60 mol%, the stability at the time of low-softening point glass molding is poor and devitrification tends to occur, and glass may not be obtained. SiO ₂ is an oxide that forms a network, and is preferably contained in the range of 0.5 to 40 mol%. When SiO ₂ is less than 0.5 mol%, excessive flow tends to occur when firing at the time of forming the dielectric layer. If it exceeds 40 mol%, the softening point of the low softening point glass tends to be high, and it tends to be difficult to form a dielectric layer or partition walls. B ₂ O ₃ is a component that forms a glass skeleton and expands the range that can be vitrified, and is preferably contained in a range of 10 to 60 mol%. When B ₂ O ₃ is less than 10 mol%, vitrification becomes difficult, and when it exceeds 60 mol%, the softening point of the low softening point glass tends to be high, and the formation of dielectric layers and partition walls tends to be difficult. . Al ₂ O ₃ is a component that stabilizes the glass, and is preferably included in the range of 0 to 10 mol%. If it exceeds 10 mol%, the softening point of the low softening point glass tends to be high, and it tends to be difficult to form a dielectric layer or partition walls. ZrO ₂ is a component that stabilizes the glass, and is preferably included in the range of 0 to 10 mol%. If it exceeds 10 mol%, the softening point of the low softening point glass tends to be high, and it tends to be difficult to form a dielectric layer or partition walls. Li ₂ O, Na ₂ O, and K ₂ O are components that lower the thermal softening point and are preferably included in a range of 0 to 15 mol% in total. If it exceeds 15 mol%, devitrification tends to occur. MgO, CaO, SrO, and BaO are components that stabilize the glass, and are preferably included in the range of 0 to 15 mol% in total. If it exceeds 15 mol%, devitrification tends to occur.

In the glass powder having the latter composition, ZnO is a component that lowers the thermal expansion coefficient and lowers the thermal softening point, and is preferably contained in the range of 0 to 20 mol%. If it exceeds 20 mol%, devitrification tends to occur. SiO ₂ is an oxide that forms a network and is preferably contained in a range of 3 to 50 mol%. When SiO ₂ is less than 3 mol%, excessive flow of the low softening point glass tends to occur when fired, and it tends to be difficult to form a dielectric layer and partition walls. If it exceeds 50 mol%, the softening point of the low softening point glass tends to be high, and it tends to be difficult to form a dielectric layer and partition walls. B ₂ O ₃ is a component that forms a glass skeleton and widens the range that can be vitrified, and is preferably included in a range of 10 to 60 mol%. When B ₂ O ₃ is less than 10 mol%, vitrification becomes difficult, and when it exceeds 60 mol%, the softening point of the low softening point glass tends to be high, and the formation of dielectric layers and partition walls tends to be difficult. . Al ₂ O ₃ is a component that stabilizes the glass and is preferably contained in the range of 1 to 40 mol%. If Al ₂ O ₃ is less than 1 mol%, a stable glass tends not to be obtained. If it exceeds 40 mol%, the softening point of the low softening point glass tends to be high, and it tends to be difficult to form a dielectric layer or partition walls. ZrO ₂ is a component that stabilizes the glass, and is preferably included in the range of 0 to 10 mol%. When it exceeds 10 mol%, the softening point of the low softening point glass tends to be high, and the dielectric layer and the partition tend to be difficult. Li ₂ O, Na ₂ O, and K ₂ O are components that lower the thermal softening point and are preferably included in a range of 0 to 30 mol% in total. When it exceeds 30 mol%, it will become easy to devitrify. MgO, CaO, SrO, and BaO are components that stabilize the glass, and are preferably included in a total amount of 0 to 30 mol%. When it exceeds 30 mol%, it will become easy to devitrify.

  The glass transition point of the low softening point glass powder contained in the glass paste of the present invention is preferably in the range of 400 to 550 ° C and the thermal softening point is in the range of 400 to 600 ° C. When the glass transition point is less than 400 ° C. or the thermal softening point is less than 400 ° C., excessive flow of the low softening point glass tends to occur when fired, and it tends to be difficult to form a dielectric layer and partition walls. When the glass transition point exceeds 550 ° C. or the thermal softening point exceeds 600 ° C., the sintering tends to be insufficient, and the formation of the dielectric layer and the partition tends to be difficult.

  The center diameter of the volume-based distribution of these glasses is preferably in the range of 0.5 to 10 μm. When the thickness is 0.5 μm, excessive flow of the low softening point glass tends to occur when fired, and it tends to be difficult to form a dielectric layer and partition walls. When it exceeds 10 μm, the dielectric layer and the partition wall surface after firing become rough, which is not preferable as a panel.

  The particle diameter of the powder is a value measured using a particle size distribution meter (Microtrac particle size analyzer MODEL MT3000) using a laser diffraction scattering method. The measurement takes about 1 g of a sample and is 40 W in purified water for 1 to 3 minutes. This is done by dispersing with the output ultrasonic wave. The center diameter of the volume-based distribution is 50% volume particle diameter.

  It is preferable to contain such a low softening point glass powder in the range of 10 to 60% by weight with respect to the total weight of the glass paste. A particularly preferred range is 25 to 50% by weight.

  The glass paste of the present invention preferably contains a filler as an inorganic powder. The filler has effects such as reducing the shrinkage rate during firing and reducing the stress applied to the substrate. The amount of filler added is preferably in the range of 5 to 30% by weight with respect to the total weight of the glass paste. When the amount of filler added is less than 5% by weight, the shrinkage ratio during firing increases, and the effect of controlling the thermal expansion coefficient cannot be obtained. On the other hand, if the filler addition amount exceeds 30% by weight, the denseness and strength of the dielectric layer after firing cannot be maintained, and at the same time, cracks tend to occur.

  As the filler, at least one selected from the group consisting of high melting point glass having a softening point of 650 to 850 ° C., titanium oxide, aluminum oxide, silicon oxide, barium titanate and zirconium oxide is preferably used.

  The glass paste of the present invention contains an organic component. Organic components include thermal polymerization initiators, photopolymerization initiators, sensitizers, binder resins, polymerizable compounds, ultraviolet absorbers, polymerization inhibitors, plasticizers, thickeners, organic solvents, antioxidants, dispersants, Leveling agents, suspending agents and the like can be included depending on the purpose.

  The thermal polymerization initiator is used when the glass paste of the present invention is used as a thermosetting glass paste, and an organic peroxide or an azo compound can be used. Specific examples include organic peroxides such as dipropyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-butylperoxyneodeca Noate, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, t-butylperoxy (2-ethylhexanoate) ), Benzoyl peroxide, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxylaurate, t-butylperoxy- 3,3,5-trimethylhexanoate, shi Rhohexane peroxide, t-butyl peroxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, di-t-butyldiperoxyisophthalate, methyl ethyl ketone peroxide, dicumyl Examples thereof include peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide and the like. As the azo compound, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 1,1-azobis (Cyclohexane-1-carbonitrile), 1-((1-cyano-1-methylethyl) azo) formamide (2- (carbamoylazo) isobutyronitrile), 2,2′-azobis (2-methyl-N -(1,1-bis (hydroxymethyl) -2-hydroxymethyl) propionamide), 2,2'-azobis (2-methyl-N- (2- (1-hydroxybutyl)) propionamide), 2, 2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide) and the like. In the present invention, one or more of these can be used. A thermal-polymerization initiator is added in 0.05-10 weight% with respect to glass paste total weight, More preferably, it is 0.1-5 weight%. If the amount of the thermal polymerization initiator is too small, curing will not proceed and the film will be insufficient in strength. If the amount of the thermal polymerization initiator is too large, curing will proceed excessively and the film will easily peel off.

  The photopolymerization initiator is used when the glass paste of the present invention is used as a photosensitive glass paste. Specific examples 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, benzyl Methylketanol, benzyl-2-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylene Anthrone, 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 disulfide, triphenylformine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide and eosin And a combination of a photoreductive dye such as methylene blue and a reducing agent such as ascorbic acid or triethanolamine. In the present invention, one or more of these can be used. A photoinitiator is added in 0.05-10 weight% with respect to glass paste total weight, More preferably, it is 0.1-5 weight%. If the amount of the polymerization initiator is too small, the photosensitivity will be poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed area may be too small.

  A sensitizer can also be used together with the photopolymerization initiator. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) 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, N-phenylethanolamine, isoamyl dimethylaminobenzoate , Isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthio-tetrazole, 1-phenyl-5-ethoxycarbonylthio-tetrazole and the like. In the present invention, one or more of these can be used. When adding a sensitizer to the glass paste of this invention, the addition amount is 0.05-10 weight% normally with respect to the glass paste total weight, More preferably, it is 0.1-5 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.

  Specific examples of the binder resin include polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polyethylene, silicon polymer (eg, polymethylsiloxane, polymethylphenylsiloxane), polystyrene, butadiene / styrene copolymer, polyvinylpyrrolidone, polyamide, high molecular weight Examples include polyethers, copolymers of ethylene oxide and propylene oxide, polyacrylamides and various acrylic polymers and cellulose compounds. In the present invention, one or more of these can be used. The binder resin is added in the range of 0 to 30% by weight, more preferably 0 to 15% by weight, based on the total weight of the glass paste.

  The polymerizable compound is used when the glass paste of the present invention is used as a thermosetting glass paste or a photosensitive glass paste, and examples thereof include a monomer, oligomer, or polymer containing a carbon-carbon unsaturated bond. As specific examples, the monomers are 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, isobornyl 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, 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 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, diacrylate of bisphenol A-propylene oxide adduct, thiophenol acrylate, benzyl mercaptan acrylate, and among the hydrogen atoms of these aromatic rings, 1 ~ 5 monomers substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methyl Styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and intramolecular acrylate Obtained by substituting preparative part or all methacrylate, .gamma.-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. In the polyfunctional monomer, the group having an unsaturated bond may be a mixture of an acryl group, a methacryl group, a vinyl group, and an allyl group.

  Moreover, the oligomer and polymer obtained by superposing | polymerizing at least 1 type among the compounds which have the above-mentioned carbon-carbon double bond can also be used. In the polymerization, it can be copolymerized with other polymerizable monomers so that the content of these monomers is 10% by weight or more, more preferably 35% by weight or more.

  When used as a photosensitive glass paste for pattern formation by photolithography, it is possible to improve developability with an alkali developer after exposure by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid as a monomer to be copolymerized. it can. 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. The acid value (AV) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 50 to 180, more preferably 70 to 140. When the acid value is less than 50, the allowable development width becomes narrow. Further, if the acid value exceeds 180, the solubility of the unexposed portion in the developing solution is lowered. Therefore, if the concentration of the developing solution is increased, the exposed portion is peeled off and it is difficult to obtain a high-definition pattern.

  By adding a photoreactive group to the side chain or molecular end of the polymer or oligomer described above, it can be used as a photosensitive polymer or photosensitive oligomer having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of making an acid chloride or allyl chloride by addition reaction. Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, glycidyl ether of isocrotonic acid, and the like.
Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.

  In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add.

  One or more of these polymerizable compounds can be used in the glass paste of the present invention. The reactive compound is added in the range of 1 to 50% by weight with respect to the total weight of the paste, and more preferably 5 to 30% by weight.

  In addition, when a photosensitive glass paste for forming a partition wall by photolithography is used, a dielectric used for the base is formed in the photosensitive glass paste and when a partition wall is formed by a photosensitive glass paste. An ultraviolet absorber made of an organic dye can be added to the glass paste. Although it does not specifically limit as a ultraviolet absorber, The thing which does not remain in the insulating film after baking is preferable. Specifically, azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, benzophenone dyes Dyes, naphthoquinone dyes, phthalimide dyes, perinone dyes, indole dyes, and the like can be used. Of these, azo dyes, benzophenone dyes, and indole dyes are preferable. The addition amount of the organic dye is preferably 0.01 to 3% by weight with respect to the total weight of the paste.

  The polymerization inhibitor is used when the glass paste of the present invention is a thermosetting glass paste or a photosensitive glass paste, and is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p-methylphenol. , Chloranil, pyrogallol and the like. When adding a polymerization inhibitor, the addition amount is 0.001-1 weight% with respect to the glass paste total weight.

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

  The antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- ( 4-methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-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-tert-butylphenyl) butane, bis [3,3-bis -(4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like.

  In order to adjust the viscosity of the solution, an organic solvent may be added to the glass paste of the present invention. The organic solvents used at this time are 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, terpineol, ethylene glycol alkyl ether (eg ethylene glycol monoethyl ether), diethylene glycol monoalkyl ether (eg diethylene glycol monobutyl ether (butyl carbitol)), ethylene glycol Monoalkyl ether acetate, diethylene glycol monoal Ether ether acetate (eg diethylene glycol monobutyl ether acetate (butyl carbitol acetate)), diethylene glycol dialkyl ether acetate, triethylene glycol alkyl ether acetate, triethylene glycol alkyl ether, propylene glycol alkyl ether, propylene glycol phenyl ether, dipropylene glycol alkyl ether, Tripropylene glycol alkyl ether (for example, tripropylene glycol n-butyl ether), propylene glycol alkyl ether acetate, dipropylene glycol alkyl ether acetate, tripropylene glycol alkyl ether acetate, acetyl trialkyl citrate, trialkyl citrate 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate, 2,2,4-trimethyl-1,3 pentadiol diisobutyrate, dimethyl phthalate (dimethyl phthalate), diethyl phthalate (diethyl phthalate) ), And dibutyl phthalate (dibutyl phthalate) (wherein alkyl represents methyl, ethyl, propyl, butyl, hexyl, or 2-ethylhexyl), and preferably at least one selected from the group consisting of: Organic solvent mixtures containing terpineol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate, propylene glycol phenyl ether, and the like, or one or more of these Used.

  The glass paste of the present invention is usually prepared by mixing low-softening point glass and various components such as organic components so as to have a predetermined composition, and then uniformly mixing and dispersing them with a three roller or kneader. The viscosity of the paste is appropriately adjusted depending on the addition ratio of inorganic fine particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is preferably in the range of 200 mPa · s to 200 Pa · s.

  Next, specific preferred embodiments of the method for producing a plasma display of the present invention will be described. Among the PDP manufacturing methods of the present invention, the PDP back plate manufacturing method first forms an electrode pattern having a desired pattern shape on a substrate using an electrode paste. Next, a dielectric paste coating film is formed using a dielectric paste on the substrate on which the electrode pattern is formed. Further, a barrier rib pattern is formed on the dielectric paste coating film using a barrier rib paste. Then, the electrode pattern, the dielectric paste coating film, and the barrier rib pattern are collectively fired together with the substrate to form the electrode layer, the dielectric layer, and the barrier rib, and then the phosphor layer. Below, each process is explained in full detail.

As a substrate for the back plate of a plasma display, soda glass or “P” manufactured by Asahi Glass Co., Ltd. is usually used.
A glass substrate using a high strain point glass such as “D-200”, “PP-8” manufactured by Nippon Electrochemical Co., Ltd. is used. An electrode pattern is formed on the substrate using an electrode paste containing a conductive metal and a binder. The electrode pattern can be formed by a screen printing method, a photosensitive paste method, a press molding method, etc. The photosensitive paste method can be used because the pattern can be refined and the process can be simplified. The procedure of the photosensitive paste method will be described below.

  A photosensitive electrode paste is applied to the entire surface or a part of the substrate. As a coating method, methods such as a screen printing method, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, screen mesh, paste viscosity, and coating amount. The coating thickness can be determined in consideration of the desired electrode height and the shrinkage ratio of the electrode paste due to firing, but usually the preferred electrode height after firing is in the range of 1 to 10 μm, considering firing shrinkage. The thickness of the applied electrode paste coating film is preferably in the range of 1 to 15 μm.

  The applied photosensitive electrode paste is dried and exposed. The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common.

  After exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer to form an electrode pattern. For the development, an immersion method, a spray method, a brush method, or the like is used. As the developer, a solution in which an organic component in the photosensitive electrode paste, particularly a polymer can be dissolved, may be used.

  The electrode pattern may be formed in consideration of shrinkage due to firing. The size of the electrode after firing is preferably in the range of a pitch of 100 to 600 μm, a height of 1 to 10 μm, and a width of 30 to 150 μm.

  Next, in order to form a dielectric layer, a dielectric paste containing a low softening point glass powder and an organic component containing a binder resin component is applied on the entire surface or a part thereof. The dielectric layer has an effect of covering and protecting and insulating the electrode formed on the substrate, and also has an effect of improving the formability of the partition wall formed thereon. In the method for producing the PDP of the present invention, it is preferable to use the glass paste of the present invention for forming the dielectric layer, and further, as a thermosetting glass paste using a thermosetting material as the binder resin component. It is preferable to use it.

The thickness of the dielectric layer is preferably in the range of 4 to 18 μm, more preferably in the range of 8 to 15 μm after firing, in order to form a uniform and dense dielectric layer. By setting the thickness to 18 μm or less, the debinding property at the time of firing becomes good, and cracks due to the remaining binder do not occur. In addition, since the stress applied to the glass substrate is reduced, problems such as warping of the substrate do not occur. Further, when the thickness is 4 μm or more, a flat, uniform and dense dielectric layer can be formed, and problems such as cracks in the dielectric layer due to the unevenness of the electrode portion do not occur.
After forming the dielectric paste coating film, drying is performed. By drying and curing, the dielectric paste coating film can withstand the stress caused by the shrinkage of the electrode pattern and the partition pattern in the subsequent firing step. The condition for drying the dielectric paste coating film is preferably a time range of 3 to 30 minutes in a temperature range of 100 to 300 ° C. Preferably, it is a time range of 5 to 30 minutes in a temperature range of 150 to 250 ° C.

  Next, a partition pattern is formed. In the manufacturing method of the PDP of the invention, it is preferable to use the glass paste of the invention for forming the partition walls. For the formation of the partition pattern, a screen printing method, a sand blast method, a photosensitive paste method, a press molding method, or the like is used. The photosensitive paste method is particularly preferable because the pattern can be refined and the process can be simplified. Therefore, it is preferable to use the glass paste of the present invention as a photosensitive glass paste, particularly as a photopolymerizable paste. Below, the procedure of the photosensitive paste method is demonstrated.

  A photosensitive barrier rib paste is applied to the entire surface or a part of the dielectric paste coating film. The photosensitive paste can be applied by a general method such as a screen printing method, a bar coater method, a roll coater method, or a doctor blade method. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage ratio caused by baking of the paste. Usually, the preferable height of the partition walls after firing is in the range of 60 to 170 μm, and the thickness of the partition wall paste coating film to be applied is preferably in the range of 80 to 220 μm considering firing shrinkage.

  The applied photosensitive barrier rib paste is dried and exposed. The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common.

  After the exposure, development is performed using a difference in solubility between the exposed portion and the unexposed portion in the developer to form a partition pattern. For the development, an immersion method, a spray method, a brush method, or the like is used. As the developer, a solution in which the organic components in the photosensitive partition paste, particularly the polymer, can be dissolved is preferably used. In the present invention, development with an aqueous alkaline solution is preferred. The partition wall patterning may be performed in consideration of shrinkage due to baking. The size of the partition walls after firing is preferably in the range of a pitch of 100 to 600 μm, a height of 60 to 170 μm, and a width of 20 to 100 μm.

  The partition pattern is mainly formed in a stripe shape, but is not particularly limited, and may have a lattice shape. When the dielectric paste of the present invention is used, cracks do not occur in the dielectric layer even when a lattice-like partition is formed. When the partition walls have a lattice shape, it is preferable that the height of the auxiliary partition walls is lower than that of the main partition walls so that exhaust can be performed smoothly in the subsequent sealing process with the front plate. The height of the auxiliary partition wall is preferably 10 to 95% of the main partition wall, more preferably 30 to 95%, still more preferably 60 to 95%.

  After the barrier rib pattern is formed, the electrode pattern, the dielectric paste coating film and the barrier rib pattern are simultaneously fired to form the electrode layer, the dielectric layer and the barrier rib. Note that the electrode pattern, the dielectric paste coating film, and the barrier rib pattern may not be fired at the same time, but may be fired individually or only partially when each layer is provided. By firing all of these simultaneously, it is possible to produce a PDP with high productivity and low cost.

  The firing atmosphere and temperature vary depending on the characteristics of the paste and the substrate, but are usually fired in air. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. In the case of batch-type firing, a glass substrate having a partition pattern formed on a dielectric paste coating film is heated from room temperature to about 500 ° C. over several hours at a substantially constant speed, and further set as a firing temperature. It is preferable to raise the temperature to 500 to 600 ° C. for 30 to 40 minutes, and hold for 15 to 30 minutes to perform firing. By setting the firing temperature to 600 ° C. or less and the firing time to a range of 15 to 30 minutes, firing residue, sagging of the partition walls, and the like can be suppressed.

  The back plate of the plasma display panel is formed by forming phosphor layers that emit red, green, and blue light in the cells sandwiched between the barrier ribs thus obtained. The phosphor layer is a phosphor paste containing an organic component such as phosphor powder and a binder resin, pattern printing using a screen plate, pattern coating using a dispenser having a plurality of ejection holes, patterning by a photolithography method, etc. After forming a pattern by the method, it can be formed by firing.

  Next, a method for manufacturing the front plate of the plasma display will be described. As the substrate, “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) and “PD200” (manufactured by Asahi Glass Co., Ltd.), which are heat-resistant glass for soda glass and 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 powder, 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 powder include metal powder and metal oxide powder. As the metal powder, gold, silver, copper, nickel or the like that is usually used as an electrode material can be used without any 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. 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. The film thicknesses of the black electrode paste after firing and the conductive paste after firing are each preferably in the range of 1 to 5 μm. Moreover, it is preferable that the line | wire width after baking is 20-100 micrometers.

  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 electrode forming substrate by screen printing, bar coater, roll coater, die coater, blade coater, spin coater, or the like. After application, the thick film can be formed by drying using an optional oven such as a ventilating oven, a hot plate, an infrared drying oven, or vacuum drying. 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 10 to 50 μm.

  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 , Sr0.6Ca0.4Gd ₂ O ₄ , Ba0.6Sr0.4Gd ₂ O ₄ , SiO ₂ , TiO ₂ , Al ₂ O ₃ , the above-mentioned oxides At least one kind from the group is preferably used, but MgO is particularly preferable. A known technique such as electron beam evaporation or ion plating can be used as a method for forming the protective film.

  By forming a sealing member around the obtained back plate substrate, aligning with the obtained front plate and overlaying, heating, depressurizing the space formed in the front and back substrate intervals, Bonding and sealing between the back plate and the front plate are performed. After a discharge gas composed of helium, neon, xenon, or the like is sealed in the space formed between the front and rear substrates, a plasma display can be manufactured by mounting a drive circuit.

  This will be specifically described below using examples. However, the present invention is not limited to this. Moreover, the addition amount of binder resin and a crosslinking agent in an Example table | surface shows the addition amount of only resin except a solvent.

(Examples 1-14, Comparative Examples 1-10)
The compositions of the low softening point glass powders used in Examples and Comparative Examples are shown in Tables 1 and 2.

The ratio of FeO content to the total content of FeO and Fe ₂ O ₃ and the total content of FeO and Fe ₂ O _{3 in} the low softening point glass is determined by the following measurement. A certain amount of low softening point glass is etched with a mixed acid of hydrofluoric acid and hydrochloric acid. A certain amount of the etching solution is dispensed into a plastic container, and a 2,2′-dipyridyl solution and an ammonium acetate buffer solution are quickly added to color only Fe ²⁺ constituting FeO. The color developing solution is made constant with ion-exchanged water. Next, a certain amount of the etching solution is dispensed into another plastic container, and a hydroxylamine hydrochloric acid solution, a 2,2′-dipyridyl solution, and an ammonium acetate buffer solution are added to convert Fe ³⁺ constituting Fe ₂ O ₃ into Fe ^2+. To reduce the color of all iron ions. The color developing solution is made constant with ion-exchanged water.

A trivalent iron standard solution is developed in the same manner using hydroxylamine hydrochloric acid solution, 2,2′-dipyridyl solution and ammonium acetate buffer. The standard color solution is measured for absorbance at 522 nm to prepare a calibration curve. The absorbance of the sample coloring solution is measured, and the Fe ²⁺ concentration is calculated from the calibration curve. The Fe ²⁺ content and the Fe ²⁺ + Fe ³⁺ content are calculated from the measured concentration and the etching amount of the glass. Then, the ratio of FeO content to the total content of FeO + Fe ₂ O ₃ and the total content of FeO and Fe ₂ O ₃ in terms of oxides calculated from the obtained Fe ²⁺ content and Fe ³⁺ content is calculated. To do.

  On a 125 mm square glass substrate (“PD200” manufactured by Asahi Glass Co., Ltd.), an electrode paste (manufactured by Toray Industries, Inc.) is applied by a screen printing method (printing plate: SUS # 325) to a thickness of 5 μm after drying. did. After drying, a photomask having a stripe pattern with a pitch of 250 μm and a line width of 50 μm was set and exposed. After the exposure, development was performed in a 0.5% ethanolamine aqueous solution to obtain a striped electrode pattern having a pitch of 250 μm and a line width of 60 μm. Thereafter, curing was performed at 200 ° C. for 15 minutes using a hot air dryer.

  On the glass substrate with the electrode pattern, dielectric pastes 1 to 16 each containing a low softening point glass powder shown in Table 3 were applied by a screen printing method (printing plate: SUS # 325) so as to have a thickness of 15 μm after drying. And dried at 150 ° C. for 15 minutes using a hot air dryer.

The compositions of the dielectric pastes 1 to 16 are described below.
Resin binder (5% terpineol solution of ethyl cellulose having a number average molecular weight of 80,000): 20% by weight,
Polymerizable compound (trimethylolpropane triacrylate, manufactured by Nippon Kayaku Co., Ltd., “TPA330”, trifunctional): 20% by weight,
Low softening point glass powders E to M, Q to W (each listed in Table 3): 40% by weight,
Polymerization initiator (benzoyl peroxide): 3% by weight,
Dispersant (Nopcospace 092): 1% by weight,
Filler (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., “R550”), 10% by weight,
Solvent (terpineol): 6% by weight.
Dielectric pastes 1 to 16 were prepared by kneading a mixture of the above-described components with a three-roller kneader.

  Next, partition pastes 1 to 7 each containing a low softening point glass powder shown in Table 4 were applied to a thickness of 90 μm after drying and dried. After drying, a photomask having a stripe pattern with a pitch of 750 μm and a line width of 50 μm was set and exposed so as to be orthogonal to the address electrodes. After the exposure, the same partition pastes 1 to 7 were further applied and dried to form a coating film having a dry thickness of 90 μm. On this coating film, a photomask having a stripe pattern with a pitch of 250 μm and a line width of 30 μm was set in an arrangement parallel to the address electrodes and exposed. After exposure, developed in 0.5% ethanolamine aqueous solution, a lattice pattern consisting of a stripe partition pattern having a pitch of 250 μm, a line width of 40 μm, and a height of 180 μm, and an auxiliary partition pattern having a pitch of 750 μm, a line width of 50 μm, and a height of 90 μm A partition pattern was obtained.

The composition of the barrier rib pastes 1 to 7 is described below.
Polymerizable compound A (trimethylolpropane triacrylate, manufactured by Nippon Kayaku Co., Ltd., “TPA330”, trifunctional): 5% by weight,
Polymerizable compound B (acrylic polymer, addition reaction of 0.4 equivalent of glycidyl methacrylate to the carboxyl group of styrene / methyl methacrylate / methacrylic acid copolymer, weight average molecular weight 43,000, acid value 95) 40% γ-butyrolactone solution): 20% by weight,
Low softening point glass powders A to D, N to P (each listed in Table 4): 45% by weight,
Polymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone): 3% by weight
Dispersant (Nopcospace 092): 1% by weight,
Polymerization inhibitor (hydroquinone): 1% by weight,
Filler (high softening point glass powder having a softening point of 650 ° C.): 10% by weight,
Solvent (γ-butyrolactone): 15% by weight.
The partition wall pastes 1 to 7 were prepared by kneading a mixture of the above-described components with a three-roller kneader.

  Thus, after forming an electrode pattern, a dielectric paste coating layer, and a partition pattern, these were fired simultaneously. For the firing, a roller hearth firing furnace was used, and firing was performed at a firing temperature of 570 ° C. for 15 minutes. From a striped electrode having a pitch of 250 μm, a line width of 50 μm, a thickness of 3 μm, a dielectric layer having a thickness of 10 μm, a stripe partition having a pitch of 250 μm, a line width of 30 μm, and a height of 120 μm, and an auxiliary partition having a pitch of 750 μm, a line width of 50 μm, and a height of 60 μm A grid-like partition wall was obtained.

The chromaticity (b ^* value) at 25 locations in the plane of the substrate having the three layers of the partition, dielectric, and electrode was measured using CM2500d manufactured by Konica Minolta, Inc. Depending on the b ^* value obtained, the colored panel performance was evaluated as follows.
b ^* value is less than 15: good b ^* value is 15 or more: bad A phosphor paste of three colors red, green, and blue was screen printed on the groove between the barrier rib patterns on the substrate on which the barrier ribs were formed. A screen having a stripe-shaped opening pattern of # 200 mesh, a pitch of 250 μm, and a width of 30 μm was used. Printed. Thereafter, drying (150 ° C., 30 minutes) and firing (500 ° C., 30 minutes) were performed to form a phosphor layer on the side and bottom of the partition wall. The coating speed during screen printing was adjusted so that the average film thickness of the phosphor film after firing was 15 ± 0.5 μm.

  Next, the front plate was produced by the following steps. First, ITO is formed on a 125 mm square glass substrate (“PD200” manufactured by Asahi Glass Co., Ltd.) by sputtering, then resist is applied, and a transparent electrode having a thickness of 0.1 μm and a line width of 200 μm is formed by exposure, development, and etching. did. Further, a scanning electrode and a sustain electrode having a thickness of 5 μm after firing were formed by photolithography using a photosensitive silver paste made of black silver powder. Electrodes having a pitch of 750 μm and a line width of 80 μm were prepared.

  Next, a glass paste obtained by kneading 70% by weight of low melting point glass powder containing 75% by weight of lead oxide, 20% by weight of ethyl cellulose, and 10% by weight of terpineol was screen-printed to obtain a display electrode for the display portion. After coating with a thickness of 50 μm so as to be covered, baking was performed at 570 ° C. for 15 minutes to form a front dielectric.

  A magnesium oxide layer having a thickness of 0.5 μm was formed as a protective film on the substrate on which the dielectric was formed by electron beam vapor deposition to produce a front plate.

  The produced front plate and the back plate are sealed with sealing glass, Ne gas containing Xe 15% is sealed so that the internal gas pressure is 85000 Pa, and a plasma display panel is manufactured by mounting a drive circuit. did.

A voltage of 140 V and a voltage of 70 V were applied to the scan electrode of the fabricated PDP, the voltage of the sustain electrode was gradually increased, and the voltage required for lighting the entire surface was measured to obtain the minimum sustain pulse voltage. The power consumption performance was determined as follows according to the obtained minimum sustain pulse voltage.
Minimum sustain pulse voltage is 171 V or less: Excellent minimum sustain pulse voltage is greater than 171 V and less than 173 V: Good Minimum sustain pulse voltage is greater than 173 V: Impossible When power consumption performance is excellent or good and coloring evaluation is good If the panel evaluation passed, power consumption performance or coloring evaluation was poor, the panel evaluation was rejected.

  The evaluation results are shown in Tables 5 and 6. A good display with a low sustain electrode minimum applied voltage could be obtained.

  In Examples 1 to 13, since the glass paste of the present invention was used for forming the dielectric layer or the barrier rib, a good plasma display panel having a low minimum sustain pulse voltage and excellent power consumption performance and no coloration is obtained. I was able to.

In Comparative Examples 1-8, since the low softening point glass powder with a small ratio of the content of FeO to the total content of FeO and Fe ₂ O ₃ was used, the minimum sustain pulse voltage was high and the power consumption performance Niotake panel It became. In Comparative Example 9, since a glass paste containing a low softening point glass powder having a large total content of FeO and Fe ₂ O ₃ was used for forming the dielectric, a colored plasma display was obtained.

DESCRIPTION OF SYMBOLS 1 Front glass substrate 2a, 2b Display electrode 3a, 3b Transparent electrode 4a, 4b Bus electrode 5 Transparent dielectric layer 6 Protective layer 10 Black pattern 11 Back glass substrate 12 Partition 13 Address electrode 14a Red fluorescent substance film 14b Blue fluorescent substance film 14c Green phosphor film 15 Dielectric layer

Claims (5)

A glass paste containing a low softening point glass powder and an organic component, wherein the low softening point glass contains FeO and Fe ₂ O ₃ in a total range of 1 to 1000 ppm by weight, and contains FeO and Fe ₂ O ₃ A glass paste characterized in that the ratio of the content of FeO to the total amount is in the range of 0.40 to 0.95 on a weight basis. The glass paste according to claim 1, wherein the organic component includes a reactive compound and a thermal polymerization initiator or a photopolymerization initiator. The glass paste according to claim 1 or 2, wherein the composition of the low softening point glass powder is in the following range.
Bi ₂ O _3: 5~45 mol%
ZnO: 5 to 60 mol%
SiO _2: 0.5~40 mol%
B ₂ O _3: 10~60 mol%
Al ₂ O ₃ : 0 to 10 mol%
ZrO ₂ : 0 to 10 mol%
Li _{2 O,} Na 2 O, the sum of _{K 2} O: 0 to 15 mol%
Total of MgO, CaO, SrO, BaO: 0 to 15 mol% The glass paste according to claim 1, wherein the composition of the low softening point glass powder is in the following range.
ZnO: 0 to 20 mol%
SiO _2: 3~50 mol%
B ₂ O _3: 10~60 mol%
Al ₂ O ₃ : 1 to 40 mol%
ZrO ₂ : 0 to 10 mol%
Li _{2 O,} Na 2 O, the sum of _{K 2} O: 0 to 30 mol%
Total of MgO, CaO, SrO, BaO: 0 to 30 mol% A method for producing a plasma display panel, wherein a dielectric layer or a partition is formed using the glass paste according to claim 1.

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