CN101506116A - Dielectric material for plasma display panel - Google Patents
Dielectric material for plasma display panel Download PDFInfo
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- CN101506116A CN101506116A CNA2007800291058A CN200780029105A CN101506116A CN 101506116 A CN101506116 A CN 101506116A CN A2007800291058 A CNA2007800291058 A CN A2007800291058A CN 200780029105 A CN200780029105 A CN 200780029105A CN 101506116 A CN101506116 A CN 101506116A
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Abstract
A dielectric material for plasma display panels which comprises a lead-free glass powder and, despite this, gives a dielectric layer less apt to yellow, excellent in transparency, and having a coefficient of thermal expansion suitable for glass substrates, and can be burned at a temperature of 600 DEG C or lower. Also provided are a method of forming a dielectric layer and a glass plate for plasma display panels which is formed by that method. The dielectric material for plasma display panels comprises a ZnO/B2O3-based glass powder, and is characterized in that the glass powder contains substantially no PbO and comprises a glass containing, in terms of mass%, 46-80% of ZnO+B2O3, 0.3-10% of TiO2, and 0.01-6% of CuO+MoO3+CeO2+MnO2+CoO.
Description
Technical field
The present invention relates to the formation method of dielectric material for plasma display panel, dielectric layer and the plasma display sheet glass that forms by this method.
Background technology
Plasma display is the emissive type flat-panel monitor, possesses excellent characteristics such as light, thin, that the visual angle is wide, and can realize big pictureization, therefore as one of display unit that possesses future and noticeable.
Plasma display is that front glass substrate and back side glass substrate is opposed at certain intervals, has the structure that gas-tight seal around it is formed with sealing glass.And, be filled with rare gas such as Ne, Xe in panel inside.
Being used for being formed with the plasma discharge scan electrode on the front glass substrate of such use, on this, be formed with the front glass substrate dielectric layer (transparency dielectric layer) that is used to protect scan electrode.
In addition, be formed with the address electrode of the position that is used for the regulation plasma discharge overleaf on the glass substrate, on this, also be formed with the back side glass substrate dielectric layer (address protection dielectric layer) that is used to protect the address.Further, on the address protection dielectric layer, be formed with the next door that is used for the interval discharge cell, in addition; in inside, unit; be coated with red (R), green (G), blue (B) fluor, constituting and cause plasma discharge generation ultraviolet ray, fluor is excited and luminous structure thus.
Generally, the front glass substrate of plasma display and back side glass substrate use soda-lime glass or high deformation temperature glass, and scan electrode and address electrode then extensively adopt can be by the film forming Ag electrode of silk screen print method cheaply.When on being formed with the glass substrate of electrode, forming dielectric layer, for the distortion that prevents glass substrate and the reaction of inhibition and electrode, the method for firing in the temperature range of employing about 500～600 ℃.Therefore, people need be fit to the thermal expansivity of glass substrate, the dielectric substance with high withstand voltage that can fire under 500～600 ℃.
In addition, because transparency dielectric layer is except above-mentioned characteristic, also require to have high transparent, therefore, the dielectric substance that is used to form transparency dielectric layer is easy to the exhaust bubble when also needing to fire.
As the dielectric substance that satisfies above-mentioned requirements, once used and adopted PbO-B
2O
3-SiO
2The dielectric substance of ekalead glass powder (with reference to patent documentation 1), but because the trend that the use of the raising of environment protection in recent years and carrying capacity of environment material is cut down, people expect that dielectric substance uses non-lead glass powder.Proposed to use the ZnO-B that is easier to realize low melting pointization for this reason
2O
3The dielectric substance of the non-lead glass powder of class (with reference to patent documentation 2)
Patent documentation 1: the spy opens flat 11-No. 11979 communiques
Patent documentation 2: the spy opens flat 9-No. 278482 communiques
Summary of the invention
But, on the glass substrate that is formed with the Ag electrode, shown in patent documentation 2, use by ZnO-B
2O
3When the dielectric substance that the non-lead glass of class constitutes formed dielectric layer, in firing, electrical conductor and Ag electrode reaction were as the Ag of electrode
0Be dissolved in the glass, form Ag
+, valence mumber is varied to Ag again
0, form colloid, make the dielectric layer of Ag electrode perimeter be coloured to yellow～brown (xanthochromia) thus, produce the problem that portrait is difficult to see clearly.
Known, by in glass, adding the CuO of minute quantity, utilize Cu
2++ Ag
0→ Cu
++ Ag
+Reaction, can prevent in the glass by Ag
+To Ag
0Valence mumber change, suppress xanthochromia.But, at ZnO-B
2O
3Under the situation of the non-lead glass of class, since stronger than the xanthochromia degree of other class glass, therefore be difficult to reach unusual effect.
The objective of the invention is to, adopt that non-plumbous class glass powder, dielectric layer also are difficult to take place xanthochromia, the transparency is excellent and have the thermal expansivity of suitable glass substrate, the dielectric material for plasma display panel that can fire under the temperature below 600 ℃, the formation method of dielectric layer and the plasma display sheet glass that is formed by this method even provide.
After the inventor etc. have carried out various tests, found that: on the glass substrate that is formed with the Ag electrode, even adopt by ZnO-B
2O
3The dielectric substance that the non-lead glass powder of class constitutes forms dielectric layer, contains TiO in the glass by making
2And be selected from CuO, MoO
3, CeO
2, MnO
2With more than one composition among the CoO as essential composition, just can suppress the xanthochromia that causes by Ag.
That is, dielectric material for plasma display panel of the present invention is characterised in that, by ZnO-B
2O
3The class glass powder constitutes, and this glass powder contains ZnO+B in Quality Percentage by not containing PbO in fact
2O
346～80%, TiO
20.3 CuO+MoO～10%,
3+ CeO
2+ MnO
2The glass of+CoO 0.01～6% constitutes.
In addition, plasma display of the present invention is characterised in that with the formation method of dielectric layer, forms above-mentioned dielectric substance on the glass substrate of electrode and fires being formed with.
In addition, plasma display of the present invention is characterised in that to have the dielectric layer that is formed by above-mentioned dielectric substance with sheet glass.
(effect of invention)
Dielectric material for plasma display panel of the present invention can obtain being difficult for causing the dielectric medium that xanthochromia, the transparency are excellent, can fire and have the thermal expansivity that is suitable for glass substrate under the temperature below 600 ℃ because of Ag.In addition, because plasma display adopts the dielectric substance that constitutes because of the painted non-lead glass powder of Ag generation by being difficult for sheet glass, therefore can make plasma display with high transparent.Therefore, be suitable for as the formation method of dielectric material for plasma display panel, dielectric layer and the plasma display sheet glass that forms by this method.
Embodiment
Even dielectric material for plasma display panel of the present invention does not contain PbO, also can more easily realize the low melting pointization of glass, and to be easy to reach the ZnO-B of the thermal expansivity that is suitable for glass substrate
2O
3The non-lead glass of class is that substrate is formed.When this class glass uses the Ag electrode at electrode, dielectric medium and Ag reaction, the dielectric layer of Ag electrode perimeter is easy to take place xanthochromia.Especially when this class glass contained the alkalimetal oxide composition, it is remarkable that xanthochromia is tending towards.But, in the present invention, in this class glass, add TiO
2And be selected from CuO, MoO
3, CeO
2, MnO
2With among the CoO more than one composition (being designated hereinafter simply as M) the two as essential composition.Thus, even by easily xanthochromic ZnO-B taking place because of Ag causes dielectric layer
2O
3The dielectric substance that the non-lead glass of class constitutes also can obtain being difficult to produce xanthochromia, transparent excellent dielectric layer.
Usually, at ZnO-B
2O
3In the non-lead glass of class, M although taken place in an added ingredients M in glass
X++ Ag
0→ M
X-1+ Ag
+Valence mumber change but because ZnO-B
2O
3The non-lead glass of class is stronger than the xanthochromia degree of other class glass, therefore is difficult to reach unusual effect.In addition, in glass, only add TiO
2, pass through Ti
4++ Ag
0→ Ti
3++ Ag
+Reaction, can prevent in the glass by Ag
+To Ag
0Valence mumber change, can suppress xanthochromia, but because Ti
4+Become Ti
3+, the dielectric layer variable color is brown (titanium dioxide is amber).But by and use TiO
2With composition M, improve xanthochromia, the Ti of generation
3+Combine generation Ti-O-M key with composition M, prevent brownization, think that therefore the variable color that can make xanthochromia and cause because of the Ti ion is difficult to take place.
In addition, in dielectric substance of the present invention,, need make the TiO that contains 0.3～10 quality % in the glass that constitutes dielectric substance for the xanthochromia that makes the dielectric layer that causes because of Ag and the variable color that causes because of the Ti ion are difficult for producing
2With the composition M that counts 0.01～6 quality % with the total amount.
TiO
2Content be lower than at 0.3% o'clock, be difficult to reach the xanthochromic effect of dielectric layer that inhibition causes because of Ag.On the other hand, when being higher than 10%, even contain composition M, it is brown that dielectric layer also is easy to variable color.In addition, the softening temperature of glass is risen, be difficult to fire under the temperature below 600 ℃, the glass crystallization is difficult to obtain the transparent film of firing.TiO
2Preferable range be 0.5～8%.
Composition M (is selected from CuO, MoO
3, CeO
2, MnO
2With more than one the composition among the CoO) content be lower than at 0.01% o'clock to close quantifier, the xanthochromic effect of dielectric layer that is difficult to reach the effect of the dielectric layer variable color that inhibition causes because of the Ti ion and suppresses to cause because of Ag.On the other hand, when being higher than 6%, the dielectric layer that Yi Fashengyin composition M causes painted.The preferable range of composition M is 0.1～4%.In composition M, CuO suppresses the effective of the variable color that causes because of the Ti ion, more preferably be essential composition with CuO, and at this moment, the content of CuO is 0.01～3.0% (being preferably 0.05～2.5%), in addition, and preferred MoO
3, CeO
2, MnO
2Be respectively 0～5% (being preferably 0.01～5%) with CoO.
In addition, in the present invention, using ZnO-B
2O
3During class glass,, make it have enough vitrifying scopes, obtain the transparent film of firing, make ZnO and B for avoiding the glass crystallization
2O
3Total content be 46～80%, important.As ZnO and B
2O
3The total amount be less than at 46% o'clock, be difficult to vitrifying.On the other hand, when more than 80% the time, the glass crystallization is difficult to obtain the transparent film of firing.ZnO and B
2O
3The preferable range of total amount be 49～75%.
In addition, the ZnO-B that uses among the present invention
2O
3Class glass powder so long as be difficult for causes that xanthochromia, the transparency are excellent, demonstrate good flowability in firing below 600 ℃, have the glass of the thermal expansivity that is suitable for glass substrate, just without limits, preferred especially the use do not contain PbO in fact, contains ZnO 25～55%, B in Quality Percentage
2O
310～40%, ZnO+B
2O
346～80%, SiO
21～20%, Bi
2O
30～50%, Li
2O 0～8%, Na
2O 0～10%, K
2O 0～15%, Li
2O+Na
2O+K
2O 0～15%, MgO 0～20%, CaO0～20%, SrO 0～20%, BaO 0～20%, MgO+CaO+SrO+BaO 0～25%, TiO
20.3 CuO+MoO～10%,
3+ CeO
2+ MnO
2The glass of the compositing range of+CoO 0.01～6%.
As mentioned above glass is formed the reasons are as follows of limiting in the present invention.
ZnO still reduces the composition of softening temperature simultaneously for constituting the main component of glass, and its content is 20～50%.When the content of ZnO after a little while, glass softening point improves, and is difficult to fire under the temperature below 600 ℃.On the other hand, content for a long time, there is easy crystalline tendency in glass, is difficult to obtain the transparent film of firing.The more preferably scope of ZnO is 28～50%.
B
2O
3Be skeleton that forms glass and the composition that enlarges the vitrifying scope, its content is 10～40%.B
2O
3Content after a little while, there is easy crystalline tendency in glass, is difficult to obtain the transparent film of firing.On the other hand, content for a long time, the tendency that exists the softening temperature of glass to increase is difficult to fire under the temperature below 600 ℃.And, there is the trend of thermal expansivity greater than the thermal expansivity of glass substrate, be difficult to matched coefficients of thermal expansion with glass substrate.B
2O
3More preferably scope be 15～35%.
In addition, for fear of the glass crystallization, have sufficient vitrifying scope, obtain the transparent film of firing, need make ZnO and B
2O
3The total amount be 46～80%.As ZnO and B
2O
3Total amount when reducing, be difficult to vitrifying.On the other hand, as ZnO and B
2O
3Total amount when increasing, the glass crystallization is difficult to obtain the transparent film of firing.ZnO and B
2O
3The preferable range of total amount be 49～75%.
SiO
2Be the composition that forms the glass skeleton, its content is 1～20%.Work as SiO
2Content when reducing, be difficult to vitrifying.On the other hand, when content increases, have the tendency of the softening temperature raising of glass, becoming is difficult to fire under the temperature below 600 ℃.SiO
2More preferably scope be 3～18%.
Bi
2O
3It is the composition of adjusting thermal expansivity.In addition, be the composition that reduces glass softening point, therefore also be to have can reduce easily to produce the xanthochromic composition Li of dielectric layer because of Ag
2O, Na
2O, K
2The composition of the effect of the alkali metal oxide content of O.Its content is 0～50%.Work as Bi
2O
3Content when increasing, have the tendency of thermal expansivity greater than the thermal expansivity of glass substrate, be difficult to matched coefficients of thermal expansion with glass substrate.Bi
2O
3More preferably scope be 1～30%.
Li
2O is the softening temperature that obviously reduces glass, and adjusts the composition of thermal expansivity, and its content is 0～8%.Li
2When the content of O increases, even contain Ti
2O and composition M also are easy to obviously reduce the xanthochromic inhibition effect of dielectric layer that causes because of Ag.In addition, there is the trend of thermal expansivity, is difficult to matched coefficients of thermal expansion with glass substrate greater than the thermal expansivity of glass substrate.Li
2The preferable range of O is 0～5%.
Na
2O is the softening temperature that reduces glass, and adjusts the composition of thermal expansivity, and its content is 0～10%.Na
2When the content of O increases, even contain TiO
2With composition M, also become and reduce the xanthochromic inhibition effect of dielectric layer that causes because of Ag easily.In addition, there is the trend of thermal expansivity, is difficult to matched coefficients of thermal expansion with glass substrate greater than the thermal expansivity of glass substrate.Na
2The preferable range of O is 0～7%.
K
2O is the softening temperature that reduces glass, and adjusts the composition of thermal expansivity, and its content is 0～15%.K
2When the content of O increases, even contain Ti
2O and composition M do not reach the xanthochromic effect of dielectric layer that inhibition causes because of Ag sometimes yet.In addition, there is the trend of thermal expansivity, is difficult to matched coefficients of thermal expansion with glass substrate greater than the thermal expansivity of glass substrate.K
2The preferable range of O is 0～13%.
In addition,, under the temperature below 600 ℃, fire, make to have the thermal expansivity that is suitable for glass substrate, preferably make Li for the dielectric layer xanthochromia that suppresses to cause because of Ag
2O, Na
2O and K
2The total amount of O is 0～15%.When the total amount of these compositions increased, becoming was easy to produce xanthochromia, had the trend of thermal expansivity greater than the thermal expansivity of glass substrate, was difficult to the matched coefficients of thermal expansion with glass substrate.The more preferably scope of the total amount of these compositions is 0.1～13%.
MgO, CaO, SrO and BaO all are the compositions that add in order to adjust thermal expansivity, and its content is respectively 0～20%.When the content of these compositions increases, there is the trend of thermal expansivity, is difficult to matched coefficients of thermal expansion with glass substrate greater than the thermal expansivity of glass substrate.The more preferably scope of these compositions is respectively 0～17%.
In addition, the total amount of MgO, CaO, SrO and BaO is preferably 0～25%.When the total amount of these compositions increases, there is the trend of thermal expansivity, is difficult to matched coefficients of thermal expansion with glass substrate greater than the thermal expansivity of glass substrate.The more preferably scope of the total amount of these compositions is 0～20%.
TiO
2Be to suppress xanthochromic composition, its content is 0.3～10%.TiO
2Content when reducing, xanthochromic effect is difficult to be inhibited.On the other hand, when content increased, even contain composition M, it was brown that dielectric layer also is easy to variable color.In addition, also can improve the softening temperature of glass, becoming is difficult to fire under the temperature below 600 ℃, and glass generation crystallization is difficult to obtain the transparent film of firing.TiO
2Preferable range be 0.5～8%.
Composition M (is selected from CuO, MoO
3, CeO
2, MnO
2With more than one the composition among the CoO) be to suppress because of adding TiO
2Dielectric layer variable color that causes and xanthochromic composition.The content of composition M counts 0.01～6% with the total amount.When the content of composition M reduces, be difficult to obtain above-mentioned effect.On the other hand, when more than 6% the time, be easy to take place the painted of the dielectric layer that causes because of composition M.The preferable range of composition M is 0.1～4%.In composition M, CuO suppresses the effective of the variable color that causes because of the Ti ion, more preferably with CuO as essential composition, at this moment, the content of CuO is 0.01～0.3% (being preferably 0.05～2.5%), in addition, preferred MoO
3, CeO
2, MnO
2With the total amount of CoO be 0～5% (being preferably 0.01～5%).
In addition, except that mentioned component,, can add various compositions in desired characteristic range.For example, in order to reduce the softening temperature of glass, add Cs to close quantifier
2O, Rb
2O etc. are in 10%; In order to make stabilizationization or to improve water tolerance and acid resistance, can add Al to close quantifier
2O
3, ZrO
2, Y
2O
3, La
2O
3, Ta
2O
5, SnO
2, WO
3, Nb
2O
5, Sb
2O
5, P
2O
5Deng in 10%.In addition, P
2O
5Be to make the glass devitrification, be difficult to obtain the transparent composition of firing film, so its content is preferably below 5%.
Wherein, PbO is the composition that the glass melting point is reduced, and also is the carrying capacity of environment material, therefore should avoid importing in the glass in fact.
In addition, " avoiding importing in the glass in fact " of the present invention be mean be not initiatively with it as raw material, but, mean that specifically content is below 0.1% as the level that impurity is sneaked into.
In the granularity of the glass powder in dielectric material for plasma display panel of the present invention, preferred median size D
50Be below the 3.0 μ m, maximum particle diameter D
MaxBe below the 20 μ m.This is because any particle diameter surpasses its upper limit, all is easy to cause firing remaining air pocket in the film, reduces proof voltage.
For regulate thermal expansivity and fire after intensity and outward appearance, dielectric material for plasma display panel of the present invention can also contain ceramic powder except above-mentioned glass powder.When ceramic powder increases, can not fully carry out sintering, be difficult to form dense film.In addition, as ceramic powder, for example, can be used in combination aluminum oxide more than a kind or 2 kinds, zirconium white, zircon, titanium dioxide, trichroite, mullite, silica, willemite, stannic oxide, zinc oxide etc.In addition, for fear of causing the transparency of dielectric layer to reduce because of importing ceramic powder, part or all of ceramic powder can use the globular ceramic end.
During the described here spherical state that is meant in observing photo, particle surface is not with property at parts of edges and corners, and from the particle center to the surface whole radius in ± 20%.In addition, preferably use the ceramic powder that median size 5.0 μ m are following, maximum particle diameter 20 μ m are following.
In addition, dielectric material for plasma display panel of the present invention can be used for dielectric any purposes of back side dielectric medium or front, in addition, the also material of lower floor's dielectric layer that can be connected as dielectric and the electrode with the dielectric medium structure more than 2 layers, or as formation on lower floor's dielectric layer the material of the direct upper strata dielectric layer that is connected with electrode not.Certainly, also can be used for the dielectric substance that forms on the electrode outside the Ag electrode, and purposes in addition, for example, can be used for the next door and form material.When using with transparent dielectric material, can be to use under the condition of 0～20 quality % (being preferably 0～10 quality %) at the content of above-mentioned ceramic powder as the front glass substrate.By the content that makes ceramic powder is above-mentioned scope, can suppress the visible scattering of light that the interpolation because of ceramic powder causes, and obtains the film of firing of high-clarity.In addition, when using with back side dielectric substance or next door material as back side glass substrate, can be to use under the condition in the scope of 0～50 quality % (more preferably 5～40 quality %, more preferably 10～40 quality %) at the content of above-mentioned ceramic powder.By the content that makes ceramic powder is above-mentioned scope, can obtain having high strength, or has the excellent in resistance tart and fire film.
The using method of dielectric material for plasma display panel of the present invention then is described.Material of the present invention for example can use with forms such as mashed prod and raw cooks.
When using, use above-mentioned dielectric substance and thermoplastic resin, softening agent, solvent etc. with the form of mashed prod.In addition, account for the ratio of mashed prod integral body, be generally about 30～90 quality % as dielectric substance.
Thermoplastic resin is to improve dried film toughness, and gives the composition of flexibility, and its content is generally about 0.1～20 quality %.As thermoplastic resin, can use poly-n-butyl methacrylate, polyvinyl butyral acetal, polymethylmethacrylate, polyethyl methacrylate, ethyl cellulose etc., these are used alone or as a mixture.
Softening agent is the composition of controlling rate of drying and making desciccator diaphragm have flexibility, and its content is generally about 0～10 quality %.As softening agent, can use butyl benzyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate, phthalic acid two certain herbaceous plants with big flowers esters, dibutyl phthalate etc., these are used alone or as a mixture.
Solvent is the material that is used for the material pasty stateization, and its content is generally about 10～30 quality %.For example can be used alone or as a mixture terpinol, diethylene glycol monobutyl ether acetic ester, 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate etc. as solvent.
The making of mashed prod can be by preparation above-mentioned dielectric substance, thermoplastic resin, softening agent, solvent etc., and it is mixing and carry out with the regulation ratio.
When using such mashed prod to form transparency dielectric layer or address protection dielectric layer; at first; at the front glass substrate that is formed with scan electrode or be formed with on the back side glass substrate of address electrode; with these mashed prod of coating such as a silk screen print method or step coating methods; after forming the coating layer of specific thickness, make its drying.Then, under 500～600 ℃ temperature, keep firing in 5～20 minutes, obtain the dielectric layer of stipulating thus.In addition, firing temperature is low more, the hold-time is short more, can't carry out abundant sintering more, is difficult to form dense film more.On the other hand, firing temperature is high more, the hold-time is long more, and glass substrate is yielding more, more the xanthochromia of the dielectric layer that causes of Yi Fashengyin Ag.
In addition, when formation has the dielectric layer of the dielectric medium structure more than 2 layers,, be pre-formed coating lower floor dielectric layer formation mashed prod on the sheet glass of electrode with a silk screen print method or a step coating method etc., after making thickness be about 20～80 μ m and drying, same as above firing.Then, on this, utilize coating upper strata dielectric layers such as a silk screen print method or a step coating method to form and use mashed prod, make thickness be about 60～160 μ m and dry.Then, same as above firing and obtaining.
When material of the present invention uses with the raw cook form, use above-mentioned dielectric substance and thermoplastic resin, softening agent etc.In addition, dielectric substance proportion in raw cook is generally about 60～80 quality %.
As thermoplastic resin and softening agent, used identical thermoplastic resin and softening agent as the blending ratio of thermoplastic resin, are generally about 5～30 quality % in the time of can using with the modulation of above-mentioned mashed prod, as the blending ratio of softening agent, be generally about 0～10 quality %.
As the usual method of making raw cook, prepare above-mentioned dielectric substance, thermoplastic resin, softening agent etc.,, form slurry to wherein adding solubility promoters such as main solvent, Virahol such as toluene, the skill in using a kitchen knife in cookery is scraped in utilization, and this slurry is shaped to sheet material on polyethylene terephthalate films such as (PET).After forming sheet material,, obtain raw cook by being dried to remove solvent or solvent.
When using the raw cook that obtains as mentioned above to form front or back side dielectric layer, at the front glass substrate that is formed with scan electrode or be formed with on the back side glass substrate of address electrode and dispose raw cook, after forming the thermo-compressed coating, by with same the firing of above-mentioned mashed prod, can obtain dielectric layer.
In addition, when formation has the dielectric layer of the dielectric medium structure more than 2 layers, after being pre-formed thermo-compressed lower floor dielectric medium formation raw cook on the sheet glass of electrode, forming lower floor's dielectric film, fire equally with the situation of above-mentioned mashed prod.Then thermo-compressed upper strata dielectric medium forms and use raw cook thereon, behind the dielectric film of formation upper strata, and same as above firing and obtaining.
When formation has the dielectric layer of the dielectric medium structure more than 2 layers, when forming the upper strata dielectric layer, even any in use mashed prod and the raw cook, if the temperature of firing lower floor's dielectric layer ± fire the upper strata dielectric substance in 20 ℃ the temperature range, the xanthochromia that then can suppress the dielectric layer that causes because of Ag, and, can keep the shape of lower floor's dielectric layer, and be suppressed at the interface foaming on lower floor and upper strata.In addition, when the firing temperature of upper strata dielectric substance and lower floor dielectric substance is identical, except above-mentioned formation method, can also adopt after lower floor's dielectric film drying, after forming upper strata dielectric film and drying, under specified temperature, fire two-layer method simultaneously.
In addition, can adopt lower floor's dielectric layer to use the mixing forming method that mashed prod forms, the upper strata dielectric layer uses raw cook to form.
As mentioned above, be formed with on the glass substrate of electrode coating or disposing dielectric substance of the present invention, fire, form dielectric layer, can obtain the plasma display sheet glass of the present invention that xanthochromia is few, the transparency is excellent of the dielectric layer that causes because of Ag.
In the above description, as dielectric medium formation method, be illustrated as example with the method for using mashed prod or raw cook, but dielectric material for plasma display panel of the present invention is not limited to these methods, can also be to be suitable for other formation method such as photosensitivity mashed prod method, photosensitivity raw cook method and the material that obtains.
Embodiment
Specify the dielectric substance of plasma display of the present invention below according to embodiment.
Table 1～5 are represented embodiments of the invention (sample No.1～19) and comparative example (sample No.20～26) respectively.In addition, sample No.20 represent according to existing scheme by ZnO-B
2O
3The material that class constitutes.
Table 1
Table 2
Table 3
Table 4
Table 5
Each sample is as described below in the table modulates.
At first, raw material is mixed and mix well according to forming at the glass shown in the table in quality %.Then, put into platinum crucible, after 2 hours, melten glass is shaped to lamellar 1300 ℃ of following fusions.Then, it is pulverized and air classification with ball mill, obtain by median size D
50Below 3.0 μ m, maximum particle diameter D
MaxThe sample that glass powder below 20 μ m constitutes.About the glass powder that so obtains, the xanthochromia that stability, thermal expansivity, softening temperature, specific inductivity, the Ag of evaluation glass causes.
As seen from table, sample No.1～19 of embodiment are in the fusion operation, and the raw material vitrifying does not have crystallization to separate out in the affirmation glass fully.In addition, thermal expansivity is 69.9～77.6 * 10
-7/ ℃, with the glass substrate coupling, softening temperature is low to be reached below 594 ℃, can fire under the temperature below 600 ℃.In addition, specific inductivity is 6.8～10.0.Carry out the naked eyes evaluation at xanthochromia, confirming does not have xanthochromia, in addition, in the evaluation that utilizes colour-difference meter, a
*Below+3.9, b
*Below+19.9, confirm not have xanthochromia.
Otherwise the sample No.20 and 21 of comparative example when forming dielectric layer on the Ag electrode, produces xanthochromia in the Ag electrode perimeter.Sample No.22 and 23 variable colors are brown.And the variable color of the dielectric medium of sample No.24 own is a mazarine.And sample No.25 is in the fusion operation, and crystallization is separated out in the raw material vitrifying.Sample No.26 is in the fusion operation, and raw material is vitrifying not.
In addition, stability about glass, in table, raw materials melt is shaped to laminal glass specimen observation by light microscope, with usefulness [zero] expression that does not have crystallization to separate out fully in raw material vitrifying in the fusion operation, the affirmation glass, crystalline is separated out in raw material vitrifying in the fusion operation, or the not vitrified usefulness of raw material [*] expression in the fusion operation.
About thermal expansivity, by powder pressing forming, after carrying out under 580 ℃ firing in 10 minutes, attrition process becomes the cylindric of diameter 4mm, long 40mm, measures according to JISR3102, tries to achieve 30～300 ℃ the interior value of temperature range with each sample.
About the softening temperature of glass, use Macro type differential thermal analysis instrumentation fixed, with the 4th flex point value as softening temperature.
About electric conductivity, by powder pressing forming, after carrying out under 580 ℃ firing in 10 minutes, attrition process becomes the tabular body of 2mm, measures according to JIS C2141 with each sample, tries to achieve 25 ℃, the value during 1MHz.
About the xanthochromic evaluation that Ag causes, be the mashed prod that utilizes the silk screen print method coating to make as mentioned above on the soda-lime glass substrate of Ag electrode being formed with, obtain the film of firing of about 30 μ m, and it is dry, after firing 10 minutes under 580 ℃, visual observation electrode perimeter portion measures a with colour-difference meter
*And b
*In addition, a
*Be worth high more, the expression color redden a
*Below+5.0, then be judged as nondiscoloration, in addition, b
*Be worth high more, the expression its colour changed into yellow, b
*+ 25.0 when following, be judged as and do not produce xanthochromia.
Claims (9)
1. a dielectric material for plasma display panel is characterized in that: by ZnO-B
2O
3The class glass powder constitutes, and this glass powder contains ZnO+B in Quality Percentage by not containing PbO in fact
2O
346～80%, TiO
20.3 CuO+MoO～10%,
3+ CeO
2+ MnO
2The glass of+CoO 0.01～6% constitutes.
2. dielectric material for plasma display panel as claimed in claim 1 is characterized in that: glass powder contains ZnO 25～55%, B in Quality Percentage by not containing PbO in fact
2O
310～40%, ZnO+B
2O
346～80%, SiO
21～20%, Bi
2O
30～50%, Li
2O 0～8%, Na
2O 0～10%, K
2O 0～15%, Li
2O+Na
2O+K
2O0～15%, MgO 0～20%, CaO 0～20%, SrO 0～20%, BaO 0～20%, MgO+CaO+SrO+BaO 0～25%, TiO
20.3 CuO+MoO～10%,
3+ CeO
2+ MnO
2The glass of+CoO 0.01～6% constitutes.
3. dielectric material for plasma display panel as claimed in claim 1 or 2 is characterized in that: the glass by the CuO that contains 0.01～3 quality % constitutes.
4. as each described dielectric material for plasma display panel in the claim 1～3, it is characterized in that: in the granularity of glass powder, median size D
50Be below the 3.0 μ m, maximum particle diameter D
MaxBe below the 20 μ m.
5. as each described dielectric material for plasma display panel in the claim 1～4, it is characterized in that: be used to form dielectric layer, this dielectric layer is connected with Ag electrode on being formed on glass substrate.
6. as each described dielectric material for plasma display panel in the claim 1～5, it is characterized in that: the transparent dielectric material of using as the front glass substrate uses.
7. the formation method of a plasma display usefulness dielectric layer is characterized in that: form each described dielectric substance in the claim 1～6 on being formed with the glass substrate of electrode, firing at 500～600 ℃.
8. the plasma display as claimed in claim 7 formation method of dielectric layer, it is characterized in that: electrode is the Ag electrode.
9. a plasma display sheet glass is characterized in that: have the dielectric layer that is formed by each described dielectric substance in the claim 1～6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006213125 | 2006-08-04 | ||
| JP213125/2006 | 2006-08-04 | ||
| JP121359/2007 | 2007-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101506116A true CN101506116A (en) | 2009-08-12 |
Family
ID=40977649
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800291058A Pending CN101506116A (en) | 2006-08-04 | 2007-05-17 | Dielectric material for plasma display panel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082056A (en) * | 2010-09-30 | 2011-06-01 | 四川虹欧显示器件有限公司 | Dielectric glass powder for plasma display panel |
-
2007
- 2007-05-17 CN CNA2007800291058A patent/CN101506116A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102082056A (en) * | 2010-09-30 | 2011-06-01 | 四川虹欧显示器件有限公司 | Dielectric glass powder for plasma display panel |
| CN102082056B (en) * | 2010-09-30 | 2013-12-25 | 四川虹欧显示器件有限公司 | Dielectric glass powder for plasma display panel |
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Open date: 20090812 |